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Sample records for amorphous phase separation

  1. Amorphous-Amorphous Phase Separation in API/Polymer Formulations.

    PubMed

    Luebbert, Christian; Huxoll, Fabian; Sadowski, Gabriele

    2017-02-15

    The long-term stability of pharmaceutical formulations of poorly-soluble drugs in polymers determines their bioavailability and therapeutic applicability. However, these formulations do not only often tend to crystallize during storage, but also tend to undergo unwanted amorphous-amorphous phase separations (APS). Whereas the crystallization behavior of APIs in polymers has been measured and modeled during the last years, the APS phenomenon is still poorly understood. In this study, the crystallization behavior, APS, and glass-transition temperatures formulations of ibuprofen and felodipine in polymeric PLGA excipients exhibiting different ratios of lactic acid and glycolic acid monomers in the PLGA chain were investigated by means of hot-stage microscopy and DSC. APS and recrystallization was observed in ibuprofen/PLGA formulations, while only recrystallization occurred in felodipine/PLGA formulations. Based on a successful modeling of the crystallization behavior using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), the occurrence of APS was predicted in agreement with experimental findings.

  2. Self-assembly of amorphous biophotonic nanostructures by phase separation

    SciTech Connect

    Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar; Mochrie, Simon G.J.; Cao, Hui; Prum, Richard O.

    2009-04-23

    Some of the most vivid colors in the animal kingdom are created not by pigments, but by wavelength-selective scattering of light from nanostructures. Here we investigate quasi-ordered nanostructures of avian feather barbs which produce vivid non-iridescent colors. These {beta}-keratin and air nanostructures are found in two basic morphologies: tortuous channels and amorphous packings of spheres. Each class of nanostructure is isotropic and has a pronounced characteristic length scale of variation in composition. These local structural correlations lead to strong backscattering over a narrow range of optical frequencies and little variation with angle of incidence. Such optical properties play important roles in social and sexual communication. To be effective, birds need to precisely control the development of these nanoscale structures, yet little is known about how they grow. We hypothesize that multiple lineages of birds have convergently evolved to exploit phase separation and kinetic arrest to self-assemble spongy color-producing nanostructures in feather barbs. Observed avian nanostructures are strikingly similar to those self-assembled during the phase separation of fluid mixtures; the channel and sphere morphologies are characteristic of phase separation by spinodal decomposition and nucleation and growth, respectively. These unstable structures are locked-in by the kinetic arrest of the {beta}-keratin matrix, likely through the entanglement or cross-linking of supermolecular {beta}-keratin fibers. Using the power of self-assembly, birds can robustly realize a diverse range of nanoscopic morphologies with relatively small physical and chemical changes during feather development.

  3. Characterization of Phase Separation Propensity for Amorphous Spray Dried Dispersions.

    PubMed

    McNamara, Daniel; Yin, Shawn; Pan, Duohai; Crull, George; Timmins, Peter; Vig, Balvinder

    2017-02-06

    A generalized screening approach, applying isothermal calorimetry at 37 °C 100% RH, to formulations of spray dried dispersions (SDDs) for two active pharmaceutical ingredients (APIs) (BMS-903452 and BMS-986034) is demonstrated. APIs 452 and 034, with similar chemotypes, were synthesized and promoted during development for oral dosing. Both APIs were formulated as SDDs for animal exposure studies using the polymer hydroxypropylmethlycellulose acetyl succinate M grade (HPMCAS-M). 452 formulated at 30% (wt/wt %) was an extremely robust SDD that was able to withstand 40 °C 75% RH open storage conditions for 6 months with no physical evidence of crystallization or loss of dissolution performance. Though 034 was a chemical analogue with similar physical chemical properties to 452, a physically stable SDD of 034 could not be formulated in HPMCAS-M at any of the drug loads attempted. This study was used to develop experience with specific physical characterization laboratory techniques to evaluate the physical stability of SDDs and to characterize the propensity of SDDs to phase separate and possibly crystallize. The screening strategy adopted was to stress the formulated SDDs with a temperature humidity screen, within the calorimeter, and to apply orthogonal analytical techniques to gain a more informed understanding of why these SDDs formulated with HPMCAS-M demonstrated such different physical stability. Isothermal calorimetry (thermal activity monitor, TAM) was employed as a primary stress screen wherein the SDD formulations were monitored for 3 days at 37 °C 100% RH for signs of phase separation and possible crystallization of API. Powder X-ray diffraction (pXRD), modulated differential scanning calorimetry (mDSC), Fourier transform infrared spectroscopy (FTIR), and solid state nuclear magnetic resonance (ssNMR) were all used to examine formulated SDDs and neat amorphous drug. 452 SDDs formulated at 30% (wt/wt %) or less did not show phase separation behavior upon

  4. Phase separation kinetics in amorphous solid dispersions upon exposure to water.

    PubMed

    Purohit, Hitesh S; Taylor, Lynne S

    2015-05-04

    The purpose of this study was to develop a novel fluorescence technique employing environment-sensitive fluorescent probes to study phase separation kinetics in hydrated matrices of amorphous solid dispersions (ASDs) following storage at high humidity and during dissolution. The initial miscibility of the ASDs was confirmed using infrared (IR) spectroscopy and differential scanning calorimetry (DSC). Fluorescence spectroscopy, as an independent primary technique, was used together with conventional confirmatory techniques including DSC, X-ray diffraction (XRD), fluorescence microscopy, and IR spectroscopy to study phase separation phenomena. By monitoring the emission characteristics of the environment-sensitive fluorescent probes, it was possible to successfully monitor amorphous-amorphous phase separation (AAPS) as a function of time in probucol-poly(vinylpyrrolidone) (PVP) and ritonavir-PVP ASDs after exposure to water. In contrast, a ritonavir-hydroxypropylmethylcellulose acetate succinate (HPMCAS) ASD, did not show AAPS and was used as a control to demonstrate the capability of the newly developed fluorescence method to differentiate systems that showed no phase separation following exposure to water versus those that did. The results from the fluorescence studies were in good agreement with results obtained using various other complementary techniques. Thus, fluorescence spectroscopy can be utilized as a fast and efficient tool to detect and monitor the kinetics of phase transformations in amorphous solid dispersions during hydration and will help provide mechanistic insight into the stability and dissolution behavior of amorphous solid dispersions.

  5. Structure and Phase Separation in Ultrathin Ag/Cu Amorphous Alloy System

    NASA Astrophysics Data System (ADS)

    Chen, Hao

    2005-03-01

    The structure of disordered metallic alloys is an important but unsolved problem. Previous studies on Ag-Cu system showed that relatively homogeneous solid solutions formed at liquid nitrogen temperature decompose into separate phases or evolve into crystalline structure at a higher temperature. In this research project, we prepared ultra-thin Ag-Cu films on amorphous carbon support by HV magnetron sputtering with both targets. With high energy Ag and Cu atoms bombarding on the carbon substrate, they are forced to form amorphous alloy or nano-crystalline thin film at room temperature. We have investigated the structure of ultra-thin Ag-Cu films by examining their pair distribution function (PDF) using electron diffraction and observed phase separation process directly in STEM images. In the STEM Z-contrast images, since the contrast is directly related to the atomic number (Z) of the components, we can see clearly the phase separation process. Experimental results show that the sample morphology evolutions are different in samples with different thickness, and the phase separation depends on various Ag/Cu atomic ratios. In Ag50Cu50 sample, early stage phase separation is associated with increasing Cu crystallite size, indicates that Cu diffuse out of Ag-Cu solid solution phase.

  6. Anisotropic imprint of amorphization and phase separation in manganite thin films via laser interference irradiation.

    PubMed

    Ding, Junfeng; Lin, Zhipeng; Wu, Jianchun; Dong, Zhili; Wu, Tom

    2015-02-04

    Materials with mesoscopic structural and electronic phase separation, either inherent from synthesis or created via external means, are known to exhibit functionalities absent in the homogeneous counterparts. One of the most notable examples is the colossal magnetoresistance discovered in mixed-valence manganites, where the coexistence of nano- to micrometer-sized phase-separated domains dictates the magnetotransport. However, it remains challenging to pattern and process such materials into predesigned structures and devices. In this work, a direct laser interference irradiation (LII) method is employed to produce periodic stripes in thin films of a prototypical phase-separated manganite Pr0.65 (Ca0.75 Sr0.25 )0.35 MnO3 (PCSMO). LII induces selective structural amorphization within the crystalline PCSMO matrix, forming arrays with dimensions commensurate with the laser wavelength. Furthermore, because the length scale of LII modification is compatible to that of phase separation in PCSMO, three orders of magnitude of increase in magnetoresistance and significant in-plane transport anisotropy are observed in treated PCSMO thin films. Our results show that LII is a rapid, cost-effective and contamination-free technique to tailor and improve the physical properties of manganite thin films, and it is promising to be generalized to other functional materials.

  7. Amorphous-Amorphous Phase Separation of Freeze-Concentrated Protein and Amino Acid Excipients for Lyophilized Formulations.

    PubMed

    Izutsu, Ken-Ichi; Yoshida, Hiroyuki; Shibata, Hiroko; Goda, Yukihiro

    2016-01-01

    The objective of this study was to elucidate the mixing state of proteins and amino acid excipients concentrated in the amorphous non-ice region of frozen solutions. Thermal analysis of frozen aqueous solutions was performed in heating scans before and after a heat treatment. Frozen aqueous solutions containing a protein (e.g., recombinant human albumin, gelatin) or a polysaccharide (dextran) and an amino acid excipient (e.g., L-arginine, L-arginine hydrochloride, L-arginine monophosphate, sodium L-glutamate) at varied mass ratios showed single or double Tg' (glass transition temperature of maximally freeze-concentrated solutes). Some mixture frozen solutions rich in the polymers maintained the single Tg' of the freeze-concentrated amorphous solute-mixture phase. In contrast, amino acid-rich mixture frozen solutions revealed two Tg's that suggested transition of concentrated non-crystalline solute-mixture phase and excipient-dominant phase. Post-freeze heat treatment induced splitting of the Tg' in some intermediate mass ratio mixture solutions. The mixing state of proteins and amino acids varied depending on their structure, salt types, mass ratio, composition of co-solutes (e.g., NaCl) and thermal history. Information on the varied mixing states should be valuable for the rational use of amino acid excipients in lyophilized protein pharmaceuticals.

  8. Phase separations of amorphous CoW films during oxidation and reactions with Si and Al

    SciTech Connect

    Wang, S.Q.; Mayer, J.W.

    1989-03-01

    Reactions of thin Co/sub 55/ W/sub 45/ films in contact with Si(100) substrates and aluminum overlayers annealed in vacuum in the temperature ranges of 625--700 /sup 0/C and 500--600 /sup 0/C, respectively, and of thin Co/sub 55/W/sub 45/ films in air from 500 to 600 /sup 0/C were investigated by Rutherford backscattering spectrometry, glancing angle x-ray diffraction, and scanning electron microscope techniques. CoW alloy films were amorphous and have a crystallization temperature of 850 /sup 0/C on SiO/sub 2/ substrates. The compound formed is Co/sub 7/ W/sub 6/. Phase separations were found in all the reactions. A layer of cobalt compounds (CoSi/sub 2/ in Si/CoW, Co/sub 2/ Al/sub 9/ in CoW/Al, and Co/sub 3/ O/sub 4/ in CoW with air) was found to form at the reaction interfaces. In addition, a layer of mainly tungsten compounds (WSi/sub 2/ in Si/CoW, WAl/sub 12/ in CoW/Al, and WO/sub 3/ in CoW with air) was found next to cobalt compound layers, but further away from the reaction interfaces. The reactions started at temperatures comparable to those required for the formation of corresponding tungsten compounds.

  9. Anisotropic phase separation through the metal-insulator transition in amorphous Mo-Ge and Fe-Ge alloys

    SciTech Connect

    Regan, Michael J.

    1993-12-01

    Since an amorphous solid is often defined as that which lacks long-range order, the atomic structure is typically characterized in terms of the high-degree of short-range order. Most descriptions of vapor-deposited amorphous alloys focus on characterizing this order, while assuming that the material is chemically homogeneous beyond a few near neighbors. By coupling traditional small-angle x-ray scattering which probes spatial variations of the electron density with anomalous dispersion which creates a species-specific contrast, one can discern cracks and voids from chemical inhomogeneity. In particular, one finds that the chemical inhomogeneities which have been previously reported in amorphous FexGe1-x and MoxGe1-x are quite anisotropic, depending significantly on the direction of film growth. With the addition of small amounts of metal atoms (x<0.2), no films appear isotropic nor homogeneous through the metal/insulator transition. The results indicate that fluctuations in the growth direction play a pivotal role in preventing simple growth models of a columnar structure or one that evolves systematically as it grows. The anomalous scattering measurements identify the metal atoms (Fe or Mo) as the source of the anisotropy, with the Ge atoms distributed homogeneously. The author has developed a method for using these measurements to determine the compositions of the phase-separating species. The results indicate phase separation into an amorphous Ge and an intermetallic phase of stoichiometry close to FeGe2or MoGe3. Finally, by manipulating the deposited power flux and rates of growth, FexGe1-x films which have the same Fe composition x can be grown to different states of phase separation. These results may help explain the difficulty workers have had in isolating the metal/insulator transition for these and other vapor-deposited amorphous alloys.

  10. The study of amorphous phase separation in a model polymer phase-separating system using Raman microscopy and a low-temperature stage: effect of cooling rate and nucleation temperature.

    PubMed

    Padilla, Adora M; Chou, Shin G; Luthra, Sumit; Pikal, Michael J

    2011-04-01

    The freezing process is a source of product instability in many freeze-dried pharmaceuticals. During freezing, the solute is concentrated in the interstitial spaces between ice crystals, and phase separation may occur, with likely negative stability implications. Phase separation may involve crystallization but may also occur in completely amorphous systems even though there is little direct evidence to support this speculation in protein formulation applications. Previous work in our laboratory focused on the application of a novel Raman mapping technique to the study of amorphous phase separation in freeze-dried polymer systems. We report here the application of a similar Raman mapping technique to frozen systems, using a low-temperature stage. We study the impact of nucleation temperature and thermal history on phase separation using a model 1:1 polyvinylpyrrolidone:dextran phase separating system. Although cooling rate and nucleation temperature had a small effect on the extent of phase separation, it was clear that the large latent heat of crystallization controls the thermal history and propensity for phase separation in practical applications. The results suggest that phase separation can be somewhat controlled by minimizing fill depth and controlling nucleation temperature. Copyright © 2010 Wiley-Liss, Inc.

  11. Non-saturating linear magnetoresistance in phase separated amorphous Ag10Ge15Te75 films

    NASA Astrophysics Data System (ADS)

    Xu, Hanni; Lu, JianXin; Xia, Yidong; Yin, Jiang; Liu, Zhiguo

    2012-07-01

    We report non-saturating linear magnetoresistance (LMR) in silver-poor composite thin films of Ag10Ge15Te75 (AGT). The LMR increases with decreasing temperature and reaches a value of 110% at 200 K under a magnetic field of 70 kOe. The observed magnetoresistance is proportional to carrier mobility due to identical temperature dependencies. The microstructures of AGT films annealed at different temperature are investigated by TEM observations. The observed LMR effect is resulting from the inhomogeneous distribution of conductivity caused by highly conductive Ag2Te and GeTe4 precipitates, which generate a current distortion in the surrounding amorphous silver-poor Ag-Ge-Te matrix.

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

    SciTech Connect

    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 - homogeneous 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}.

  13. Small-angle x-ray scattering study of phase separation in amorphous alloys during heating with use of synchrotron radiation

    SciTech Connect

    Yavari, A.R.; Osamura, K.; Okuda, H.; Amemia, Y.

    1988-05-01

    Some recent reports suggest that amorphous Pd/sub 46/Ni/sub 36/P/sub 18/ and Cu/sub 50/Zr/sub 50/ alloys phase separate during heating at temperatures 50--200 K below their crystallization temperatures. We have therefore obtained improved small-angle x-ray scattering (SAXS) measurements during heating of these alloys using a new experimental setup. The experimental improvements included in-the-beam heating using the very-high-intensity x-ray radiation available at the Synchrotron Radiation Laboratory, K.E.K., the use of Joule self-heating of the samples, which is made possible by the high resistivity of the amorphous phase and the use of regularly shaped, constant thickness amorphous tapes obtained by planar flow casting. No evidence of phase separation during heating prior to crystallization was obtained in glassy Pd/sub 46/Ni/sub 36/P/sub 18/ and Cu/sub 50/Zr/sub 50/ alloys.

  14. Amorphous Phases on the Surface of Mars

    NASA Technical Reports Server (NTRS)

    Rampe, E. B.; Morris, R. V.; Ruff, S. W.; Horgan, B.; Dehouck, E.; Achilles, C. N.; Ming, D. W.; Bish, D. L.; Chipera, S. J.

    2014-01-01

    Both primary (volcanic/impact glasses) and secondary (opal/silica, allophane, hisingerite, npOx, S-bearing) amorphous phases appear to be major components of martian surface materials based on orbital and in-situ measurements. A key observation is that whereas regional/global scale amorphous components include altered glass and npOx, local scale amorphous phases include hydrated silica/opal. This suggests widespread alteration at low water-to-rock ratios, perhaps due to snow/ice melt with variable pH, and localized alteration at high water-to-rock ratios. Orbital and in-situ measurements of the regional/global amorphous component on Mars suggests that it is made up of at least three phases: npOx, amorphous silicate (likely altered glass), and an amorphous S-bearing phase. Fundamental questions regarding the composition and the formation of the regional/global amorphous component(s) still remain: Do the phases form locally or have they been homogenized through aeolian activity and derived from the global dust? Is the parent glass volcanic, impact, or both? Are the phases separate or intimately mixed (e.g., as in palagonite)? When did the amorphous phases form? To address the question of source (local and/or global), we need to look for variations in the different phases within the amorphous component through continued modeling of the chemical composition of the amorphous phases in samples from Gale using CheMin and APXS data. If we find variations (e.g., a lack of or enrichment in amorphous silicate in some samples), this may imply a local source for some phases. Furthermore, the chemical composition of the weathering products may give insight into the formation mechanisms of the parent glass (e.g., impact glasses contain higher Al and lower Si [30], so we might expect allophane as a weathering product of impact glass). To address the question of whether these phases are separate or intimately mixed, we need to do laboratory studies of naturally altered samples made

  15. Amorphous phase separation in crystallizable polymer blends based on poly (aryl ether ketones) and poly (ether imide)

    SciTech Connect

    Kalika, D.S.; Bristow, J.F.

    1996-12-31

    The morphology of a series of miscible crystallizable blends based on poly (aryl ether ketones) [PAEK] and poly (ether imide) [PEI] has been investigated as a function of blend composition and crystallization condition by dielectric relaxation spectroscopy. For blends of poly (ether ether ketone) [PEEK] and PEI, dielectric scans of the crystallized samples reveal two glass-rubber relaxations corresponding to the coexistence of a mixed interlamellar amorphous phase, and a pure PEI phase located in interfibrillar/interspherulitic regions. The exclusion of a significant fraction of PEI outside of the crystal lamellae reflects a fundamental change in the nature of interaction between the interlamellar PEEK segments and the PEI chains owing to the constraints imposed on the PEEK segments by the crystal surfaces. The degree of PEI exclusion is dependent upon kinetic factors, i.e. the rate of PEEK crystallization relative to the rate of PEI diffusion away from the advancing crystal front. As a result, lower crystallization temperatures lead to an increase in the amount of PEI trapped in the interlamellar regions. In this work, the morphological characteristics of the PEEK/PEI blends are compared with those of blends comprised of poly (ether ketone ketone) [PEKK] and PEI. The introduction of the {open_quotes}kinked{close_quote} isophthalate moiety in the PEKK backbone has been shown to disrupt the persistence of order at the crystal-amorphous interface, and thereby leads to a reduction in the degree of constraint imposed by the crystal lamellae on the amorphous (interlamellar) PEKK segments. The impact of this reduction in crystalline constraint on the nature of the PEKK/PEI intersegmental interactions and the corresponding PEI segregation is discussed.

  16. Insights into Nano- and Micron-Scale Phase Separation in Amorphous Solid Dispersions Using Fluorescence-Based Techniques in Combination with Solid State Nuclear Magnetic Resonance Spectroscopy.

    PubMed

    Purohit, Hitesh S; Ormes, James D; Saboo, Sugandha; Su, Yongchao; Lamm, Matthew S; Mann, Amanda K P; Taylor, Lynne S

    2017-07-01

    Miscibility between the drug and the polymer in an amorphous solid dispersion (ASD) is considered to be one of the most important factors impacting the solid state stability and dissolution performance of the active pharmaceutical ingredient (API). The research described herein utilizes emerging fluorescence-based methodologies to probe (im)miscibility of itraconazole (ITZ)-hydroxypropyl methylcellulose (HPMC) ASDs. The ASDs were prepared by solvent evaporation with varying evaporation rates and were characterized by steady-state fluorescence spectroscopy, confocal imaging, differential scanning calorimetry (DSC), and solid state nuclear magnetic resonance (ssNMR) spectroscopy. The size of the phase separated domains for the ITZ-HPMC ASDs was affected by the solvent evaporation rate. Smaller domains (<10 nm) were observed in spray-dried ASDs, whereas larger domains (>30 nm) were found in ASDs prepared using slower evaporation rates. Confocal imaging provided visual confirmation of phase separation along with chemical specificity, achieved by selectively staining drug-rich and polymer-rich phases. ssNMR confirmed the results of fluorescence-based techniques and provided information on the size of phase separated domains. The fluorescence-based methodologies proved to be sensitive and rapid in detecting phase separation, even at the nanoscale, in the ITZ-HPMC ASDs. Fluorescence-based methods thus show promise for miscibility evaluation of spray-dried ASDs.

  17. Nanostructures having crystalline and amorphous phases

    DOEpatents

    Mao, Samuel S; Chen, Xiaobo

    2015-04-28

    The present invention includes a nanostructure, a method of making thereof, and a method of photocatalysis. In one embodiment, the nanostructure includes a crystalline phase and an amorphous phase in contact with the crystalline phase. Each of the crystalline and amorphous phases has at least one dimension on a nanometer scale. In another embodiment, the nanostructure includes a nanoparticle comprising a crystalline phase and an amorphous phase. The amorphous phase is in a selected amount. In another embodiment, the nanostructure includes crystalline titanium dioxide and amorphous titanium dioxide in contact with the crystalline titanium dioxide. Each of the crystalline and amorphous titanium dioxide has at least one dimension on a nanometer scale.

  18. Phosphate-water interplay tunes amorphous calcium carbonate metastability: spontaneous phase separation and crystallization vs stabilization viewed by solid state NMR.

    PubMed

    Kababya, Shifi; Gal, Assaf; Kahil, Keren; Weiner, Steve; Addadi, Lia; Schmidt, Asher

    2015-01-21

    Organisms tune the metastability of amorphous calcium carbonates (ACC), often by incorporation of additives such as phosphate ions and water molecules, to serve diverse functions, such as modulating the availability of calcium reserves or constructing complex skeletal scaffolds. Although the effect of additive distribution on ACC was noted for several biogenic and synthetic systems, the molecular mechanisms by which additives govern ACC stability are not well understood. By precipitating ACC in the presence of different PO4(3-) concentrations and regulating the initial water content, we identify conditions yielding either kinetically locked or spontaneously transforming coprecipitates. Solid state NMR, supported by FTIR, XRD, and electron microscopy, define the interactions of phosphate and water within the initial amorphous matrix, showing that initially the coprecipitates are homogeneous molecular dispersions of structural water and phosphate in ACC, and a small fraction of P-rich phases. Monitoring the transformations of the homogeneous phase shows that PO4(3-) and waters are extracted first, and they phase separate, leading to solid-solid transformation of ACC to calcite; small part of ACC forms vaterite that subsequently converts to calcite. The simultaneous water-PO4(3-) extraction is the key for the subsequent water-mediated accumulation and crystallization of hydroxyapatite (HAp) and carbonated hydroxyapatite. The thermodynamic driving force for the transformations is calcite crystallization, yet it is gated by specific combinations of water-phosphate levels in the initial amorphous coprecipitates. The molecular details of the spontaneously transforming ACC and of the stabilized ACC modulated by phosphate and water at ambient conditions, provide insight into biogenic and biomimetic pathways.

  19. Amorphous phase separation in polypropylene block copolymers as revealed by thermostimulated depolarization measurements. II. Thermal sampling analysis

    NASA Astrophysics Data System (ADS)

    Ronarc'h, D.; Audren, P.; Moura, J. L.

    1985-07-01

    We achieved a thermal sampling scanning of the β-relaxation region of polypropylene (PP) block copolymers together with the β process of isotactic polypropylene, high-density polyethylene, propylene-ethylene rubber, and part of the PP bloc copolymer soluble in xylene and insoluble in ether. The comparison of activation parameters determined in the above relaxations confirmed the hypotheses drawn from complex spectra studies concerning phase separation and the origin of dielectric relaxations in PP block copolymers. One of the dielectric relaxations of the part of PP block copolymer soluble in xylene and insoluble in ether could be attributed to polypropylene blocks. We related the preexponential factor of the relaxation time to chain environment. Then we discussed the compensation phenomenon in distributed relaxations and the relation between the compensation temperature and variation of thermal expansion coefficient through the compensating relaxation.

  20. Amorphous Silk Fibroin Membranes for Separation of CO2

    NASA Technical Reports Server (NTRS)

    Aberg, Christopher M.; Patel, Anand K.; Gil, Eun Seok; Spontak, Richard J.; Hagg, May-Britt

    2009-01-01

    Amorphous silk fibroin has shown promise as a polymeric material derivable from natural sources for making membranes for use in removing CO2 from mixed-gas streams. For most applications of silk fibroin, for purposes other than gas separation, this material is used in its highly crystalline, nearly natural form because this form has uncommonly high tensile strength. However, the crystalline phase of silk fibroin is impermeable, making it necessary to convert the material to amorphous form to obtain the high permeability needed for gas separation. Accordingly, one aspect of the present development is a process for generating amorphous silk fibroin by treating native silk fibroin in an aqueous methanol/salt solution. The resulting material remains self-standing and can be prepared as thin film suitable for permeation testing. The permeability of this material by pure CO2 has been found to be highly improved, and its mixed-gas permeability has been found to exceed the mixed-gas permeabilities of several ultrahigh-CO2-permeable synthetic polymers. Only one of the synthetic polymers poly(trimethylsilylpropyne) [PTMSP] may be more highly permeable by CO2. PTMSP becomes unstable with time, whereas amorphous silk should not, although at the time of this reporting this has not been conclusively proven.

  1. Magnetic Phases in Amorphous Alloys.

    NASA Astrophysics Data System (ADS)

    Mazumdar, Prosenjit

    In magnetic amorphous alloy with competiting exchange interactions, there exists a multicritical point (MCP) in the temperature (T) vs. concentration (x) phase diagram (x(,c), (theta)(,c)). In the present work, the static (equilibrium) magnetic response near the MCP is thoroughly investigated using low, d.c. fields (B(,a) < 10 Oe) in two systems of alloys: (I) Fe(,x)Ni(,75-x)P(,16)B(,6)Al(,3) and (II) Fe(,x)Ni(,80-x)P(,14)B(,6). From the measurements of the reversible magnetization M(x, T, B(,a)), the following notable results are found: (1) The phase diagram exhibits a non-montonic FM-SG transition line (i.e. T(,f)'s) in both the systems. (2) There is a dramatic change in the magnetic response as x goes across x(,c). (3) The magnetization collapses as M(,P) (TURN) (x - x(,c))('0.3(+OR-)0.1) when x (--->) x(,c)('+). (4) The peak susceptibility diverges as (chi)(,P) (TURN) (x(,c) - x)('-1.5(+OR-)0.2) when x (--->) x(,c)('-). (5) The results (2), (3), and (4) are highly suggestive of a percolation transition in the magnetic network at the critical concentration for ferromagnetism (i.e. x(,c)). (6) Dramatic changes in the transition temperatures and a perceptible shift in x(,c) are observed when normal boron is replaced by enriched boron ((TURN)100% B('11)) in the series (I) samples. (7) The non-linear susceptibility ((chi)(,H)) exhibits the expected divergence at T(,g) with 'universal' exponents in concentrated spin glasses. (8) In the latter, a divergence in the linear susceptibility ((chi)(,o)) is observed for the first time. This is attributed to the close proximity of the ferromagnetic phase at x(,c). The study of the irreversible moment M(,i) (x, T, B(,a)) reveals the following: (9) Depending on the various methods of preparation, it is possible to generate states with different values of M(,i) at low T, all of which are stable (metastable) in time. This implies non -ergodic behavior. (10) For re-entrants (x > x(,c)), the amount of freezing achieved viz. M

  2. Amorphous carbon buffer layers for separating free gallium nitride films

    NASA Astrophysics Data System (ADS)

    Altakhov, A. S.; Gorbunov, R. I.; Kasharina, L. A.; Latyshev, F. E.; Tarala, V. A.; Shreter, Yu. G.

    2016-11-01

    The possibility of using amorphous diamond-like carbon (DLC) films for self-separation of gallium nitride (GaN) layers grown by hydride vapor-phase epitaxy has been analyzed. DLC films have been synthesized by plasma-enhanced chemical vapor deposition under low pressure on sapphire (Al2O3) substrates with a (0001) crystallographic orientation. The samples have been studied by the methods of Raman scattering and X-ray diffraction analysis. It is shown that thin DLC films affect only slightly the processes of nucleation and growth of gallium nitride films. Notably, the strength of the "GaN film-Al2O3" substrate interface decreases, which facilitates separation of the GaN layers.

  3. Phase transitions in biogenic amorphous calcium carbonate

    PubMed Central

    Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.

    2012-01-01

    Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931

  4. Process for phase separation

    DOEpatents

    Comolli, Alfred G.

    1979-01-01

    This invention provides a continuous process for separating a gaseous phase from a hydrocarbon liquid containing carbonaceous particulates and gases. The liquid is fed to a cylindrical separator, with the gaseous phase being removed therefrom as an overhead product, whereas the hydrocarbon liquid and the particulates are withdrawn as a bottoms product. By feeding the liquid tangentially to the separator and maintaining a particulate-liquid slurry downward velocity of from about 0.01 to about 0.25 fps in the separator, a total solids weight percent in the slurry of from about 0.1 to about 30%, a slurry temperature of from about 550.degree. to about 900.degree. F., a slurry residence time in the separator of from about 30 to about 360 seconds, and a length/diameter ratio for the separator of from about 20/1 to about 50/1, so that the characterization factor, .alpha., defined as ##STR1## DOES NOT EXCEED ABOUT 48 (.degree.R sec.sup.2)/ft, the deposit of carbonaceous materials on the interior surface of the separator may be substantially eliminated.

  5. Role of diffusion in amorphous-phase formation and crystallization of amorphous Ni--Zr

    SciTech Connect

    Barbour, J.C.; de Reus, R.; Denier van der Gon, A.W.; Saris, F.W.

    1987-03-01

    The Ni--Zr system is examined as a representative system for the formation of an amorphous phase by diffusion and for the crystallization of an amorphous phase by diffusion. High-resolution electron microscopy (HREM) is used to show that the amorphous phase grows by bulk diffusion through the amorphous material rather than by short-circuit diffusion. Also, the HREM shows that the amorphous phase formed by diffusion appears to be the same as the vapor-deposited amorphous phase. A correlation between crystallization temperatures (T/sub x/) and the enthalpy of large-atom hole formation is given. This correlation predicts values of T/sub x/ that are lower than those predicted from the small-atom hole-formation model. The difference in hole-formation enthalpies for the large and small atoms is given as a criterion for amorphous-phase formation via diffusion.

  6. Disappearance and Creation of Constrained Amorphous Phase

    NASA Astrophysics Data System (ADS)

    Cebe, Peggy; Lu, Sharon X.

    1997-03-01

    We report observation of the disappearance and recreation of rigid, or constrained, amorphous phase by sequential thermal annealing. Tempera- ture modulated differential scanning calorimetry (MDSC) is used to study the glass transition and lower melting endotherm after annealing. Cold crystallization of poly(phenylene sulfide), PPS, at a temperature just above Tg creates an initial large fraction of rigid amorphous phase (RAP). Brief, rapid annealing to a higher temperature causes RAP almost to disappear completely. Subsequent reannealing at the original lower temperature restores RAP to its original value. At the same time that RAP is being removed, Tg decreases; when RAP is restored, Tg also returns to its initial value. The crystal fraction remains unaffected by the annealing sequence.

  7. Phase transitions in biogenic amorphous calcium carbonate

    NASA Astrophysics Data System (ADS)

    Gong, Yutao

    Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

  8. Amorphous Alloy Membranes for High Temperature Hydrogen Separation

    SciTech Connect

    Coulter, K

    2013-09-30

    At the beginning of this project, thin film amorphous alloy membranes were considered a nascent but promising new technology for industrial-scale hydrogen gas separations from coal- derived syngas. This project used a combination of theoretical modeling, advanced physical vapor deposition fabricating, and laboratory and gasifier testing to develop amorphous alloy membranes that had the potential to meet Department of Energy (DOE) targets in the testing strategies outlined in the NETL Membrane Test Protocol. The project is complete with Southwest Research Institute® (SwRI®), Georgia Institute of Technology (GT), and Western Research Institute (WRI) having all operated independently and concurrently. GT studied the hydrogen transport properties of several amorphous alloys and found that ZrCu and ZrCuTi were the most promising candidates. GT also evaluated the hydrogen transport properties of V, Nb and Ta membranes coated with different transition-metal carbides (TMCs) (TM = Ti, Hf, Zr) catalytic layers by employing first-principles calculations together with statistical mechanics methods and determined that TiC was the most promising material to provide catalytic hydrogen dissociation. SwRI developed magnetron coating techniques to deposit a range of amorphous alloys onto both porous discs and tubular substrates. Unfortunately none of the amorphous alloys could be deposited without pinhole defects that undermined the selectivity of the membranes. WRI tested the thermal properties of the ZrCu and ZrNi alloys and found that under reducing environments the upper temperature limit of operation without recrystallization is ~250 °C. There were four publications generated from this project with two additional manuscripts in progress and six presentations were made at national and international technical conferences. The combination of the pinhole defects and the lack of high temperature stability make the theoretically identified most promising candidate amorphous alloys

  9. Local Crystalline Structure in an Amorphous Protein Dense Phase.

    PubMed

    Greene, Daniel G; Modla, Shannon; Wagner, Norman J; Sandler, Stanley I; Lenhoff, Abraham M

    2015-10-20

    Proteins exhibit a variety of dense phases ranging from gels, aggregates, and precipitates to crystalline phases and dense liquids. Although the structure of the crystalline phase is known in atomistic detail, little attention has been paid to noncrystalline protein dense phases, and in many cases the structures of these phases are assumed to be fully amorphous. In this work, we used small-angle neutron scattering, electron microscopy, and electron tomography to measure the structure of ovalbumin precipitate particles salted out with ammonium sulfate. We found that the ovalbumin phase-separates into core-shell particles with a core radius of ∼2 μm and shell thickness of ∼0.5 μm. Within this shell region, nanostructures comprised of crystallites of ovalbumin self-assemble into a well-defined bicontinuous network with branches ∼12 nm thick. These results demonstrate that the protein gel is comprised in part of nanocrystalline protein.

  10. Local Crystalline Structure in an Amorphous Protein Dense Phase

    PubMed Central

    Greene, Daniel G.; Modla, Shannon; Wagner, Norman J.; Sandler, Stanley I.; Lenhoff, Abraham M.

    2015-01-01

    Proteins exhibit a variety of dense phases ranging from gels, aggregates, and precipitates to crystalline phases and dense liquids. Although the structure of the crystalline phase is known in atomistic detail, little attention has been paid to noncrystalline protein dense phases, and in many cases the structures of these phases are assumed to be fully amorphous. In this work, we used small-angle neutron scattering, electron microscopy, and electron tomography to measure the structure of ovalbumin precipitate particles salted out with ammonium sulfate. We found that the ovalbumin phase-separates into core-shell particles with a core radius of ∼2 μm and shell thickness of ∼0.5 μm. Within this shell region, nanostructures comprised of crystallites of ovalbumin self-assemble into a well-defined bicontinuous network with branches ∼12 nm thick. These results demonstrate that the protein gel is comprised in part of nanocrystalline protein. PMID:26488663

  11. Microgravity Passive Phase Separator

    NASA Technical Reports Server (NTRS)

    Paragano, Matthew; Indoe, William; Darmetko, Jeffrey

    2012-01-01

    A new invention disclosure discusses a structure and process for separating gas from liquids in microgravity. The Microgravity Passive Phase Separator consists of two concentric, pleated, woven stainless- steel screens (25-micrometer nominal pore) with an axial inlet, and an annular outlet between both screens (see figure). Water enters at one end of the center screen at high velocity, eventually passing through the inner screen and out through the annular exit. As gas is introduced into the flow stream, the drag force exerted on the bubble pushes it downstream until flow stagnation or until it reaches an equilibrium point between the surface tension holding bubble to the screen and the drag force. Gas bubbles of a given size will form a front that is moved further down the length of the inner screen with increasing velocity. As more bubbles are added, the front location will remain fixed, but additional bubbles will move to the end of the unit, eventually coming to rest in the large cavity between the unit housing and the outer screen (storage area). Owing to the small size of the pores and the hydrophilic nature of the screen material, gas does not pass through the screen and is retained within the unit for emptying during ground processing. If debris is picked up on the screen, the area closest to the inlet will become clogged, so high-velocity flow will persist farther down the length of the center screen, pushing the bubble front further from the inlet of the inner screen. It is desired to keep the velocity high enough so that, for any bubble size, an area of clean screen exists between the bubbles and the debris. The primary benefits of this innovation are the lack of any need for additional power, strip gas, or location for venting the separated gas. As the unit contains no membrane, the transport fluid will not be lost due to evaporation in the process of gas separation. Separation is performed with relatively low pressure drop based on the large surface

  12. Four phases of amorphous water: Simulations versus experiment.

    PubMed

    Brovchenko, Ivan; Oleinikova, Alla

    2006-04-28

    Multiplicity of the liquid-liquid phase transitions in supercooled water, first obtained in computer simulations [Brovchenko et al., J. Chem. Phys. 118, 9473 (2003)], has got strong support from the recent experimental observation of the two phase transitions between amorphous ices [Loerting et al., Phys. Rev. Lett. 96, 025702 (2006)]. These experimental results allow assignment of the four amorphous water phases (I-IV) obtained in simulations to the three kinds of amorphous ices. Water phase I (rho approximately 0.90 gcm(3)) corresponds to the low-density amorphous ice, phase III (rho approximately 1.10 gcm(3)) to the high-density amorphous ice, and phase IV (rho approximately 1.20 gcm(3)) to the very-high-density amorphous ice. Phase II of model water with density rho approximately 1.00 gcm(3) corresponds to the normal-density water. Such assignment is confirmed by the comparison of the structural functions of the amorphous phases of model water and real water. In phases I and II the first and second coordination shells are clearly divided. Phase I consists mainly of the four coordinated tetrahedrally ordered water molecules. Phase II is enriched with molecules, which have tetrahedrally ordered four nearest neighbors and up six molecules in the first coordination shell. Majority of the molecules in phase III still have tetrahedrally ordered four nearest neighbors. Transition from phase III to phase IV is characterized by a noticeable drop of tetrahedral order, and phase IV consists mainly of molecules with highly isotropic angular distribution of the nearest neighbors. Relation between the structures of amorphous water phases, crystalline ices, and liquid water is discussed.

  13. REVIEW ARTICLE: Viscoelastic phase separation

    NASA Astrophysics Data System (ADS)

    Tanaka, Hajime

    2000-04-01

    Descriptions of phase separation in condensed matter have so far been classified into a solid model (model B) and a fluid model (model H). In the former the diffusion is the only transport process, while in the latter material can be transported by both diffusion and hydrodynamic flow. It has recently been found that in addition to these well-known models a new model of phase separation, the `viscoelastic model', is required to describe the phase-separation behaviour of a dynamically asymmetric mixture, which is composed of fast and slow components. Such `dynamic asymmetry' can be induced by either the large size difference or the difference in glass-transition temperature between the components of a mixture. The former often exists in so-called complex fluids, such as polymer solutions, micellar solutions, colloidal suspensions, emulsions and protein solutions. The latter, on the other hand, can exist in any mixture in principle. This new type of phase separation is called `viscoelastic phase separation' since viscoelastic effects play a dominant role. Viscoelastic phase separation may be a `general' model of phase separation, which includes solid and fluid models as special cases: for example, fluid phase separation described by model H, which is believed to be the usual case, can be viewed as a `special' (rather rare) case of viscoelastic phase separation. Here we review the experiments, theories and numerical simulations for viscoelastic phase separation. In dynamically asymmetric mixtures, phase separation generally leads to the formation of a long-lived `interaction network' (a transient gel) of slow-component molecules (or particles), if the attractive interactions between them are strong enough. Because of its long relaxation time, it cannot catch up with the deformation rate of the phase separation itself and as a result the stress is asymmetrically divided between the components. This leads to the transient formation of networklike or spongelike

  14. Microcellular foams via phase separation

    SciTech Connect

    Young, A.T.

    1985-01-01

    A study of wide variety of processes for making plastic foams shows that phase separation processes for polymers from solutions offers the most viable methods for obtaining rigid plastic foams which met the physical requirements for fusion target designs. Four general phase separation methods have been shown to give polymer foams with densities less than 0.1 g/cm/sup 3/ and cell sizes of 30..mu..m or less. These methods involve the utilization of non-solvent, chemical or thermal cooling processes to achieve a controlled phase separation wherein either two distinct phases are obtained where the polymer phase is a continuous phase or two bicontinuous phases are obtained where both the polymer and solvent are interpenetrating, continuous, labyrinthine phases. Subsequent removal of the solvent gives the final foam structure.

  15. Phase separation in lanthanum manganites

    NASA Astrophysics Data System (ADS)

    Sedykh, Vera D.

    2016-10-01

    The structural transformations in doped lanthanum manganites La1-xMexMnO3+δ (Me = Ca, Sr, Ba) (with a small amount of 57Fe (2%) for Mössbauer experiments) have been studied in a wide concentration range of a doping element (0 < x < 0.2) by Mössbauer spectroscopy and X-ray diffraction analysis. A mixture of three orthorhombic phases has been shown to be formed in all these compounds of a stoichiometric composition, i.e., a structural phase separation takes place. The phase relations for different doping element types and contents significantly differ. The reasons of phase separation in lanthanum manganites are discussed.

  16. X-Ray Amorphous Phases in Terrestrial Analog Volcanic Sediments: Implications for Amorphous Phases in Gale Crater, Mars

    NASA Technical Reports Server (NTRS)

    Smith, R. J.; Horgan, B.; Rampe, E.; Dehouck, E.; Morris, R. V.

    2017-01-01

    X-ray diffraction (XRD) amorphous phases have been found as major components (approx.15-60 wt%) of all rock and soil samples measured by the CheMin XRD instrument in Gale Crater, Mars. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., allophane) phases. Amorphous phases form in abundance during surface weathering on Earth. Yet, these materials are poorly characterized, and it is not certain how properties like composition and structure change with formation environment. The presence of poorly crystalline phases can be inferred from XRD patterns by the appearance of a low angle rise (< or approx.10deg 2(theta)) or broad peaks in the background at low to moderate 2(theta) angles (amorphous humps). CheMin mineral abundances combined with bulk chemical composition measurements from the Alpha Particle X-ray Spectrometer (APXS) have been used to estimate the abundance and composition of the XRD amorphous materials in soil and rock samples on Mars. Here we apply a similar approach to a diverse suite of terrestrial samples - modern soils, glacial sediments, and paleosols - in order to determine how formation environment, climate, and diagenesis affect the abundance and composition of X-ray amorphous phases.

  17. Two-phase electrochemical lithiation in amorphous silicon.

    PubMed

    Wang, Jiang Wei; He, Yu; Fan, Feifei; Liu, Xiao Hua; Xia, Shuman; Liu, Yang; Harris, C Thomas; Li, Hong; Huang, Jian Yu; Mao, Scott X; Zhu, Ting

    2013-02-13

    Lithium-ion batteries have revolutionized portable electronics and will be a key to electrifying transport vehicles and delivering renewable electricity. Amorphous silicon (a-Si) is being intensively studied as a high-capacity anode material for next-generation lithium-ion batteries. Its lithiation has been widely thought to occur through a single-phase mechanism with gentle Li profiles, thus offering a significant potential for mitigating pulverization and capacity fade. Here, we discover a surprising two-phase process of electrochemical lithiation in a-Si by using in situ transmission electron microscopy. The lithiation occurs by the movement of a sharp phase boundary between the a-Si reactant and an amorphous Li(x)Si (a-Li(x)Si, x ~ 2.5) product. Such a striking amorphous-amorphous interface exists until the remaining a-Si is consumed. Then a second step of lithiation sets in without a visible interface, resulting in the final product of a-Li(x)Si (x ~ 3.75). We show that the two-phase lithiation can be the fundamental mechanism underpinning the anomalous morphological change of microfabricated a-Si electrodes, i.e., from a disk shape to a dome shape. Our results represent a significant step toward the understanding of the electrochemically driven reaction and degradation in amorphous materials, which is critical to the development of microstructurally stable electrodes for high-performance lithium-ion batteries.

  18. Structural transformations in amorphous ↔ crystalline phase change of Ga-Sb alloys

    SciTech Connect

    Edwards, T. G.; Sen, S.; Hung, I.; Gan, Z.; Kalkan, B.; Raoux, S.

    2013-12-21

    Ga-Sb alloys with compositions ranging between ∼12 and 50 at. % Ga are promising materials for phase change random access memory applications. The short-range structures of two such alloys with compositions Ga{sub 14}Sb{sub 86} and Ga{sub 46}Sb{sub 54} are investigated, in their amorphous and crystalline states, using {sup 71}Ga and {sup 121}Sb nuclear magnetic resonance spectroscopy and synchrotron x-ray diffraction. The Ga and Sb atoms are fourfold coordinated in the as-deposited amorphous Ga{sub 46}Sb{sub 54} with nearly 40% of the constituent atoms being involved in Ga-Ga and Sb-Sb homopolar bonding. This necessitates extensive bond switching and elimination of homopolar bonds during crystallization. On the other hand, Ga and Sb atoms are all threefold coordinated in the as-deposited amorphous Ga{sub 14}Sb{sub 86}. Crystallization of this material involves phase separation of GaSb domains in Sb matrix and a concomitant increase in the Ga coordination number from 3 to 4. Results from crystallization kinetics experiments suggest that the melt-quenching results in the elimination of structural “defects” such as the homopolar bonds and threefold coordinated Ga atoms in the amorphous phases of these alloys, thereby rendering them structurally more similar to the corresponding crystalline states compared to the as-deposited amorphous phases.

  19. Amorphous intergranular phases control the properties of rodent tooth enamel

    NASA Astrophysics Data System (ADS)

    Gordon, Lyle M.; Cohen, Michael J.; MacRenaris, Keith W.; Pasteris, Jill D.; Seda, Takele; Joester, Derk

    2015-02-01

    Dental enamel, a hierarchical material composed primarily of hydroxylapatite nanowires, is susceptible to degradation by plaque biofilm-derived acids. The solubility of enamel strongly depends on the presence of Mg2+, F-, and CO32-. However, determining the distribution of these minor ions is challenging. We show—using atom probe tomography, x-ray absorption spectroscopy, and correlative techniques—that in unpigmented rodent enamel, Mg2+ is predominantly present at grain boundaries as an intergranular phase of Mg-substituted amorphous calcium phosphate (Mg-ACP). In the pigmented enamel, a mixture of ferrihydrite and amorphous iron-calcium phosphate replaces the more soluble Mg-ACP, rendering it both harder and more resistant to acid attack. These results demonstrate the presence of enduring amorphous phases with a dramatic influence on the physical and chemical properties of the mature mineralized tissue.

  20. The effect of liquid-liquid phase separation of glass on the properties and crystallization behavior

    NASA Technical Reports Server (NTRS)

    Li, J. Z.

    1985-01-01

    A theoretical discussion is given of the phase separation mechanism of amorphous materials. This includes nucleus growth, spinoidal decomposition, and nuclei agglomeration and coarsening. Various types of glass are analyzed.

  1. Amorphous phase formation in mechanically alloyed iron-based systems

    NASA Astrophysics Data System (ADS)

    Sharma, Satyajeet

    Bulk metallic glasses have interesting combination of physical, chemical, mechanical, and magnetic properties which make them attractive for a variety of applications. Consequently there has been a lot of interest in understanding the structure and properties of these materials. More varied applications can be sought if one understands the reasons for glass formation and the methods to control them. The glass-forming ability (GFA) of alloys can be substantially increased by a proper selection of alloying elements and the chemical composition of the alloy. High GFA will enable in obtaining large section thickness of amorphous alloys. Ability to produce glassy alloys in larger section thicknesses enables exploitation of these advanced materials for a variety of different applications. The technique of mechanical alloying (MA) is a powerful non-equilibrium processing technique and is known to produce glassy (or amorphous) alloys in several alloy systems. Metallic amorphous alloys have been produced by MA starting from either blended elemental metal powders or pre-alloyed powders. Subsequently, these amorphous alloy powders could be consolidated to full density in the temperature range between the glass transition and crystallization temperatures, where the amorphous phase has a very low viscosity. This Dissertation focuses on identifying the various Fe-based multicomponent alloy systems that can be amorphized using the MA technique, studying the GFA of alloys with emphasis on improving it, and also on analyzing the effect of extended milling time on the constitution of the amorphous alloy powder produced at earlier times. The Dissertation contains seven chapters, where the lead chapter deals with the background, history and introduction to bulk metallic glasses. The following four chapters are the published/to be published work, where the criterion for predicting glass formation, effect of Niobium addition on glass-forming ability (GFA), lattice contraction on

  2. Aging mechanisms in amorphous phase-change materials.

    PubMed

    Raty, Jean Yves; Zhang, Wei; Luckas, Jennifer; Chen, Chao; Mazzarello, Riccardo; Bichara, Christophe; Wuttig, Matthias

    2015-06-24

    Aging is a ubiquitous phenomenon in glasses. In the case of phase-change materials, it leads to a drift in the electrical resistance, which hinders the development of ultrahigh density storage devices. Here we elucidate the aging process in amorphous GeTe, a prototypical phase-change material, by advanced numerical simulations, photothermal deflection spectroscopy and impedance spectroscopy experiments. We show that aging is accompanied by a progressive change of the local chemical order towards the crystalline one. Yet, the glass evolves towards a covalent amorphous network with increasing Peierls distortion, whose structural and electronic properties drift away from those of the resonantly bonded crystal. This behaviour sets phase-change materials apart from conventional glass-forming systems, which display the same local structure and bonding in both phases.

  3. Crystalline-amorphous interaction in relation to the phase diagrams of binary polymer blends containing a crystalline constituent.

    PubMed

    Rathi, Pankaj; Huang, Tsang-Min; Dayal, Pratyush; Kyu, Thein

    2008-05-22

    The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.

  4. Motility-Induced Phase Separation

    NASA Astrophysics Data System (ADS)

    Cates, Michael E.; Tailleur, Julien

    2015-03-01

    Self-propelled particles include both self-phoretic synthetic colloids and various microorganisms. By continually consuming energy, they bypass the laws of equilibrium thermodynamics. These laws enforce the Boltzmann distribution in thermal equilibrium: The steady state is then independent of kinetic parameters. In contrast, self-propelled particles tend to accumulate where they move more slowly. They may also slow down at high density for either biochemical or steric reasons. This creates positive feedback, which can lead to motility-induced phase separation (MIPS) between dense and dilute fluid phases. At leading order in gradients, a mapping relates variable-speed, self-propelled particles to passive particles with attractions. This deep link to equilibrium phase separation is confirmed by simulations but generally breaks down at higher order in gradients: New effects, with no equilibrium counterpart, then emerge. We give a selective overview of the fast-developing field of MIPS, focusing on theory and simulation but including a brief speculative survey of its experimental implications.

  5. Dielectric properties of amorphous phase-change materials

    NASA Astrophysics Data System (ADS)

    Chen, C.; Jost, P.; Volker, H.; Kaminski, M.; Wirtssohn, M.; Engelmann, U.; Krüger, K.; Schlich, F.; Schlockermann, C.; Lobo, R. P. S. M.; Wuttig, M.

    2017-03-01

    The dielectric function of several amorphous phase-change materials has been determined by employing a combination of impedance spectroscopy (9 kHz-3 GHz) and optical spectroscopy from the far- (20 c m-1 , 0.6 THz) to the near- (12 000 c m-1 , 360 THz) infrared, i.e., from the DC limit to the first interband transition. While phase-change materials undergo a change from covalent bonding to resonant bonding on crystallization, the amorphous and crystalline phases of ordinary chalcogenide semiconductors are both governed by virtually the same covalent bonds. Here, we study the dielectric properties of amorphous phase-change materials on the pseudobinary line between GeTe and S b2T e3 . These data provide important insights into the charge transport and the nature of bonding in amorphous phase-change materials. No frequency dependence of permittivity and conductivity is discernible in the impedance spectroscopy measurements. Consequently, there are no dielectric relaxations. The frequency-independent conductivity is in line with charge transport via extended states. The static dielectric constant significantly exceeds the optical dielectric constant. This observation is corroborated by transmittance measurements in the far infrared, which show optical phonons. From the intensity of these phonon modes, a large Born effective charge is derived. Nevertheless, it is known that crystalline phase-change materials such as GeTe possess even significantly larger Born effective charges. Crystallization is hence accompanied by a huge increase in the Born effective charge, which reveals a significant change of bonding upon crystallization. In addition, a clear stoichiometry trend in the static dielectric constant along the pseudobinary line between GeTe and S b2T e3 has been identified.

  6. Thermodynamically controlled crystallization of glucose pentaacetates from amorphous phase

    SciTech Connect

    Wlodarczyk, P. Hawelek, L.; Hudecki, A.; Kolano-Burian, A.; Wlodarczyk, A.

    2016-08-15

    The α and β glucose pentaacetates are known sugar derivatives, which can be potentially used as stabilizers of amorphous phase of active ingredients of drugs (API). In the present work, crystallization behavior of equimolar mixture of α and β form in comparison to both pure anomers is revealed. It was shown that despite the same molecular interactions and similar molecular dynamics, crystallization from amorphous phase is significantly suppressed in equimolar mixture. Time dependent X-ray diffraction studies confirmed higher stability of the quenched amorphous equimolar mixture. Its tendency to crystallization is about 10 times lower than for pure anomers. Calorimetric studies revealed that the α and β anomers don’t form solid solutions and have eutectic point for x{sub α} = 0.625. Suppressed crystallization tendency in the mixture is probably caused by the altered thermodynamics of the system. The factors such as difference of free energy between crystalline and amorphous state or altered configurational entropy are probably responsible for the inhibitory effect.

  7. Thermodynamically controlled crystallization of glucose pentaacetates from amorphous phase

    NASA Astrophysics Data System (ADS)

    Wlodarczyk, P.; Hawelek, L.; Hudecki, A.; Wlodarczyk, A.; Kolano-Burian, A.

    2016-08-01

    The α and β glucose pentaacetates are known sugar derivatives, which can be potentially used as stabilizers of amorphous phase of active ingredients of drugs (API). In the present work, crystallization behavior of equimolar mixture of α and β form in comparison to both pure anomers is revealed. It was shown that despite the same molecular interactions and similar molecular dynamics, crystallization from amorphous phase is significantly suppressed in equimolar mixture. Time dependent X-ray diffraction studies confirmed higher stability of the quenched amorphous equimolar mixture. Its tendency to crystallization is about 10 times lower than for pure anomers. Calorimetric studies revealed that the α and β anomers don't form solid solutions and have eutectic point for xα = 0.625. Suppressed crystallization tendency in the mixture is probably caused by the altered thermodynamics of the system. The factors such as difference of free energy between crystalline and amorphous state or altered configurational entropy are probably responsible for the inhibitory effect.

  8. Vapors-liquid phase separator

    NASA Astrophysics Data System (ADS)

    Frederking, T. H. K.; Brown, G. S.; Chuang, C.; Kamioka, Y.; Kim, Y. I.; Lee, J. M.; Yuan, S. W. K.

    1980-10-01

    The use of porous plugs, mostly with in the form of passive devices with constant area were considered as vapor-liquid phase separators for helium 2 storage vessels under reduced gravity. The incorporation of components with variable cross sectional area as a method of flow rate modification was also investigated. A particular device which uses a shutter-type system for area variation was designed and constructed. This system successfully permitted flor rate changes of up to plus or minus 60% from its mean value.

  9. Viscous friction between crystalline and amorphous phase of dragline silk.

    PubMed

    Patil, Sandeep P; Xiao, Senbo; Gkagkas, Konstantinos; Markert, Bernd; Gräter, Frauke

    2014-01-01

    The hierarchical structure of spider dragline silk is composed of two major constituents, the amorphous phase and crystalline units, and its mechanical response has been attributed to these prime constituents. Silk mechanics, however, might also be influenced by the resistance against sliding of these two phases relative to each other under load. We here used atomistic molecular dynamics (MD) simulations to obtain friction forces for the relative sliding of the amorphous phase and crystalline units of Araneus diadematus spider silk. We computed the coefficient of viscosity of this interface to be in the order of 10(2) Ns/m(2) by extrapolating our simulation data to the viscous limit. Interestingly, this value is two orders of magnitude smaller than the coefficient of viscosity within the amorphous phase. This suggests that sliding along a planar and homogeneous surface of straight polyalanine chains is much less hindered than within entangled disordered chains. Finally, in a simple finite element model, which is based on parameters determined from MD simulations including the newly deduced coefficient of viscosity, we assessed the frictional behavior between these two components for the experimental range of relative pulling velocities. We found that a perfectly relative horizontal motion has no significant resistance against sliding, however, slightly inclined loading causes measurable resistance. Our analysis paves the way towards a finite element model of silk fibers in which crystalline units can slide, move and rearrange themselves in the fiber during loading.

  10. Viscous Friction between Crystalline and Amorphous Phase of Dragline Silk

    PubMed Central

    Patil, Sandeep P.; Xiao, Senbo; Gkagkas, Konstantinos; Markert, Bernd; Gräter, Frauke

    2014-01-01

    The hierarchical structure of spider dragline silk is composed of two major constituents, the amorphous phase and crystalline units, and its mechanical response has been attributed to these prime constituents. Silk mechanics, however, might also be influenced by the resistance against sliding of these two phases relative to each other under load. We here used atomistic molecular dynamics (MD) simulations to obtain friction forces for the relative sliding of the amorphous phase and crystalline units of Araneus diadematus spider silk. We computed the coefficient of viscosity of this interface to be in the order of 102 Ns/m2 by extrapolating our simulation data to the viscous limit. Interestingly, this value is two orders of magnitude smaller than the coefficient of viscosity within the amorphous phase. This suggests that sliding along a planar and homogeneous surface of straight polyalanine chains is much less hindered than within entangled disordered chains. Finally, in a simple finite element model, which is based on parameters determined from MD simulations including the newly deduced coefficient of viscosity, we assessed the frictional behavior between these two components for the experimental range of relative pulling velocities. We found that a perfectly relative horizontal motion has no significant resistance against sliding, however, slightly inclined loading causes measurable resistance. Our analysis paves the way towards a finite element model of silk fibers in which crystalline units can slide, move and rearrange themselves in the fiber during loading. PMID:25119288

  11. The existence of amorphous phase in Portland cements: Physical factors affecting Rietveld quantitative phase analysis

    SciTech Connect

    Snellings, Ruben Bazzoni, Amélie Scrivener, Karen

    2014-05-01

    Rietveld quantitative phase analysis has become a widespread tool for the characterization of Portland cement, both for research and production control purposes. One of the major remaining points of debate is whether Portland cements contain amorphous content or not. This paper presents detailed analyses of the amorphous phase contents in a set of commercial Portland cements, clinker, synthetic alite and limestone by Rietveld refinement of X-ray powder diffraction measurements using both external and internal standard methods. A systematic study showed that the sample preparation and comminution procedure is closely linked to the calculated amorphous contents. Particle size reduction by wet-grinding lowered the calculated amorphous contents to insignificant quantities for all materials studied. No amorphous content was identified in the final analysis of the Portland cements under investigation.

  12. Comprehensive phase characterization of crystalline and amorphous phases of a Class F fly ash

    SciTech Connect

    Chancey, Ryan T.; Stutzman, Paul; Juenger, Maria C.G.; Fowler, David W.

    2010-01-15

    A comprehensive approach to qualitative and quantitative characterization of crystalline and amorphous constituent phases of a largely heterogeneous Class F fly ash is presented. Traditionally, fly ash composition is expressed as bulk elemental oxide content, generally determined by X-ray fluorescence spectroscopy. However, such analysis does not discern between relatively inert crystalline phases and highly reactive amorphous phases of similar elemental composition. X-ray diffraction was used to identify the crystalline phases present in the fly ash, and the Rietveld quantitative phase analysis method was applied to determine the relative proportion of each of these phases. A synergistic method of X-ray powder diffraction, scanning electron microscopy, energy dispersive spectroscopy, and multispectral image analysis was developed to identify and quantify the amorphous phases present in the fly ash.

  13. Phase transformations in amorphous fullerite C60 under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Borisova, P. A.; Blanter, M. S.; Brazhkin, V. V.; Somenkov, V. A.; Filonenko, V. P.

    2015-08-01

    First phase transformations of amorphous fullerite C60 at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С60 molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature-pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.

  14. Factor analysis of 27Al MAS NMR spectra for identifying nanocrystalline phases in amorphous geopolymers.

    PubMed

    Urbanova, Martina; Kobera, Libor; Brus, Jiri

    2013-11-01

    Nanostructured materials offer enhanced physicochemical properties because of the large interfacial area. Typically, geopolymers with specifically synthesized nanosized zeolites are a promising material for the sorption of pollutants. The structural characterization of these aluminosilicates, however, continues to be a challenge. To circumvent complications resulting from the amorphous character of the aluminosilicate matrix and from the low concentrations of nanosized crystallites, we have proposed a procedure based on factor analysis of (27)Al MAS NMR spectra. The capability of the proposed method was tested on geopolymers that exhibited various tendencies to crystallize (i) completely amorphous systems, (ii) X-ray amorphous systems with nanocrystalline phases, and (iii) highly crystalline systems. Although the recorded (27)Al MAS NMR spectra did not show visible differences between the amorphous systems (i) and the geopolymers with the nanocrystalline phase (ii), the applied factor analysis unambiguously distinguished these materials. The samples were separated into the well-defined clusters, and the systems with the evolving crystalline phase were identified even before any crystalline fraction was detected by X-ray powder diffraction. Reliability of the proposed procedure was verified by comparing it with (29)Si MAS NMR spectra. Factor analysis of (27)Al MAS NMR spectra thus has the ability to reveal spectroscopic features corresponding to the nanocrystalline phases. Because the measurement time of (27)Al MAS NMR spectra is significantly shorter than that of (29)Si MAS NMR data, the proposed procedure is particularly suitable for the analysis of large sets of specifically synthesized geopolymers in which the formation of the limited fractions of nanocrystalline phases is desired.

  15. Amorphous Calcium Carbonate in Biomineralization: Stable and Precursor Phases

    NASA Astrophysics Data System (ADS)

    Weiner, S.

    2003-12-01

    The biological formation of the crystalline polymorphs of calcium carbonate, aragonite and calcite, is widespread. The less stable polymorphs, vaterite and monohydrocalcite are also formed by some organisms. Surprisingly, the highly unstable phase, amorphous calcium carbonate (ACC), is formed by a variety of organisms from different phyla. Most of these are stable at least within the lifetime of the organism. The stable forms all have a stoichiometry of CaCO3.H2O. Despite the fact that they do not diffract X-rays. Studies of their short range order by EXAFS, reveal species specific variations in the number and distances of atoms that surround the calcium ion. Proteins extracted from stable biogenic ACC are able to stabilize the phase in vitro. ACC has also been identified as a transient precursor phase during the formation of the calcitic larval spicule of the sea urchin and the formation of the larval shell of a bivalve. The transient form has little or no water associated with the CaCO3. Preliminary EXAFS data suggest that the short range order of the sea urchin spicule transient ACC resembles calcite. Proteins extracted from these spicules are able to stabilize ACC provided Mg is present in the solution. As the mollusks and the echinoderms are on two different branches of the animal phylogenetic tree, it is conceivable that the strategy of using ACC as a precursor phase at least for larval mineralization may be widespread. It has yet to be shown that it is used by adults of either phylum. The manner in which organisms precipitate, stabilize and destabilize if necessary, this highly metastable phase of calcium carbonate presents many fascinating and enigmatic questions, whose solutions could well contribute to a better understanding of basic processes in biomineralization. For more details and references, see Addadi, L., Raz, S. and Weiner, S. (2003). Taking advantage of disorder: Amorphous calcium carbonate and its roles in biomineralization. Adv. Mat.15, 959-970.

  16. Viscoelastic Phase Separation of Protein Solutions

    NASA Astrophysics Data System (ADS)

    Tanaka, Hajime; Nishikawa, Yuya

    2005-08-01

    In addition to the known behavior of normal phase separation and gelation, we report novel phase-separation behavior of protein solutions as their intermediate case. A network structure of the protein-rich phase may be formed even if it is the minority phase, contrary to the conventional wisdom. This behavior is characteristic of viscoelastic phase separation found in polymer solutions. This kinetic pathway may play crucial roles in the complex phase ordering of protein solutions, in particular, protein network formation in biological systems and foods.

  17. Two-Phase Flow Separator Investigation

    NASA Image and Video Library

    The goal of the Two-Phase Flow Separator investigation is to help increase understanding of how to separate gases and liquids in microgravity. Many systems on the space station contain both liquids...

  18. Role of the nano amorphous interface in the crystallization of Sb2Te3 towards non-volatile phase change memory: insights from first principles.

    PubMed

    Wang, Xue-Peng; Chen, Nian-Ke; Li, Xian-Bin; Cheng, Yan; Liu, X Q; Xia, Meng-Jiao; Song, Z T; Han, X D; Zhang, S B; Sun, Hong-Bo

    2014-06-14

    The nano amorphous interface is important as it controls the phase transition for data storage. Yet, atomic scale insights into such kinds of systems are still rare. By first-principles calculations, we obtain the atomic interface between amorphous Si and amorphous Sb2Te3, which prevails in the series of Si-Sb-Te phase change materials. This interface model reproduces the experiment-consistent phenomena, i.e. the amorphous stability of Sb2Te3, which defines the data retention in phase change memory, and is greatly enhanced by the nano interface. More importantly, this method offers a direct platform to explore the intrinsic mechanism to understand the material function: (1) by steric effects through the atomic "channel" of the amorphous interface, the arrangement of the Te network is significantly distorted and is separated from the p-orbital bond angle in the conventional phase-change material; and (2) through the electronic "channel" of the amorphous interface, high localized electrons in the form of a lone pair are "projected" to Sb2Te3 from amorphous Si by a proximity effect. These factors set an effective barrier for crystallization and improve the amorphous stability, and thus data retention. The present research and scheme sheds new light on the engineering and manipulation of other key amorphous interfaces, such as Si3N4/Ge2Sb2Te5 and C/Sb2Te3, through first-principles calculations towards non-volatile phase change memory.

  19. Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

    NASA Astrophysics Data System (ADS)

    Kim, H.; McIntyre, P. C.

    2002-11-01

    Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

  20. The structure and dynamics of amorphous and crystalline phases of ice

    SciTech Connect

    Klug, D. D.; Tse, J. S.; Tulk, C. A.; Svensson, E. C.; Swainson, I.; Loong, C.-K.

    2000-07-14

    The structures of the high and low-density amorphous phases of ice are studied using several techniques. The diffraction patterns of high and low density amorphous ice are analyzed using reverse Monte Carlo methods and compared with molecular dynamics simulations of these phases. The spectra of crystalline and amorphous phases of ice obtained by Raman and incoherent inelastic neutron scattering are analyzed to yield structural features for comparison with the results of molecular dynamics and Reverse Monte Carlo analysis. The structural details obtained indicate that there are significant differences between the structure of liquid water and the amorphous phases of ice.

  1. Modeling the amorphous-to-crystalline phase transformation in network materials

    NASA Astrophysics Data System (ADS)

    Kohary, K.; Burlakov, V. M.; Pettifor, D. G.

    2005-06-01

    We have developed a computationally efficient rate equation model to study transformations between amorphous and crystalline phases of network forming materials. Amorphous and crystalline phases are treated in terms of their atomic ring distributions. The transformation between the two phases is considered to be driven by the conversion of one set of rings into another, following the Wooten-Winer-Weaire bond-switching algorithm. Our rate equation model describes both the generation and collapse of amorphous regions in thin crystalline films, the processes crucial for phase-change data storage materials. It is found that the amorphous spot collapse is assisted by the motion of certain crystal facets.

  2. Identification of phases in thin amorphous films of zinc phosphides

    SciTech Connect

    Aleinikova, K. B.; Zinchenko, E. N. Lesovoi, M. V.

    2007-03-15

    Analysis of the experimental atomic radial distribution functions for thin amorphous films of zinc phosphides obtained by explosive laser sputtering has been performed within a fragmentary model. The experiment was carried out with an Emp-10a electron diffractometer in transmitted light at accelerating voltages of 50 and 75 kV. The films obtained by sputtering of {beta}-ZnP{sub 2} single crystals contained nanoparticles of this phase. The films based on Zn{sub 3}P{sub 2} turned out to be two-phase and consisted of dispersed Zn{sub 3}P{sub 2} and {beta}-ZnP{sub 2} nanoparticles. The composition of the film obtained on the basis of {alpha}-ZnP{sub 2} corresponded neither to any one of the known phases in the Zn-P system nor to any mixture of these phases. Crystallization of films in a divergent electron beam confirmed the results of the phase analysis performed using the model atomic radial distribution functions.

  3. Electronic transport in mixed-phase hydrogenated amorphous/nanocrystalline silicon thin films

    NASA Astrophysics Data System (ADS)

    Wienkes, Lee Raymond

    Interest in mixed-phase silicon thin film materials, composed of an amorphous semiconductor matrix in which nanocrystalline inclusions are embedded, stems in part from potential technological applications, including photovoltaic and thin film transistor technologies. Conventional mixed-phase silicon films are produced in a single plasma reactor, where the conditions of the plasma must be precisely tuned, limiting the ability to adjust the film and nanoparticle parameters independently. The films presented in this thesis are deposited using a novel dual-plasma co-deposition approach in which the nanoparticles are produced separately in an upstream reactor and then injected into a secondary reactor where an amorphous silicon film is being grown. The degree of crystallinity and grain sizes of the films are evaluated using Raman spectroscopy and X-ray diffraction respectively. I describe detailed electronic measurements which reveal three distinct conduction mechanisms in n-type doped mixed-phase amorphous/nanocrystalline silicon thin films over a range of nanocrystallite concentrations and temperatures, covering the transition from fully amorphous to ~30% nanocrystalline. As the temperature is varied from 470 to 10 K, we observe activated conduction, multiphonon hopping (MPH) and Mott variable range hopping (VRH) as the nanocrystal content is increased. The transition from MPH to Mott-VRH hopping around 100K is ascribed to the freeze out of the phonon modes. A conduction model involving the parallel contributions of these three distinct conduction mechanisms is shown to describe both the conductivity and the reduced activation energy data to a high accuracy. Additional support is provided by measurements of thermal equilibration effects and noise spectroscopy, both done above room temperature (>300 K). This thesis provides a clear link between measurement and theory in these complex materials.

  4. Self-organization of a periodic structure between amorphous and crystalline phases in a GeTe thin film induced by femtosecond laser pulse amorphization

    SciTech Connect

    Katsumata, Y.; Morita, T.; Morimoto, Y.; Shintani, T.; Saiki, T.

    2014-07-21

    A self-organized fringe pattern in a single amorphous mark of a GeTe thin film was formed by multiple femtosecond pulse amorphization. Micro Raman measurement indicates that the fringe is a periodic alternation between crystalline and amorphous phases. The period of the fringe is smaller than the irradiation wavelength and the direction is parallel to the polarization direction. Snapshot observation revealed that the fringe pattern manifests itself via a complex but coherent process, which is attributed to crystallization properties unique to a nonthermally amorphized phase and the distinct optical contrast between crystalline and amorphous phases.

  5. Dehydration-induced amorphous phases of calcium carbonate.

    PubMed

    Saharay, Moumita; Yazaydin, A Ozgur; Kirkpatrick, R James

    2013-03-28

    Amorphous calcium carbonate (ACC) is a critical transient phase in the inorganic precipitation of CaCO3 and in biomineralization. The calcium carbonate crystallization pathway is thought to involve dehydration of more hydrated ACC to less hydrated ACC followed by the formation of anhydrous ACC. We present here computational studies of the transition of a hydrated ACC with a H2O/CaCO3 ratio of 1.0 to anhydrous ACC. During dehydration, ACC undergoes reorganization to a more ordered structure with a significant increase in density. The computed density of anhydrous ACC is similar to that of calcite, the stable crystalline phase. Compared to the crystalline CaCO3 phases, calcite, vaterite, and aragonite, the computed local structure of anhydrous ACC is most-similar to those of calcite and vaterite, but the overall structure is not well described by either. The strong hydrogen bond interaction between the carbonate ions and water molecules plays a crucial role in stabilizing the less hydrated ACC compositions compared to the more hydrated ones, leading to a progressively increasing hydration energy with decreasing water content.

  6. 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.

  7. Bandgap and Carrier Transport Engineering of Quantum Confined Mixed Phase Nanocrystalline/Amorphous Silicon

    SciTech Connect

    Guan, Tianyuan; Klafehn, Grant; Kendrick, Chito; Theingi, San; Airuoyo, Idemudia; Lusk, Mark T.; Stradins, Paul; Taylor, Craig; Collins, Reuben T.

    2016-11-21

    Mixed phase nanocrystalline/amorphous-silicon (nc/a-Si:H) thin films with band-gap higher than bulk silicon are prepared by depositing silicon nanoparticles (SiNPs), prepared in a separate deposition zone, and hydrogenated amorphous silicon (a-Si:H), simultaneously. Since the two deposition phases are well decoupled, optimized parameters for each component can apply to the growth process. Photoluminescence spectroscopy (PL) shows that the embedded SiNPs are small enough to exhibit quantum confinement effects. The low temperature PL measurements on the mixed phase reveal a dominant emission feature, which is associated with SiNPs surrounded by a-Si:H. In addition, we compare time dependent low temperature PL measurements for both a-Si:H and mixed phase material under intensive laser exposure for various times up to two hours. The PL intensity of a-Si:H with embedded SiNPs degrades much less than that of pure a-Si:H. We propose this improvement of photostability occurs because carriers generated in the a-Si:H matrix quickly transfer into SiNPs and recombine there instead of recombining in a-Si:H and creating defect states (Staebler-Wronski Effect).

  8. 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.

  9. 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.

  10. Fundamental Mechanisms Driving the Amorphous to Crystalline Phase Transformation

    SciTech Connect

    Reed, B W; Browning, N D; Santala, M K; LaGrange, T; Gilmer, G H; Masiel, D J; Campbell, G H; Raoux, S; Topuria, T; Meister, S; Cui, Y

    2011-01-04

    Phase transformations are ubiquitous, fundamental phenomena that lie at the heart of many structural, optical and electronic properties in condensed matter physics and materials science. Many transformations, especially those occurring under extreme conditions such as rapid changes in the thermodynamic state, are controlled by poorly understood processes involving the nucleation and quenching of metastable phases. Typically these processes occur on time and length scales invisible to most experimental techniques ({micro}s and faster, nm and smaller), so our understanding of the dynamics tends to be very limited and indirect, often relying on simulations combined with experimental study of the ''time infinity'' end state. Experimental techniques that can directly probe phase transformations on their proper time and length scales are therefore key to providing fundamental insights into the whole area of transformation physics and materials science. LLNL possesses a unique dynamic transmission electron microscope (DTEM) capable of taking images and diffraction patterns of laser-driven material processes with resolution measured in nanometers and nanoseconds. The DTEM has previously used time-resolved diffraction patterns to quantitatively study phase transformations that are orders of magnitude too fast for conventional in situ TEM. More recently the microscope has demonstrated the ability to directly image a reaction front moving at {approx}13 nm/ns and the nucleation of a new phase behind that front. Certain compound semiconductor phase change materials, such as Ge{sub 2}Sb{sub 2}Te{sub 5} (GST), Sb{sub 2}Te and GeSb, exhibit a technologically important series of transformations on scales that fall neatly into the performance specifications of the DTEM. If a small portion of such material is heated above its melting point and then rapidly cooled, it quenches into an amorphous state. Heating again with a less intense pulse leads to recrystallization into a vacancy

  11. 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.

  12. Crystalline Phase Separation in Phosphate Containing Waste Glasses: Relevance to INEEL HAW

    SciTech Connect

    Jantzen, C.M.

    2000-09-21

    As part of the Tanks Focus Area's (TFA) effort to increase waste loading for high-level waste vitrification at various facilities in the Department of Energy (DOE) complex, the occurrence of phase separation in waste glasses spanning the Savannah River Site (SRS) and Idaho National Engineering and Environmental Laboratory (INEEL) composition ranges have been studied. The type of phase separation that occurs in the phosphate rich borosilicate waste glasses, such as those investigated for INEEL, crystallizes upon cooling. This type of phase separation mechanism is less well studied than amorphous phase separation in phosphate poor borosilicate waste glasses. Therefore, the type of phase separation, extent, and impact of phase separation on glass durability for a series of INEEL-type glasses were examined and the data statistically analyzed in this study.

  13. 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 .

  14. 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.

  15. Addressing the amorphous content issue in quantitative phase analysis

    NASA Astrophysics Data System (ADS)

    Cline, J. P.; Dreele, R. B. Von; Winburn, R.; Stephens, P. W.; Filliben, J. J.

    2011-07-01

    A novel method is used to determine the amorphous content in the certification of NIST standard reference material (SRM) 676a (corundum). Extrapolation of diffraction measurements from mixtures with Si powders of varying surface-to-volume ratio show that approximately 1% by weight of SRM 676a is amorphous.

  16. Selective Separation of Fe-Concentrates in EAF Slags Using Mechanical Dissimilarity of Solid Phases

    NASA Astrophysics Data System (ADS)

    Jung, Sung Suk; Jung, Keeyoung; Sohn, Il

    2017-02-01

    We sought to develop an optimized particle size-dependent separation method to lower the Fe content of pulverized glass-ceramic electric arc furnace (EAF) slag for its improved reclamation as construction materials by considering the structures and the mechanical behavior of the discrete solid phases. After an isothermal crystallization process to enhance the spinel growth, the Vickers hardness and fracture toughness were measured on the spinel and amorphous phases separately from the solidified slag using indentation methods. The characteristic differences in the hardness of the phases were magnified when this glass-ceramic composite was isothermally crystallized. The hardness of the spinel was observed to be lower in slags with higher FetO/Al2O3 mass ratios due to the triclinic unit cell expansion of the spinel, whereas the hardness of the amorphous phase decreased with increasing isothermal period because of the structural transformation into a silicate-dominant network. Fracture toughness could be calculated based on the hardness and crack length, where the Young's modulus was determined using nanoindentation. The amorphous phase with a lower Fe content and lower fracture toughness resulted in finer powder distribution after pulverization, allowing better separation of the primary crystalline spinel containing higher Fe content from the Fe-deficient amorphous phase according to the particle size.

  17. Glass-liquid phase separation in highly supersaturated aqueous solutions of telaprevir.

    PubMed

    Mosquera-Giraldo, Laura I; Taylor, Lynne S

    2015-02-02

    Amorphous solid dispersions are of great current interest because they can improve the delivery of poorly water-soluble compounds. It has been recently noted that the highly supersaturated solutions generated by dissolution of some ASDs can undergo a phase transition to a colloidal, disordered, drug-rich phase when the concentration exceeds the "amorphous solubility" of the drug. The purpose of this study was to investigate the phase behavior of supersaturated solutions of telaprevir, which is formulated as an amorphous solid dispersion in the commercial product. Different analytical techniques including proton nuclear magnetic resonance spectroscopy (NMR), ultraviolet spectroscopy (UV), fluorescence spectroscopy and flux measurements were used to evaluate the properties of aqueous supersaturated solutions of telaprevir. It was found that highly supersaturated solutions of telaprevir underwent glass-liquid phase separation (GLPS) when the concentration exceeded 90 μg/mL, forming a water-saturated colloidal, amorphous drug-rich phase with a glass transition temperature of 52 °C. From flux measurements, it was observed that the "free" drug concentration reached a maximum at the concentration where GLPS occurred, and did not increase further as the concentration was increased. This phase behavior, which results in a precipitate and a metastable equilibrium between a supersaturated solution and a drug-rich phase, is obviously important in the context of evaluating amorphous solid dispersion formulations and their crystallization routes.

  18. Phase separations in a copolymer copolymer mixture

    NASA Astrophysics Data System (ADS)

    Zhang, Jin-Jun; Jin, Guojun; Ma, Yuqiang

    2006-01-01

    We propose a three-order-parameter model to study the phase separations in a diblock copolymer-diblock copolymer mixture. The cell dynamical simulations provide rich information about the phase evolution and structural formation, especially the appearance of onion-rings. The parametric dependence and physical reason for the domain growth of onion-rings are discussed.

  19. Crystalline-to-amorphous phase transition in irradiated silicon

    SciTech Connect

    Seidman, D.N.; Averback, R.S.; Okamoto, P.R.; Baily, A.C.

    1986-01-01

    The amorphous(a)-to-crystalline (c) phase transition has been studied in electron(e ) and/or ion irradiated silicon (Si). The irradiations were performed in situ in the Argonne High Voltage Microscope-Tandem Facility. The irradiation of Si, at <10K, with 1-MeV e to a fluence of 14 dpa failed to induce the c-to-a transition. Whereas an irradiation, at <10K, with 1.0 or 1.5-MeV Kr+ ions induced the c-to-a transition by a fluence of approx.0.37 dpa. Alternatively a dual irradiation, at 10K, with 1.0-MeV e and 1.0 or 1.5-MeV Kr+ to a Kr+ fluence of 1.5 dpa - where the ratio of the displacement rates for e to ions was approx.0.5 - resulted in the Si specimen retaining a degree of crystallinity. These results are discussed in terms of the degree of dispersion of point defects in the primary state of damage and the mobilities of point defects.

  20. Nature of phase transitions in crystalline and amorphous GeTe-Sb2Te3 phase change materials.

    PubMed

    Kalkan, B; Sen, S; Clark, S M

    2011-09-28

    The thermodynamic nature of phase stabilities and transformations are investigated in crystalline and amorphous Ge(1)Sb(2)Te(4) (GST124) phase change materials as a function of pressure and temperature using high-resolution synchrotron x-ray diffraction in a diamond anvil cell. The phase transformation sequences upon compression, for cubic and hexagonal GST124 phases are found to be: cubic → amorphous → orthorhombic → bcc and hexagonal → orthorhombic → bcc. The Clapeyron slopes for melting of the hexagonal and bcc phases are negative and positive, respectively, resulting in a pressure dependent minimum in the liquidus. When taken together, the phase equilibria relations are consistent with the presence of polyamorphism in this system with the as-deposited amorphous GST phase being the low entropy low-density amorphous phase and the laser melt-quenched and high-pressure amorphized GST being the high entropy high-density amorphous phase. The metastable phase boundary between these two polyamorphic phases is expected to have a negative Clapeyron slope. © 2011 American Institute of Physics

  1. First principles prediction of amorphous phases using evolutionary algorithms.

    PubMed

    Nahas, Suhas; Gaur, Anshu; Bhowmick, Somnath

    2016-07-07

    We discuss the efficacy of evolutionary method for the purpose of structural analysis of amorphous solids. At present, ab initio molecular dynamics (MD) based melt-quench technique is used and this deterministic approach has proven to be successful to study amorphous materials. We show that a stochastic approach motivated by Darwinian evolution can also be used to simulate amorphous structures. Applying this method, in conjunction with density functional theory based electronic, ionic and cell relaxation, we re-investigate two well known amorphous semiconductors, namely silicon and indium gallium zinc oxide. We find that characteristic structural parameters like average bond length and bond angle are within ∼2% of those reported by ab initio MD calculations and experimental studies.

  2. First principles prediction of amorphous phases using evolutionary algorithms

    NASA Astrophysics Data System (ADS)

    Nahas, Suhas; Gaur, Anshu; Bhowmick, Somnath

    2016-07-01

    We discuss the efficacy of evolutionary method for the purpose of structural analysis of amorphous solids. At present, ab initio molecular dynamics (MD) based melt-quench technique is used and this deterministic approach has proven to be successful to study amorphous materials. We show that a stochastic approach motivated by Darwinian evolution can also be used to simulate amorphous structures. Applying this method, in conjunction with density functional theory based electronic, ionic and cell relaxation, we re-investigate two well known amorphous semiconductors, namely silicon and indium gallium zinc oxide. We find that characteristic structural parameters like average bond length and bond angle are within ˜2% of those reported by ab initio MD calculations and experimental studies.

  3. Charge regularization in phase separating polyelectrolyte solutions.

    PubMed

    Muthukumar, M; Hua, Jing; Kundagrami, Arindam

    2010-02-28

    Theoretical investigations of phase separation in polyelectrolyte solutions have so far assumed that the effective charge of the polyelectrolyte chains is fixed. The ability of the polyelectrolyte chains to self-regulate their effective charge due to the self-consistent coupling between ionization equilibrium and polymer conformations, depending on the dielectric constant, temperature, and polymer concentration, affects the critical phenomena and phase transitions drastically. By considering salt-free polyelectrolyte solutions, we show that the daughter phases have different polymer charges from that of the mother phase. The critical point is also altered significantly by the charge self-regularization of the polymer chains. This work extends the progress made so far in the theory of phase separation of strong polyelectrolyte solutions to a higher level of understanding by considering chains which can self-regulate their charge.

  4. Charge regularization in phase separating polyelectrolyte solutions

    PubMed Central

    Muthukumar, M.; Hua, Jing; Kundagrami, Arindam

    2010-01-01

    Theoretical investigations of phase separation in polyelectrolyte solutions have so far assumed that the effective charge of the polyelectrolyte chains is fixed. The ability of the polyelectrolyte chains to self-regulate their effective charge due to the self-consistent coupling between ionization equilibrium and polymer conformations, depending on the dielectric constant, temperature, and polymer concentration, affects the critical phenomena and phase transitions drastically. By considering salt-free polyelectrolyte solutions, we show that the daughter phases have different polymer charges from that of the mother phase. The critical point is also altered significantly by the charge self-regularization of the polymer chains. This work extends the progress made so far in the theory of phase separation of strong polyelectrolyte solutions to a higher level of understanding by considering chains which can self-regulate their charge. PMID:20192314

  5. Simulation of pressure-induced phase transition in liquid and amorphous Al2 O3

    NASA Astrophysics Data System (ADS)

    Hoang, Vo Van; Oh, Suhk Kun

    2005-08-01

    We investigated the pressure-induced structural transformation in liquid and amorphous Al2O3 by the molecular dynamics (MD) method. Simulations were done in the basic cube under periodic boundary conditions containing 3000 ions with Born-Mayer type pair potentials. The structure of the amorphous Al2O3 model with real density at ambient pressure is in good agreement with Lamparter’s experiment. In order to study the amorphous-amorphous phase transition, 23 models of amorphous alumina at the temperature of 350K and at densities ranging from 2.83to5.0gcm-3 had been built. The microstructure of the Al2O3 systems had been analyzed through pair radial distribution functions, coordination number distributions, interatomic distances, and bond-angle distributions. Here we found clear evidence of a structural transition in amorphous alumina from a tetrahedral to an octahedral network upon compression. According to our results, this transformation occurred at densities ranging from 3.6to4.05gcm-3 . We also presented the amorphous-amorphous phase transition from an octahedral to a tetrahedral network structure upon decompression at densities ranging from 5.00to2.83gcm-3 . Also, the same study was carried out for the liquid state of the system at the temperature of 3500K , and the liquid-liquid phase transition had been discussed.

  6. Maxwell rigidity and topological constraints in amorphous phase-change networks

    SciTech Connect

    Micoulaut, M.; Otjacques, C.; Raty, J.-Y.; Bichara, C.

    2011-12-12

    By analyzing first-principles molecular-dynamics simulations of different telluride amorphous networks, we develop a method for the enumeration of radial and angular topological constraints, and show that the phase diagram of the most popular system Ge-Sb-Te can be split into two compositional elastic phases: a tellurium rich flexible phase and a stressed rigid phase that contains most of the materials used in phase-change applications. This sound atomic scale insight should open new avenues for the understanding of phase-change materials and other complex amorphous materials from the viewpoint of rigidity.

  7. Frustrated phase separation and high temperature superconductivity

    SciTech Connect

    Emery, V.J. ); Kivelson, S.A. . Dept. of Physics)

    1992-01-01

    A dilute system of neutral holes in an antiferromagnet separates into a hole-rich and a hole-poor phase. The phase separation is frustrated by long-range Coulomb interactions but, provided the dielectric constant is sufficiently large, there remain large-amplitude low-energy fluctuations in the hole density at intermediate length scales. The extensive experimental evidence showing that this behavior giver, a reasonable picture of high temperature superconductors is surveyed. Further, it is shown that the scattering of mobile holes from the local density fluctuations may account for the anomalous normal-state properties of high temperature superconductors and also provide the mechanism of pairing.

  8. Frustrated phase separation and high temperature superconductivity

    SciTech Connect

    Emery, V.J.; Kivelson, S.A.

    1992-09-01

    A dilute system of neutral holes in an antiferromagnet separates into a hole-rich and a hole-poor phase. The phase separation is frustrated by long-range Coulomb interactions but, provided the dielectric constant is sufficiently large, there remain large-amplitude low-energy fluctuations in the hole density at intermediate length scales. The extensive experimental evidence showing that this behavior giver, a reasonable picture of high temperature superconductors is surveyed. Further, it is shown that the scattering of mobile holes from the local density fluctuations may account for the anomalous normal-state properties of high temperature superconductors and also provide the mechanism of pairing.

  9. THE IMPACT OF PARTIAL CRYSTALLIZATION ON THE PERMEATION PROPERTIES BULK AMORPHOUS GLASS HYDROGEN SEPARATION MEMBRANES

    SciTech Connect

    Brinkman, K; Paul Korinko, P; Thad Adams, T; Elise Fox, E; Arthur Jurgensen, A

    2008-11-25

    It is recognized that hydrogen separation membranes are a key component of the emerging hydrogen economy. A potentially exciting material for membrane separations are bulk metallic glass materials due to their low cost, high elastic toughness and resistance to hydrogen 'embrittlement' as compared to crystalline Pd-based membrane systems. However, at elevated temperatures and extended operation times structural changes including partial crystallinity may appear in these amorphous metallic systems. A systematic evaluation of the impact of partial crystallinity/devitrification on the diffusion and solubility behavior in multi-component Metallic Glass materials would provide great insight into the potential of these materials for hydrogen applications. This study will report on the development of time and temperature crystallization mapping and their use for interpretation of 'in-situ' hydrogen permeation at elevated temperatures.

  10. Polymerization and phase separation studies in liquids

    NASA Astrophysics Data System (ADS)

    Venkateshan, Karthik

    In technology, a thermosetting polymer's electrical, thermal and mechanical properties are modified by incorporating an elastomer phase in its matrix. This is achieved by phase separation of the dissolved elastomer during the course of polymerization until the liquid vitrifies. The phase separation mechanism and nature of interface formed determine the negative effect of phase separation on polymerization and the transition of mass-controlled kinetics to diffusion-controlled kinetics. This thesis provides an experimental study of polymerization, phase separation and vitrification processes by using real time measurements of dielectric relaxation, calorimetric changes, elastic constants and thermal conductivity of diepoxide-amine mixtures with and without the phase separating amine-terminated butadiene acrylonitrile elastomer. The results are discussed in general terms of mutual slowing of molecular diffusion and polymerization, and of the development of diffused interfaces between regions of elastomer and polymer matrix, that form as a result of, (i) high degree of spatial heterogeneity in the intermingled regions of non-stoichiometric amounts of polymer and elastomer, (ii) high degree of compatibility between the elastomer and polymer matrix and (iii) large size of the elastomer and polymer molecules. The consequence of molecular diffusional constraints and manifestation of spatial heterogeneity is confirmed by the appearance of Johari-Goldstein relaxation which acts as the precursor for the significantly broadened alpha-relaxation and higher values of dielectric permittivity in the frequency range of 1 kHz and greater. Spatial heterogeneity in the intermingled regions of non-stoichiometric amounts of polymer and elastomer is also confirmed by calorimetry studies. With increasing diffusional limitation, the total heat of polymerization varies from values obtained for stoichiometric amounts of reactants with no change in calorimetric peak temperature. Furthermore

  11. Vapor-liquid phase separator permeability results

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

    Continued studies are described in the area of vapor-liquid phase separator work with emphasis on permeabilities of porous sintered plugs (stainless steel, nominal pore size 2 micrometer). The temperature dependence of the permeability has been evaluated in classical fluid using He-4 gas at atmospheric pressure and in He-2 on the basis of a modified, thermosmotic permeability of the normal fluid.

  12. Rate-Dependent Behavior of the Amorphous Phase of Spider Dragline Silk

    PubMed Central

    Patil, Sandeep P.; Markert, Bernd; Gräter, Frauke

    2014-01-01

    The time-dependent stress-strain behavior of spider dragline silk was already observed decades ago, and has been attributed to the disordered sequences in silk proteins, which compose the soft amorphous matrix. However, the actual molecular origin and magnitude of internal friction within the amorphous matrix has remained inaccessible, because experimentally decomposing the mechanical response of the amorphous matrix from the embedded crystalline units is challenging. Here, we used atomistic molecular dynamics simulations to obtain friction forces for the relative sliding of peptide chains of Araneus diadematus spider silk within bundles of these chains as a representative unit of the amorphous matrix in silk fibers. We computed the friction coefficient and coefficient of viscosity of the amorphous phase to be in the order of 10−6 Ns/m and 104 Ns/m2, respectively, by extrapolating our simulation data to the viscous limit. Finally, we used a finite element method for the amorphous phase, solely based on parameters derived from molecular dynamics simulations including the newly determined coefficient of viscosity. With this model the time scales of stress relaxation, creep, and hysteresis were assessed, and found to be in line with the macroscopic time-dependent response of silk fibers. Our results suggest the amorphous phase to be the primary source of viscosity in silk and open up the avenue for finite element method studies of silk fiber mechanics including viscous effects. PMID:24896131

  13. Nature of metastable amorphous-to-crystalline reversible phase transformations in GaSb

    SciTech Connect

    Kalkan, B.; Edwards, T. G.; Sen, S.; Raoux, S.

    2013-08-28

    The structural, thermodynamic, and kinetic aspects of the transformations between the metastable amorphous and crystalline phases of GaSb are investigated as a function of pressure at ambient temperature using synchrotron x-ray diffraction experiments in a diamond anvil cell. The results are consistent with the hypothesis that the pressure induced crystallization of amorphous GaSb into the β-Sn crystal structure near ∼5 GPa is possibly a manifestation of an underlying polyamorphic phase transition between a semiconducting, low density and a metallic, high density amorphous (LDA and HDA, respectively) phases. In this scenario, the large differences in the thermal crystallization kinetics between amorphous GaSb deposited in thin film form by sputtering and that prepared by laser melt quenching may be related to the relative location of the glass transition temperature of the latter in the pressure-temperature (P-T) space with respect to the location of the critical point that terminate the LDA ↔ HDA transition. The amorphous →β-Sn phase transition is found to be hysteretically reversible as the β-Sn phase undergoes decompressive amorphization near ∼2 GPa due to the lattice instabilities that give rise to density fluctuations in the crystal upon decompression.

  14. Addressing the amorphous content issue in quantitative phase analysis : the certification of NIST SRM 676a.

    SciTech Connect

    Cline, J. P.; Von Dreele, R. B.; Winburn, R.; Stephens, P. W.; Filliben, J. J.

    2011-07-01

    A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Under the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.

  15. Phase transformation during mechano-synthesis of nanocrystalline/amorphous Fe–32Mn–6Si alloys

    SciTech Connect

    Amini, Rasool; Shamsipoor, Ali; Ghaffari, Mohammad; Alizadeh, Morteza; Okyay, Ali Kemal

    2013-10-15

    Mechano-synthesis of Fe–32Mn–6Si alloy by mechanical alloying of the elemental powder mixtures was evaluated by running the ball milling process under an inert argon gas atmosphere. In order to characterize the as-milled powders, powder sampling was performed at predetermined intervals from 0.5 to 192 h. X-ray florescence analyzer, X-ray diffraction, scanning electron microscope, and high resolution transmission electron microscope were utilized to investigate the chemical composition, structural evolution, morphological changes, and microstructure of the as-milled powders, respectively. According to the results, the nanocrystalline Fe–Mn–Si alloys were completely synthesized after 48 h of milling. Moreover, the formation of a considerable amount of amorphous phase during the milling process was indicated by quantitative X-ray diffraction analysis as well as high resolution transmission electron microscopy image and its selected area diffraction pattern. It was found that the α-to-γ and subsequently the amorphous-to-crystalline (especially martensite) phase transformation occurred by milling development. - Graphical abstract: Mechano-synthesis of nanocrystalline/amorphous Fe–32Mn–6Si shape memory alloys in the powder form: amorphous phase formation, α-to-γ phase transformation, mechano-crystallization of the amorphous, and martensite phase formation during the process. Highlights: • During MA, the α-to-γ phase transformation and amorphization occurred. • Mechano-crystallization of the amorphous phase occurred at sufficient milling time. • The formation of high amount of ε-martensite was evidenced at high milling times. • The platelet, spherical, and then irregular particle shapes was extended by MA. • By MA, the particles size was increased, then reduced, and afterward re-increased.

  16. Does dynamic vulcanization induce phase separation?

    PubMed

    Abolhasani, Mohammad Mahdi; Zarejousheghani, Fatemeh; Naebe, Minoo; Guo, Qipeng

    2014-08-14

    Immiscible and miscible blends of poly(vinylidene fluoride) (PVDF) and acrylic rubber (ACM) were subjected to dynamic vulcanization to investigate the effect of crosslinking on phase separation. As a result of different processability, mixing torque behavior of miscible and immiscible blends was significantly different from one another. Scanning electron microscopy (SEM) was used to investigate the morphology of the system. After dynamic vulcanization, submicron ACM droplets were observed in the samples near the binodal curve of the system under mixing conditions. Small angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) analysis were used to investigate the effect of dynamic vulcanization on the lamellar structure of the system. It was shown that for samples near the boundary of phase separation, increasing the crosslink density led to a decrease in the lamellar long period (L) as a sign of increment of crosslink density induced phase decomposition. Effects of shear rate on the final morphology of the system were investigated by changing the mixing temperature and by comparing the results of dynamic vulcanization at one phase and two phase regions.

  17. Plastic Deformation, Amorphization, and Phase Changes in Extreme Laser Shock Compression of Ta and Si

    NASA Astrophysics Data System (ADS)

    Meyers, Marc

    2015-06-01

    High-amplitude pulsed lasers probe the response of materials at pressures up to 100s of GPa and strain rates of 108 s-1, revealing plastic deformation, phase transformations, and amorphization. Molecular dynamics simulations provide modeling at comparable strain rates and time durations. Shock compression of monocrystalline Ta reveals dislocations at low pressures and twinning at higher pressures (above 24 GPa). Results are compared with predictions from homogeneous dislocation generation and multiplication and the latter mechanism is dominant. The formation of an Omega phase was observed in monocrystalline tantalum at a shock amplitude of approximately 70 GPa. The shear stresses may play a role in the transformation. As shock energy increases, the following structural changes in monocrystalline Si are observed: dislocations and stacking faults; bands of amorphized Si forming on crystallographic orientations consistent with slip; broad regions of amorphized Si; nanocrystalline Si resulting from re-crystallization. MD simulations display similar amorphous regions. Funding: UCOP and DOE SSAP.

  18. Thermocapillary-Induced Phase Separation with Coalescence

    NASA Technical Reports Server (NTRS)

    Davis, Robert H.

    2003-01-01

    Research has been undertaken on interactions of two or more deformable drops (or bubbles) in a viscous fluid and subject to a temperature, gravitational, or flow field. An asymptotic theory for nearly spherical drops shows that small deformations reduce the coalescence and phase separation rates. Boundary-integral simulations for large deformations show that bubbles experience alignment and enhanced coalescence, whereas more viscous drops may break as a result of hydrodynamic interactions. Experiments for buoyancy motion confirm these observations. Simulations of the sedimentation of many drops show clustering phenomena due to deformations, which lead to enhanced phase separation rates, and simulations of sheared emulsions show that deformations cause a reduction in the effective viscosity.

  19. Simualting the Phase Separated rp-ash

    NASA Astrophysics Data System (ADS)

    Caplan, Matthew; Horowitz, Chuck; Berry, Donald

    2017-01-01

    The composition and phase separation of rp-ash on accreting neutron stars determine the thermal properties of the crust which must be understood to interpret observations of crust cooling in X-ray bursts. In this work, we report on recent large scale molecular dynamics simulations of the outer crust. Using the crust compositions calculated by Mckinven et al. 2016, we study the structure of the crystal that forms, as well as diffusion and thermal properties of the crust.

  20. Phase separation kinetics in immiscible liquids

    NASA Technical Reports Server (NTRS)

    Ng, Lee H.; Sadoway, Donald R.

    1987-01-01

    The kinetics of phase separation in the succinonitrile-water system are being investigated. Experiments involve initial physical mixing of the two immiscible liquids at a temperature above the consolute, decreasing the temperature into the miscibility gap, followed by iamging of the resultant microstructure as it evolves with time. Refractive index differences allow documentation of the changing microstructures by noninvasive optical techniques without the need to quench the liquid structures for analysis.

  1. Phase separation kinetics in immiscible liquids

    NASA Technical Reports Server (NTRS)

    Sadoway, D. R.

    1986-01-01

    The kinetics of phase separation in the succinonitrile-water system are being investigated. Experiments involve initial physical mixing of the two immiscible liquids at a temperature above the consolute, decreasing the temperature into the miscibility gap, followed by imaging of the resultant microstructure as it evolves with time. Refractive index differences allow documentation of the changing microstructures by noninvasive optical techniques without the need to quench the liquid structures for analysis.

  2. Multivariate Quantification of the Solid State Phase Composition of Co-Amorphous Naproxen-Indomethacin.

    PubMed

    Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian; Rades, Thomas; Leopold, Claudia S

    2015-10-27

    To benefit from the optimized dissolution properties of active pharmaceutical ingredients in their amorphous forms, co-amorphisation as a viable tool to stabilize these amorphous phases is of both academic and industrial interest. Reports dealing with the physical stability and recrystallization behavior of co-amorphous systems are however limited to qualitative evaluations based on the corresponding X-ray powder diffractograms. Therefore, the objective of the study was to develop a quantification model based on X-ray powder diffractometry (XRPD), followed by a multivariate partial least squares regression approach that enables the simultaneous determination of up to four solid state fractions: crystalline naproxen, γ-indomethacin, α-indomethacin as well as co-amorphous naproxen-indomethacin. For this purpose, a calibration set that covers the whole range of possible combinations of the four components was prepared and analyzed by XRPD. In order to test the model performances, leave-one-out cross validation was performed and revealed root mean square errors of validation between 3.11% and 3.45% for the crystalline molar fractions and 5.57% for the co-amorphous molar fraction. In summary, even four solid state phases, involving one co-amorphous phase, can be quantified with this XRPD data-based approach.

  3. Influence of Neutralization on Amorphous-Phase Properties in Semicrystalline Ionomers

    NASA Astrophysics Data System (ADS)

    Wakabayashi, Katsuyuki

    2005-03-01

    Ethylene-methacrylic acid (E-MAA) ionomers contain lamellar polyethylene crystallites, amorphous copolymer segments and ionic aggregates, each of which affects the mechanical properties of the material. For a quantitative assessment of the contributions from each of the three structural motifs, we measured the ionomer modulus at 70 ^oC, where the materials still contain substantial crystallinity, and applied a two-phase composite treatment (Davies Model) to extract the modulus of the amorphous phase. The amorphous phase modulus at 70 ^oC increases with neutralization level as a consequence of physical crosslinking by the ionic aggregates; amorphous phase moduli for ionomers with varying comonomer content and neutralization levels approximately collapsed when plotted against the number density of ionic groups, with the modulus increasing with ion content in general agreement with simple rubber elasticity theory. Between 25 and 70 ^oC, the relaxation behavior of ionomers differs substantially from that for unneutralized E-MAA copolymers. The ionomers exhibit two-step drops in the storage modulus prior to primary crystal melting, which we attribute to melting of secondary crystallites and devitrification of the amorphous phase, whose glass transition is elevated by neutralization.

  4. Electron Irradiation Induced Phase Transition of an Amorphous Phase and Face-Centered Cubic Solid Solutions in Zr66.7Pd33.3 Metallic Glass

    NASA Astrophysics Data System (ADS)

    Nagase, Takeshi; Hosokawa, Takashi; Umakoshi, Yukichi

    2007-02-01

    Both amorphization and crystallization were observed in Zr66.7Pd33.3 metallic glass under electron irradiation. The melt-spun amorphous phase was not stable under 2.0 MV electron irradiation and two kinds of fcc-solid solution were precipitated through electron irradiation induced crystallization at 103 and 298 K. The fcc-solid solution obtained by electron irradiation induced crystallization at 298 K transformed to an amorphous phase during irradiation at 103 K. Electron irradiation induced phase transformation behavior in Zr66.7Pd33.3 metallic glass can be explained by phase stability of an amorphous phase and crystalline phases against electron irradiation.

  5. Wetting and phase separation in soft adhesion

    PubMed Central

    Jensen, Katharine E.; Sarfati, Raphael; Style, Robert W.; Boltyanskiy, Rostislav; Chakrabarti, Aditi; Chaudhury, Manoj K.; Dufresne, Eric R.

    2015-01-01

    In the classic theory of solid adhesion, surface energy drives deformation to increase contact area whereas bulk elasticity opposes it. Recently, solid surface stress has been shown also to play an important role in opposing deformation of soft materials. This suggests that the contact line in soft adhesion should mimic that of a liquid droplet, with a contact angle determined by surface tensions. Consistent with this hypothesis, we observe a contact angle of a soft silicone substrate on rigid silica spheres that depends on the surface functionalization but not the sphere size. However, to satisfy this wetting condition without a divergent elastic stress, the gel phase separates from its solvent near the contact line. This creates a four-phase contact zone with two additional contact lines hidden below the surface of the substrate. Whereas the geometries of these contact lines are independent of the size of the sphere, the volume of the phase-separated region is not, but rather depends on the indentation volume. These results indicate that theories of adhesion of soft gels need to account for both the compressibility of the gel network and a nonzero surface stress between the gel and its solvent. PMID:26553989

  6. Wetting and phase separation in soft adhesion.

    PubMed

    Jensen, Katharine E; Sarfati, Raphael; Style, Robert W; Boltyanskiy, Rostislav; Chakrabarti, Aditi; Chaudhury, Manoj K; Dufresne, Eric R

    2015-11-24

    In the classic theory of solid adhesion, surface energy drives deformation to increase contact area whereas bulk elasticity opposes it. Recently, solid surface stress has been shown also to play an important role in opposing deformation of soft materials. This suggests that the contact line in soft adhesion should mimic that of a liquid droplet, with a contact angle determined by surface tensions. Consistent with this hypothesis, we observe a contact angle of a soft silicone substrate on rigid silica spheres that depends on the surface functionalization but not the sphere size. However, to satisfy this wetting condition without a divergent elastic stress, the gel phase separates from its solvent near the contact line. This creates a four-phase contact zone with two additional contact lines hidden below the surface of the substrate. Whereas the geometries of these contact lines are independent of the size of the sphere, the volume of the phase-separated region is not, but rather depends on the indentation volume. These results indicate that theories of adhesion of soft gels need to account for both the compressibility of the gel network and a nonzero surface stress between the gel and its solvent.

  7. Amorphous Phase Formation Analysis of Rapidly Solidified CoCr Droplets

    NASA Astrophysics Data System (ADS)

    Bogno, Abdoul-Aziz; Riveros, Carlos; Henein, Hani; Li, Delin

    2016-12-01

    This paper investigates amorphous phase formation and rapid solidification characteristics of a CoCr alloy. High cooling rate and high undercooling-induced rapid solidification of the alloy was achieved by impulse atomization in helium atmosphere. Two atomization experiments were carried out to generate powders of a wide size range from liquid CoCr at two different temperatures. Amorphous fraction and kinetic crystallization properties of impulse atomized powders were systematically quantified by means of differential scanning calorimetry. In addition, different but complementary characterization tools were used to analyze the powders microstructures. The fraction of amorphous phase within the investigated powders is found to be promoted by high cooling rate or smaller powder size. The critical cooling rate for amorphous phase formation, which is influenced by the oxygen content in the melt, is found to be 3 × 104 K s-1 and corresponds to a 160- µm-diameter powder atomized in helium. Hardness of the powders is found to follow a trend that is described by the Hall-Petch relation when a relatively high fraction of crystalline structures is present and decreases with the fraction of amorphous phase.

  8. Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

    PubMed

    Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

    2014-11-26

    We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

  9. Ultrafast characterization of phase-change material crystallization properties in the melt-quenched amorphous phase.

    PubMed

    Jeyasingh, Rakesh; Fong, Scott W; Lee, Jaeho; Li, Zijian; Chang, Kuo-Wei; Mantegazza, Davide; Asheghi, Mehdi; Goodson, Kenneth E; Wong, H-S Philip

    2014-06-11

    Phase change materials are widely considered for application in nonvolatile memories because of their ability to achieve phase transformation in the nanosecond time scale. However, the knowledge of fast crystallization dynamics in these materials is limited because of the lack of fast and accurate temperature control methods. In this work, we have developed an experimental methodology that enables ultrafast characterization of phase-change dynamics on a more technologically relevant melt-quenched amorphous phase using practical device structures. We have extracted the crystallization growth velocity (U) in a functional capped phase change memory (PCM) device over 8 orders of magnitude (10(-10) < U < 10(-1) m/s) spanning a wide temperature range (415 < T < 580 K). We also observed direct evidence of non-Arrhenius crystallization behavior in programmed PCM devices at very high heating rates (>10(8) K/s), which reveals the extreme fragility of Ge2Sb2Te5 in its supercooled liquid phase. Furthermore, these crystallization properties were studied as a function of device programming cycles, and the results show degradation in the cell retention properties due to elemental segregation. The above experiments are enabled by the use of an on-chip fast heater and thermometer called as microthermal stage (MTS) integrated with a vertical phase change memory (PCM) cell. The temperature at the PCM layer can be controlled up to 600 K using MTS and with a thermal time constant of 800 ns, leading to heating rates ∼10(8) K/s that are close to the typical device operating conditions during PCM programming. The MTS allows us to independently control the electrical and thermal aspects of phase transformation (inseparable in a conventional PCM cell) and extract the temperature dependence of key material properties in real PCM devices.

  10. Phase separation in doped Mott insulators

    NASA Astrophysics Data System (ADS)

    Yee, Chuck-Hou; Balents, Leon

    2014-03-01

    Motivated by the commonplace observation of Mott insulators away from integer filling, we construct a simple thermodynamic argument for phase separation in first-order doping-driven Mott transitions. The theory predicts the transition is percolative and should exhibit Coulomb frustration. As an application, we consider the titanate family of perovskites, an ideal test case since both the doping and correlation strength can be tuned. We compute the critical dopings required to drive the Mott transition using first-principles methods combined with dynamical mean-field theory, finding good agreement with experiment.

  11. Active Nematics Are Intrinsically Phase Separated

    NASA Astrophysics Data System (ADS)

    Mishra, Shradha; Ramaswamy, Sriram

    2006-09-01

    Two-dimensional nonequilibrium nematic steady states, as found in agitated granular-rod monolayers or films of orientable amoeboid cells, were predicted [Europhys. Lett. 62, 196 (2003)EULEEJ0295-507510.1209/epl/i2003-00346-7] to have giant number fluctuations, with the standard deviation proportional to the mean. We show numerically that the steady state of such systems is macroscopically phase separated, yet dominated by fluctuations, as in the Das-Barma model [Phys. Rev. Lett. 85, 1602 (2000)PRLTAO0031-900710.1103/PhysRevLett.85.1602]. We suggest experimental tests of our findings in granular and living-cell systems.

  12. Borosilicate nanoparticles prepared by exothermic phase separation.

    PubMed

    Parashar, Virendra K; Orhan, Jean-Baptiste; Sayah, Abdeljalil; Cantoni, Marco; Gijs, Martin A M

    2008-10-01

    Nanoparticles play an important role in chemical and biological sciences due to their ability to bind and concentrate many molecules on their surface. Polymers and silica are widely used to make nanoparticles, but efforts to make nanoparticles from borosilicate glass--which exhibits high tolerance to chemicals and solvents, combined with excellent mechanical and thermal stability--have proved unsuccessful. Here we show that borosilicate nanoparticles (100-500 nm in size) can be synthesized by simply mixing a silicon-boron binary oxide solution, prepared using non-aqueous organic solvents, with water. This induces a vigorous exothermic phase separation in which borosilicate nanoparticles burst out of a silica phase. In addition to potential applications in the life sciences, monodisperse borosilicate particles could also have applications in the production of photonic bandgap devices with high optical contrast, contrast agents for ultrasonic microscopy or chemical filtration membranes.

  13. Crystallization and Phase Changes in Paracetamol from the Amorphous Solid to the Liquid Phase

    PubMed Central

    2014-01-01

    For the case of paracetamol, we show how terahertz time-domain spectroscopy can be used to characterize the solid and liquid phase dynamics. Heating of supercooled amorphous paracetamol from 295 K in a covered sample under vacuum leads to its crystallization at 330 K. First, form III is formed followed by the transformation of form III to form II at 375 K, to form I at 405 K, and finally melting is observed around 455 K. We discuss the difference between the featureless spectra of the supercooled liquid and its liquid melt. Lastly, we studied the onset of crystallization from the supercooled liquid in detail and quantified its kinetics based on the Avrami–Erofeev model. We determined an effective rate constant of k = 0.056 min–1 with a corresponding onset of crystallization at T = 329.5 K for a heating rate of 0.4 K min–1. PMID:24579729

  14. Crystal-amorphous transformation via defect-templating in phase-change materials

    NASA Astrophysics Data System (ADS)

    Nukala, Pavan

    Phase-change materials (PCM) such as GeTe and Ge-Sb-Te alloys are potential candidates for non-volatile memory applications, because they can reversibly and rapidly transform between a crystalline phase and an amorphous phase with medium-range order. Traditionally, crystal-amorphous transformation in these materials has been carried out via melt-quench pathway, where the crystalline phase is heated beyond its melting point by the rising edge of an electric pulse, and the melt phase is quenched by the falling edge into a glassy phase. Formation of an intermediate melt phase in this transformation pathway requires usage of large switching current densities, resulting in energy wastage, and device degradation issues. Furthermore, melt-quench pathway is a brute force strategy of amorphizing PCM, and does not utilize the peculiar structural properties in crystalline phase. It will be beneficial from a device perspective that crystal-amorphous transformation is carried out via subtler solid-state pathways. Single-crystalline nanowire phase-change memory, owing to its lateral geometry and large volumes of active material, offers a platform to construct a crystal-amorphous transformation pathway via gradually increasing disorder in the crystalline phase, and study it. Using in situ transmission electron microscopy on GeTe and Ge2Sb2Te5 systems, we showed that the application of an electric pulse (heat-shock) creates dislocations in the PCM that migrate with the hole-wind force, and interact with the already existing ferroelectric boundaries in case of GeTe, changing their nature. We adapted novel tools such as optical second harmonic generation polarimety to carefully study these defect interactions. These defects accumulate at a region of local inhomogeneity, and upon addition of defects beyond a critical limit to that region via electrical pulsing, an amorphous phase "nucleates". We also studied the effect of defect dynamics on carrier transport using temperature

  15. Study the formation of metastable crystalline phases from amorphous metallic systems with an integrated approach

    NASA Astrophysics Data System (ADS)

    Ye, Zhuo; Zhang, Feng; Sun, Yang; Mendelev, Mikhail; Ott, Ryan; Park, Eun-Soo; Besser, Matt; Kramer, Matt; Wang, Cai-Zhuang; Ho, Kai-Ming

    2015-03-01

    An efficient genetic algorithm (GA) is integrated with experimental diffraction data to solve a metastable Al20Sm4 phase that evolves during rapid solidification of an amorphous Al-10%Sm alloy produced by magnetron sputtering. The excellent match between calculated and experimental X-ray diffraction patterns confirms that this new phase appeared in the crystallization of the alloy. We discover the strong similarity of the underlying atomic structure between the amorphous alloy and this phase. Both phases share the same Sm-centered motif, providing a low-barrier pathway to form this Al20Sm4phase in the glass matrix at low temperatures. Molecular dynamic simulations of crystal growth from the liquid phase predict the formation of disordered anti-site defects in the devitrified crystal.

  16. Dental materials. Amorphous intergranular phases control the properties of rodent tooth enamel.

    PubMed

    Gordon, Lyle M; Cohen, Michael J; MacRenaris, Keith W; Pasteris, Jill D; Seda, Takele; Joester, Derk

    2015-02-13

    Dental enamel, a hierarchical material composed primarily of hydroxylapatite nanowires, is susceptible to degradation by plaque biofilm-derived acids. The solubility of enamel strongly depends on the presence of Mg(2+), F(-), and CO3(2-). However, determining the distribution of these minor ions is challenging. We show—using atom probe tomography, x-ray absorption spectroscopy, and correlative techniques—that in unpigmented rodent enamel, Mg(2+) is predominantly present at grain boundaries as an intergranular phase of Mg-substituted amorphous calcium phosphate (Mg-ACP). In the pigmented enamel, a mixture of ferrihydrite and amorphous iron-calcium phosphate replaces the more soluble Mg-ACP, rendering it both harder and more resistant to acid attack. These results demonstrate the presence of enduring amorphous phases with a dramatic influence on the physical and chemical properties of the mature mineralized tissue.

  17. Nanomechanical morphology of amorphous, transition, and crystalline domains in phase change memory thin films

    NASA Astrophysics Data System (ADS)

    Bosse, J. L.; Grishin, I.; Huey, B. D.; Kolosov, O. V.

    2014-09-01

    In the search for phase change materials (PCM) that may rival traditional random access memory, a complete understanding of the amorphous to crystalline phase transition is required. For the well-known Ge2Sb2Te5 (GST) and GeTe (GT) chalcogenides, which display nucleation and growth dominated crystallization kinetics, respectively, this work explores the nanomechanical morphology of amorphous and crystalline phases in 50 nm thin films. Subjecting these PCM specimens to a lateral thermal gradient spanning the crystallization temperature allows for a detailed morphological investigation. Surface and depth-dependent analyses of the resulting amorphous, transition and crystalline regions are achieved with shallow angle cross-sections, uniquely implemented with beam exit Ar ion polishing. To resolve the distinct phases, ultrasonic force microscopy (UFM) with simultaneous topography is implemented revealing a relative stiffness contrast between the amorphous and crystalline phases of 14% for the free film surface and 20% for the cross-sectioned surface. Nucleation is observed to occur preferentially at the PCM-substrate and free film interface for both GST and GT, while fine subsurface structures are found to be sputtering direction dependent. Combining surface and cross-section nanomechanical mapping in this manner allows 3D analysis of microstructure and defects with nanoscale lateral and depth resolution, applicable to a wide range of materials characterization studies where the detection of subtle variations in elastic modulus or stiffness are required.

  18. pH-Dependent Liquid-Liquid Phase Separation of Highly Supersaturated Solutions of Weakly Basic Drugs.

    PubMed

    Indulkar, Anura S; Box, Karl J; Taylor, Robert; Ruiz, Rebeca; Taylor, Lynne S

    2015-07-06

    Supersaturated solutions of poorly aqueous soluble drugs can be formed both in vivo and in vitro. For example, increases in pH during gastrointestinal transit can decrease the aqueous solubility of weakly basic drugs resulting in supersaturation, in particular when exiting the acidic stomach environment. Recently, it has been observed that highly supersaturated solutions of drugs with low aqueous solubility can undergo liquid-liquid phase separation (LLPS) prior to crystallization, forming a turbid solution such that the concentration of the drug in the continuous solution phase corresponds to the amorphous solubility while the colloidal phase is composed of a disordered drug-rich phase. Although it is well established that the equilibrium solubility of crystalline weakly basic drugs follows the Henderson-Hasselbalch relationship, the impact of pH on the LLPS phenomenon or the amorphous solubility has not been explored. In this work, the LLPS concentration of three weakly basic compounds-clotrimazole, nicardipine, and atazanavir-was determined as a function of pH using three different methods and was compared to the predicted amorphous solubility, which was calculated from the pH-dependent crystalline solubility and by estimating the free energy difference between the amorphous and crystalline forms. It was observed that, similar to crystalline solubility, the experimental amorphous solubility at any pH follows the Henderson-Hasselbalch relation and can be predicted if the amorphous solubility of the free base is known. Excellent agreement between the LLPS concentration and the predicted amorphous solubility was observed. Dissolution studies of amorphous drugs showed that the solution concentration can reach the corresponding LLPS concentration at that pH. Solid-state analysis of the precipitated material confirmed the amorphous nature. This work provides insight into the pH-dependent precipitation behavior of poorly water-soluble compounds and provides a

  19. Systematic comparison of crystalline and amorphous phases: Charting the landscape of water structures and transformations

    SciTech Connect

    Pietrucci, Fabio; Martoňák, Roman

    2015-03-14

    Systematically resolving different crystalline phases starting from the atomic positions, a mandatory step in algorithms for the prediction of structures or for the simulation of phase transitions, can be a non-trivial task. Extending to amorphous phases and liquids which lack the discrete symmetries, the problem becomes even more difficult, involving subtle topological differences at medium range that, however, are crucial to the physico-chemical and spectroscopic properties of the corresponding materials. Typically, system-tailored order parameters are devised, like global or local symmetry indicators, ring populations, etc. We show that a recently introduced metric provides a simple and general solution to this intricate problem. In particular, we demonstrate that a map can be traced displaying distances among water phases, including crystalline as well as amorphous states and the liquid, consistently with experimental knowledge in terms of phase diagram, structural features, and preparation routes.

  20. Dissolution of Danazol Amorphous Solid Dispersions: Supersaturation and Phase Behavior as a Function of Drug Loading and Polymer Type.

    PubMed

    Jackson, Matthew J; Kestur, Umesh S; Hussain, Munir A; Taylor, Lynne S

    2016-01-04

    Amorphous solid dispersions (ASDs) are of great interest as enabling formulations because of their ability to increase the bioavailability of poorly soluble drugs. However, the dissolution of these formulations under nonsink dissolution conditions results in highly supersaturated drug solutions that can undergo different types of phase transitions. The purpose of this study was to characterize the phase behavior of solutions resulting from the dissolution of model ASDs as well as the degree of supersaturation attained. Danazol was chosen as a poorly water-soluble model drug, and three polymers were used to form the dispersions: polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and hydroxypropylmethyl cellulose acetate succinate (HPMCAS). Dissolution studies were carried out under nonsink conditions, and solution phase behavior was characterized using several orthogonal techniques. It was found that liquid-liquid phase separation (LLPS) occurred following dissolution and prior to crystallization for most of the dispersions. Using flux measurements, it was further observed that the maximum attainable supersaturation following dissolution was equivalent to the amorphous solubility. The dissolution of the ASDs led to sustained supersaturation, the duration of which varied depending on the drug loading and the type of polymer used in the formulation. The overall supersaturation profile observed thus depended on a complex interplay between dissolution rate, polymer type, drug loading, and the kinetics of crystallization.

  1. Ion beam-induced amorphous-to-tetragonal phase transformation and grain growth of nanocrystalline zirconia.

    PubMed

    Lian, Jie; Zhang, Jiaming; Namavar, Fereydoon; Zhang, Yanwen; Lu, Fengyuan; Haider, Hani; Garvin, Kevin; Weber, W J; Ewing, Rodney C

    2009-06-17

    Nanocrystalline zirconia has recently attracted extensive research interest due to its unique mechanical, thermal and electrical properties as compared with bulk zirconia counterparts, and it is of particular importance for controlling the phase stability of different polymorphs (amorphous, cubic, tetragonal and monoclinic phases) in different size regimes. In this work, we performed ion beam bombardments on bilayers (amorphous and cubic) of nano-zirconia using 1 MeV Kr2+ irradiation. Transmission electron microscopy (TEM) analysis reveals that amorphous zirconia transforms to a tetragonal structure under irradiation at room temperature, suggesting that the tetragonal phase is more energetically favorable under these conditions. The final grain size of the tetragonal zirconia can be controlled by irradiation conditions. A slower kinetics in the grain growth from cubic nanocrystalline zirconia was found as compared with that for the tetragonal grains recrystallized from the amorphous layer. The radiation-induced nanograins of tetragonal ZrO2 are stable at ambient conditions and maintain their physical integrity over a long period of time after irradiation. These results demonstrated that ion beam methods provide the means to control the phase stability and structure of zirconia polymorphs.

  2. Porous polymers by controlling phase separation during vapor deposition polymerization.

    PubMed

    Tao, Ran; Anthamatten, Mitchell

    2013-11-01

    A template-free method is described to fabricate continuous-phase, porous polymer films by simultaneous phase separation during vapor deposition polymerization. The technique involves concurrent polymerization, crosslinking, and phase separation of condensed species and reaction products. Deposited films form open-cell, macroporous structures consisting of crosslinked and glassy poly(glycidyl methacrylate). By limiting phase separation during vapor phase deposition, spatially dependent morphologies, such as layered morphologies, can be grown. Results show that combining vapor deposition polymerization with phase separation establishes morphological control, which may be applied to applications including cellular scaffolds, thin cushions and vibration dampers, and membranes for separations.

  3. Phase separation in calcium alginate gels.

    PubMed

    Straatmann, A; Borchard, W

    2003-08-01

    Alginates are polysaccharides consisting of beta-D-mannuronate and alpha-L-guluronate units. In the presence of bivalent cations like calcium the guluronate blocks form physically cross-linked gels. The gelation properties of alginates play an important role in the stability of extracellular polymer substances and in the food industry. When stock solutions of Ca2+ ions and alginate are mixed, the gelation starts before the Ca2+ ions are evenly distributed, which leads to non-uniform gels. In this contribution, Ca alginate gels were prepared by in situ gelation using glucono-delta-lactone and CaCO3. In this way, uniform gels could be prepared directly in the measuring cell. Below a critical concentration, highly viscous solutions were obtained, which were below the critical point of gel formation. In these solutions at low rotational speeds a Schlieren peak arose, which became smaller and steeper with increasing time until a new meniscus could be detected. This behaviour is in contrast to the peak broadening due to diffusion after a synthetic boundary was formed. Evaluation of the data leads to negative diffusion coefficients. It has been shown by others that the mutual diffusion coefficient must be negative in the spinodal region. This phenomena is known as uphill diffusion and leads to phase separation of a binary system. The formation of the gel phase in this case is therefore discussed as uphill diffusion.

  4. Griffiths phase and temporal effects in phase separated manganites

    NASA Astrophysics Data System (ADS)

    Krivoruchko, V. N.; Marchenko, M. A.

    2016-08-01

    Phenomenological description of relaxation phenomena in magnetic and transport properties of perovskite manganites has been presented. The approach is based on generalization of some hypotheses appropriate to the Preisach picture of magnetization process for half-metallic ferromagnets and on an assumption that in doped manganites the phase separated state exists near the magnetic ordering temperature. For systems with the percolation type of a ferromagnet-paramagnet transition, distinctive features in relaxation of magnetization and resistivity have been found. The relaxation is shown to be most pronounced near the transition temperature, and to be an approximately logarithmic function of time. The theoretical results replicate a broad spectrum of behavior observed experimentally on time dependence of magnetization and resistivity of CMR systems and allow a direct comparison with available experimental data. We propose an additional experimental test to distinguish between the percolation scenario of magnetic and transport transitions in doped manganites, and the ferromagnetic polaron picture. In particular, an anomalously slow relaxation to zero of the order parameter can be considered as a key feature of the Griffiths-like phase transition in doped manganites. It is also shown that a system with the Griffiths-like state will exhibit nonequilibrium aging and rejuvenation phenomena, which in many aspects resemble that of a spin glass. We hope that experimental observation of a set of time decay properties will provide a settlement of apparently conflicting results obtained for different characteristics of phase-separated manganites.

  5. Absence of an abrupt phase change from polycrystalline to amorphous in silicon with deposition temperature.

    PubMed

    Voyles, P M; Gerbi, J E; Treacy, M M; Gibson, J M; Abelson, J R

    2001-06-11

    Using fluctuation electron microscopy, we have observed an increase in the mesoscopic spatial fluctuations in the diffracted intensity from vapor-deposited silicon thin films as a function of substrate temperature from the amorphous to polycrystalline regimes. We interpret this increase as an increase in paracrystalline medium-range order in the sample. A paracrystal consists of topologically crystalline grains in a disordered matrix; in this model the increase in ordering is caused by an increase in the grain size or density. Our observations are counter to the previous belief that the amorphous to polycrystalline transition is a discontinuous disorder-order phase transition.

  6. Amorphous and crystalline phases in thermal quench simulations of alumina.

    PubMed

    Rosen, J; Warschkow, O; McKenzie, D R; Bilek, M M M

    2007-05-28

    The authors report molecular dynamics simulations of alumina (Al2O3) during crystallization from the melt. Using liquid quench methods, they investigate the effect of cooling rate on the structural evolution of the alpha, kappa, and the bixbyite phases. A critical temperature window is identified, where the time spent in this window is crucial in determining the extent to which the systems approach crystallinity. A strong dependence is observed between the final structure and the quench rate, which is most pronounced for the alpha phase and to lesser extent for the other phases. The results show that the different phases have different tendencies to crystallize that are determined by energetics, complexity of crystal structure, and the number of metastable states.

  7. Atomic transport during solid-phase epitaxial recrystallization of amorphous germanium

    SciTech Connect

    Radek, M.; Bracht, H.; Johnson, B. C.; McCallum, J. C.; Posselt, M.; Liedke, B.

    2015-08-24

    The atomic mixing of matrix atoms during solid-phase epitaxy (SPE) is studied by means of isotopically enriched germanium (Ge) multilayer structures that were amorphized by Ge ion implantation up to a depth of 1.5 μm. Recrystallization of the amorphous structure is performed at temperatures between 350 °C and 450 °C. Secondary-ion-mass-spectrometry is used to determine the concentration-depth profiles of the Ge isotope before and after SPE. An upper limit of 0.5 nm is deduced for the displacement length of the Ge matrix atoms by the SPE process. This small displacement length is consistent with theoretical models and atomistic simulations of SPE, indicating that the SPE mechanism consists of bond-switching with nearest-neighbours across the amorphous-crystalline (a/c) interface.

  8. The Kinetics of Phase Separation in Asymmetric Membranes

    PubMed Central

    Wallace, Elizabeth J.; Hooper, Nigel M.; Olmsted, Peter D.

    2005-01-01

    Phase separation in a model asymmetric membrane is studied using Monte Carlo techniques. The membrane comprises two species of particles, which mimic different lipids in lipid bilayers and separately possess either zero or non-zero spontaneous curvatures. We study the influence of phase separation on membrane shape and the influence of the coupling of composition and height dynamics on phase separation and domain growth, via both the degree of shape asymmetry and relative kinetic coefficients for height relaxation. PMID:15778446

  9. Amorphous silicon photovoltaic manufacturing technology, phase 2A

    NASA Astrophysics Data System (ADS)

    Duran, G.; Mackamul, K.; Metcalf, D.; Volltrauer, H.

    1994-04-01

    Utility Power Group (UPG) and its lower-tier subcontractor, Advanced Photovoltaic Systems, Inc. (APS), continued work to develop their manufacturing lines. UPG focused on the automation of encapsulation and termination processes developed in Phase 1. APS focused on completion of the encapsulation and module design tasks while continuing process quality control, and automation projects. The goal is to produce 55-W (stabilized) EP50 modules in a new facility.

  10. Transparent, superhard amorphous carbon phase from compressing glassy carbon

    NASA Astrophysics Data System (ADS)

    Yao, Mingguang; Xiao, Junping; Fan, Xianhong; Liu, Ran; Liu, Bingbing

    2014-01-01

    Raman spectroscopy has been used to study the transformations of glassy carbon (GC) under high pressure. A GC sphere has been observed to transform into a transparent carbon phase above 33 GPa. The transformation is associated with a change in bonding character of carbon from sp2 to sp3 hybridization and an increase in hardness. The yield strength of the GC sphere reaches a value of 120 GPa at a confining pressure of 62 GPa, which is comparable to that of diamond at ambient conditions. The stress induced by the pressure medium is important for the observed transformations of GC under pressure.

  11. Characterization of Atomic Structure, Relaxation and Phase Transformation Mechanisms in Bulk and Thin Film Amorphous Chalcogenides and Gallium Antimonide

    NASA Astrophysics Data System (ADS)

    Edwards, Trenton Gerard

    intermediate between a randomly connected and a fully clustered network of GeSe4 tetrahedra and Se chains. Additionally, a new two-dimensional NMR spectroscopic technique is developed and applied to Ge-Se glasses that allowed the separation of isotropic and anisotropic chemical shifts. Through the analysis of the anisotropic sideband pattern in the second dimension it is possible to detect up to four distinct types of Se environments in the glass structure on the basis of their characteristic chemical shift anisotropies. 125Te NMR chemical shift systematics is established for coordination environments of Te atoms in a wide range of crystalline and glassy tellurides in the Ga-As-Sb-Te system. 125Te NMR spectroscopy is then used to investigate the short-range structure of amorphous and crystalline Ge1Sb2 Te4 and Ge2Sb2Te5 phase change alloys. Both alloys are found to consist of only heteropolar Ge/Sb-Te bonds in the amorphous and crystalline state and strong vacancy clustering in the nanocrystalline state that may facilitate a rapid displacive transformation between the amorphous and crystalline states without the need of significant atomic rearrangement or diffusion. Based on these 125Te NMR results a Te-centric model of the phase change mechanism in GST alloys is proposed. Structure and phase changes in amorphous Ga-Sb alloys are studied using synchrotron x-ray diffraction and 71Ga and 121Sb NMR spectroscopy. Pressure induced phase transformations in amorphous GaSb is shown to be consistent with the existence of an underlying polyamorphic phase transition between a low and a high-density amorphous phase. NMR results for amorphous Ga46Sb54 indicate that both Ga and Sb atoms are fourfold coordinated with 40% of these atoms participating in homopolar bonding in the as-deposited film. Subsequent crystallization into the zinc blend structure therefore requires extensive bond switching and elimination of homopolar bonds. For amorphous Ga14Sb86 both Ga and Sb atoms are found to be

  12. Two-phase amorphous-amorphous solid drug dispersion with enhanced stability, solubility and bioavailability resulting from ultrasonic dispersion of an immiscible system.

    PubMed

    Martínez, Luz María; Videa, Marcelo; López Silva, Tania; Castro, Samuel; Caballero, Adolfo; Lara-Díaz, Víctor J; Castorena-Torres, Fabiola

    2017-10-01

    Amorphization of active pharmaceutical ingredients (APIs) and the preparation of solid dispersions are strategies that can be synergized to improve the solubility of oral drugs. Immiscibility between an API and a carrier in the molten state that could be perceived as a problem in the preparation of solid dispersions, may actually introduce an advantage. In the present work, a two-phase amorphous-amorphous solid dispersion (AASD) was prepared by ultrasonicating a molten immiscible mixture of indomethacin (IND) and glucose (GLU) prior quenching. By introducing this novel ultrasound assisted method, the immiscible API particles were uniformly dispersed as microscopic glassy clusters of the drug in the solid amorphous GLU matrix; particle sizes of IND in the AASD range from 600nm to 1.4μm. As a result of the amorphization and particle size reduction of IND, its aqueous solubility increased to reach almost 40ppm (8 times more soluble compared to indomethacin in its crystalline state). In addition, the oral bioavailability and its resistance against crystallization were also enhanced; AASD samples have remained amorphous for more than two years of storage. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Thermomechanical Analysis on the Phase Stability of Nitrogen-Doped Amorphous Ge2Sb2Te5 Films

    NASA Astrophysics Data System (ADS)

    Park, Il-Mok; Cho, Ju-Young; Yang, Tae-Youl; Park, Eun Soo; Joo, Young-Chang

    2011-06-01

    The phase stability of amorphous Ge2Sb2Te5 (GST) films affects the performance and reliability of phase change memory (PRAM) devices. The viscosity and the glass forming ability of nitrogen (N)-doped amorphous GST films were investigated in terms of thermomechanical behavior using wafer curvature measurements. The viscosity which increased by two orders of magnitude was observed in the N-doped amorphous GST film by measuring the stress relaxation accompanied by bimolecular structural relaxation. The glass forming ability (ΔTx), difference between the glass transition temperature (Tg) and the crystallization temperature (Tc), of GST increased as the nitrogen contents increased. These increases in the viscosity and ΔTx indicate the retardation of atomic diffusion in amorphous GST and the stabilization of the amorphous phase.

  14. Thermal conductivity of the amorphous and nanocrystalline phases of the beech wood biocarbon nanocomposite

    NASA Astrophysics Data System (ADS)

    Kartenko, N. F.; Orlova, T. S.; Parfen'eva, L. S.; Smirnov, B. I.; Smirnov, I. A.

    2014-11-01

    Natural composites (biocarbons) obtained by carbonization of beech wood at different carbonization temperatures T carb in the range of 800-2400°C have been studied using X-ray diffraction. The composites consist of an amorphous matrix and nanocrystallites of graphite and graphene. The volume fractions of the amorphous and nanocrystalline phases as functions of T carb have been determined. Temperature dependences of the phonon thermal conductivity κ( T) of the biocarbons with different temperatures T carb (1000 and 2400°C) have been analyzed in the range of 5-300 K. It has been shown that the behavior of κ( T) of the biocarbon with T carb = 1000°C is controlled by the amorphous phase in the range of 5-50 K and by the nanocrystalline phase in the range of 100-300 K. The character of κ( T) of the biocarbon with T carb = 2400°C is determined by the heat transfer (scattering) in the nanocrystalline phase over the entire temperature range of 5-300 K.

  15. Ion beam-induced amorphous-to-tetragonal phase transformation and grain growth of nanocrystalline zirconia

    SciTech Connect

    Lian, Jie; Zhang, Jiaming; Namavar, Fereydoon; Zhang, Yanwen; Lu, Fengyuan; Haider, Hani; Garvin, Kevin; Weber, William J.; Ewing, Rodney C.

    2009-05-26

    Nanocrystalline zirconia has recently attracted extensive research interest due to its unique mechanical, thermal and electrical properties as compared to bulk zirconia counterparts, and it is of particular importance to control the phase stability of different polymorphs (amorphous, cubic, tetragonal and monoclinic phases) at different size regimes. In this paper, we performed ion beam bombardments on bilayers (amorphous and cubic) of pure nano-zirconia using 1 MeV Kr2+ irradiation. Transmission electron microscopy (TEM) analysis reveals that amorphous zirconia transforms to a tetragonal structure under irradiation at room temperature, suggesting that the tetragonal phase is more energetically favorable under these conditions. The final grain size of the tetragonal zirconia can be controlled by irradiation conditions. The irradiation-induced nanograins of tetragonal ZrO2 are stable at ambient conditions and maintain their physical integrity over a long period of time after irradiation. These results demonstrated that ion-beam modification methods provide the means to control the phase stability and structure of zirconia polymorphs.

  16. Fourier transform infrared analysis of ceramic powders: Quantitative determination of alpha, beta, and amorphous phases of silicon nitride

    SciTech Connect

    Trout, T.K.; Bellama, J.M.; Brinckman, F.E.; Faltynek, R.A.

    1989-03-01

    Fourier transform infrared spectroscopy (FT-IR) forms the basis for determining the morphological composition of mixtures containing alpha, beta, and amorphous phases of silicon nitride. The analytical technique, involving multiple linear regression treatment of Kubelka-Munk absorbance values from diffuse reflectance measurements, yields specific percent composition data for the amorphous phase as well as the crystalline phases in ternary mixtures of 0--1% by weight Si/sub 3/N/sub 4/ in potassium bromide.

  17. Reversible crystalline-amorphous phase transformation in Si nanosheets with lithi-/delithiation

    NASA Astrophysics Data System (ADS)

    Park, Jeong Min; Cho, Jae-Hyun; Ha, Jung Hoon; Kim, Hae-Sik; Kim, Sung-Wook; Lee, Jaejun; Chung, Kyung Yoon; Cho, Byung-Won; Choi, Heon-Jin

    2017-06-01

    Silicon (Si) has a large theoretical capacity of 4200 mAhg-1 and has great potential as a high-performance anode material for Li ion batteries (LIBs). Meanwhile, nanostructures can exploit the potential of Si and, accordingly, many zero-dimensional (0D) and one-dimensional (1D) Si nanostructures have been studied. Herein, we report on two-dimensional (2D) Si nanostructures, Si nanosheets (SiNSs), as anodes for LIBs. These 2D Si nanostructures, with a thickness as low 5 nm and widths of several micrometers, show reversible crystalline-amorphous phase transformations with the lithi-/delithiation by the dimensionality of morphology and large surface area. The reversible crystalline-amorphous phase transformation provides a structural stability of Li+ insertions and makes SiNSs promising candidates for reliable high-performance LIBs anode materials.

  18. Solid-phase epitaxy of silicon amorphized by implantation of the alkali elements rubidium and cesium

    SciTech Connect

    Maier, R.; Haeublein, V.; Ryssel, H.; Voellm, H.; Feili, D.; Seidel, H.; Frey, L.

    2012-11-06

    The redistribution of implanted Rb and Cs profiles in amorphous silicon during solid-phase epitaxial recrystallization has been investigated by Rutherford backscattering spectroscopy and secondary ion mass spectroscopy. For the implantation dose used in these experiments, the alkali atoms segregate at the a-Si/c-Si interface during annealing resulting in concentration peaks near the interface. In this way, the alkali atoms are moved towards the surface. Rutherford backscattering spectroscopy in ion channeling configuration was performed to measure average recrystallization rates of the amorphous silicon layers. Preliminary studies on the influence of the alkali atoms on the solid-phase epitaxial regrowth rate reveal a strong retardation compared to the intrinsic recrystallization rate.

  19. Crystallization and phase transformations in amorphous NiTi thin films for microelectromechanical systems

    SciTech Connect

    Lee, Hoo-Jeong; Ramirez, Ainissa G.

    2004-08-16

    Amorphous sputtered nickel-titanium thin films were deposited onto micromachined silicon-nitride membranes and subjected to heating and cooling conditions. Their associated microstructure was monitored directly and simultaneously with in situ transmission electron microscopy. These electron-transparent membranes constrained the NiTi films and rendered it possible for observation of the complete transformation cycle, which includes: the crystallization of the amorphous phase to austenite phase (cubic B2 structure) with heating; and the conversion of austenite (B2) to martensite (monoclinic B19{sup '} structure) with cooling. Electron micrographs show the nucleation and growth of grains occurs at a temperature of 470 deg. C and at a rate that indicates a polymorphic transformation. The onset of martensitic transformation occurs between 25 and 35 deg. C. Calorimetric measurements are consistent with the observed crystallization.

  20. Field Performance of Three-Phase Amorphous Metal Core Distribution Transformers at Pearl Harbor, Hawaii

    DTIC Science & Technology

    1990-08-01

    37 Waste water management and sanitary engineering Airfields and pavements 38 O1 pollution removal and recovery3 Air polution ADVANCED BASE AND...utility systems at Ford Island, Barbers Point Naval Air Station, the Naval Shipyard, and the Naval Supply Center at Pearl Harbor, Hawaii. The main...Power Meter connected to a three-phase 4-wire amorphous core transformer under test at Barbers Point Naval Air Station. This testing procedure was

  1. Superconductivity in the amorphous phase of topological insulator Bi x Sb100-x alloys

    NASA Astrophysics Data System (ADS)

    Barzola-Quiquia, J.; Lauinger, C.; Zoraghi, M.; Stiller, M.; Sharma, S.; Häussler, P.

    2017-01-01

    In this work we investigated the electrical properties of rapidly quenched amorphous Bi x Sb{}100-x alloys in the temperature range of 1.2 K to 345 K. The resistance reveals that for a broad range of different compositions, including that for the topological insulator (TI), a superconducting state in the amorphous phase is present. After crystallization and annealing at an intermediate temperature, we found that in pure Bi and Bi x Sb{}100-x alloys with composition corresponding to the TI, the superconductivity persists, but the transition shifts to a lower temperature. The highest superconducting transition temperature {T}{{C}0} was found for pure Bi and those TI’s, with a shift to low temperatures when the Sb content is increased. After annealing at a maximum temperature of T = 345 K, the samples are non-superconducting within the experimental range and the behavior changes from semiconducting-like for pure Bi, to metallic-like for pure Sb. Transition temperature {T}{{C}0} of the amorphous Bi x Sb{}100-x alloys have been calculated in the BCS-Eliashberg-McMillan framework, modified for binary alloys. The results can explain the experimental results and show that amorphous Bi x Sb{}100-x exhibits a strong to intermediate electron-phonon coupling.

  2. On the thermodynamically stable amorphous phase of polymer-derived silicon oxycarbide

    NASA Astrophysics Data System (ADS)

    Yu, Liping; Raj, Rishi

    2015-09-01

    A model for the thermodynamic stability of amorphous silicon oxycarbide (SiCO) is presented. It builds upon the reasonably accepted model of SiCO which is conceived as a nanodomain network of graphene. The domains are expected to be filled with SiO2 molecules, while the interface with graphene is visualized to contain mixed bonds described as Si bonded to C as well as to O atoms. Normally these SiCO compositions would be expected to crystallize. Instead, calorimetric measurements have shown that the amorphous phase is thermodynamically stable. In this article we employ first-principles calculations to estimate how the interfacial energy of the graphene networks is favorably influenced by having mixed bonds attached to them. We analyze the ways in which this reduction in interfacial energy can stabilize the amorphous phase. The approach highlights how density functional theory computations can be combined with the classical analysis of phase transformations to explain the behavior of a complex material. In addition we discover a two-dimensional lattice structure, with the composition Si2C4O3 that is constructed from a single layer of graphene congruent with silicon and oxygen bonds on either side.

  3. Hard magnetic phase evolution in nanocrystalline mechanically milled amorphous Pr2Co14B powder

    NASA Astrophysics Data System (ADS)

    Nlebedim, Cajetan; Ucar, Huseyin; Paranthaman, Parans; McCallum, R. W.

    2015-03-01

    In this work, the evolution of the structural and magnetic properties of Pr2Co14B with mechanical milling and heat-treatment is presented. Understanding the phase evolution of magnetic properties in hard magnetic materials is crucial for developing high performance permanent magnets. Mechanical alloying/milling offers a traditional and easily deployable approach to synthesizing nanostructured materials. Nevertheless, such can result in amorphization due to high defect density leading to disorder in atomic arrangement. The crystalline phase can be thermally recovered but requires the understanding of how the properties evolve with temperature, in order to achieve useful hard magnetic properties desired for developing permanent magnets. This work shows how properties such as energy product, coercivity, remanent magnetization, saturation magnetization and Curie temperature evolve when PrCoB alloy transitions from amorphous to crystalline phase. The presentation will also include how different levels of amorphization affect the magnetic properties. This work was supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office.

  4. Creation and formation mechanism of new carbon phases constructed by amorphous carbon

    NASA Astrophysics Data System (ADS)

    Yao, Mingguang; Cui, Wen; Liu, Bingbing

    Our recent effort is focusing on the creation of new hard/superhard carbon phases constructed by disordered carbons or amorphous carbon clusters under high pressure. We showed that the pressure-induced amorphous hard carbon clusters from collapsed fullerenes can be used as building blocks (BBs) for constructing novel carbon structures. This new strategy has been verified by compressing a series of intercalated fullerides, pre-designed by selecting various dopants with special features. We demonstrate that the boundaries of the amorphous BBs are mediated by intercalated dopants and several new superhard materials have been prepared. We also found that the dopant-mediated BBs can be arranged in either ordered or disordered structures, both of which can be hard enough to indent the diamond anvils. The hardening mechanisms of the new phases have also been discussed. For the glassy carbon (GC) constructructed by disordered fullerene-like nanosized fragments, we also found that these disordered fragments can bond and the compressed GC transformed into a transparent superhard phase. Such pressure-induced transformation has been discovered to be driven by a novel mechanism (unpublished). By understanding the mechanisms we can clarify the controversial results on glassy carbon reported recently. The authors would like to thank the financial support from the National Natural Science Foundation of China (No. 11474121, 51320105007).

  5. On the thermodynamically stable amorphous phase of polymer-derived silicon oxycarbide

    PubMed Central

    Yu, Liping; Raj, Rishi

    2015-01-01

    A model for the thermodynamic stability of amorphous silicon oxycarbide (SiCO) is presented. It builds upon the reasonably accepted model of SiCO which is conceived as a nanodomain network of graphene. The domains are expected to be filled with SiO2 molecules, while the interface with graphene is visualized to contain mixed bonds described as Si bonded to C as well as to O atoms. Normally these SiCO compositions would be expected to crystallize. Instead, calorimetric measurements have shown that the amorphous phase is thermodynamically stable. In this article we employ first-principles calculations to estimate how the interfacial energy of the graphene networks is favorably influenced by having mixed bonds attached to them. We analyze the ways in which this reduction in interfacial energy can stabilize the amorphous phase. The approach highlights how density functional theory computations can be combined with the classical analysis of phase transformations to explain the behavior of a complex material. In addition we discover a two-dimensional lattice structure, with the composition Si2C4O3 that is constructed from a single layer of graphene congruent with silicon and oxygen bonds on either side. PMID:26419962

  6. Formation of a crystalline phase in amorphous hydrogenated carbon-germanium films by electron beam irradiation

    SciTech Connect

    Tyczkowski, J.; Pietrzyk, B.; Mazurczyk, R.; Polanski, K.; Balcerski, J.; Delamar, M.

    1997-11-01

    The influence of electron beam irradiation on morphology of plasma deposited amorphous hydrogenated carbon-germanium films produced from tetramethylgermanium in a three-electrode af reactor has been studied. It has been found that the insulating films are insensitive to this treatment, whereas a crystalline phase occurs in the semiconducting films. Although the molar content of germanium in these films amounts only to about 0.2, the crystalline phase is composed of pure germanium nanocrystals which contain about 70{percent} of the whole amount of germanium existing in the films. The nanocrystals are agglomerated in globules of 50{endash}500 nm in diameter. {copyright} {ital 1997 American Institute of Physics.}

  7. Current status of amorphous formulation and other special dosage forms as formulations for early clinical phases.

    PubMed

    Kawakami, Kohsaku

    2009-09-01

    Although most chemists in the pharmaceutical industry have a good understanding on favorable physicochemical properties for drug candidates, formulators must still deal with many challenging candidates. On the other hand, formulators are not allowed to spend much time on formulation development for early phases of the clinical studies. Thus, it is basically difficult to apply special dosage form technologies to the candidates for the first-in-human formulations. Despite the availability of numerous reviews on oral special dosage forms, information on their applicability as the early phase formulation has been limited. This article describes quick review on the oral special dosage forms that may be applied to the early clinical formulations, followed by discussion focused on the amorphous formulations, which still has relatively many issues to be proved for the general use. The major problems that inhibit the use of the amorphous formulation are difficulty in the manufacturing and the poor chemical/physical stability. Notably, the poor physical stability can be critical, because of not the poor stability itself but the difficulty in the timely evaluation in the preclinical developmental timeframes. Research directions of the amorphous formulations are suggested to utilize this promising technology without disturbing the preclinical developmental timelines.

  8. Solid-phase crystallization of amorphous silicon nanowire array and optical properties

    NASA Astrophysics Data System (ADS)

    Ishikawa, Ryousuke; Kato, Shinya; Yamazaki, Tatsuya; Kurokawa, Yasuyoshi; Miyajima, Shinsuke; Konagai, Makoto

    2014-02-01

    An amorphous silicon nanowire (a-SiNW) array perpendicular to a glass substrate can be successfully obtained through the metal-assisted chemical etching of amorphous silicon (a-Si) thin films. The solid-phase crystallization of a-SiNWs was carried out by thermal annealing in a forming gas in the temperature range from 600 to 900 °C. The effects of hydrogen in the film and the film morphology on the crystallization of a-SiNWs were investigated by Raman spectroscopy and transmission electron microscopy. A higher hydrogen concentration of a-SiNWs reduced the crystallization temperature, as in a-Si thin films. It was also revealed that the large surface area of the a-SiNW array affected the crystallization process. We also studied the optical property of the fabricated SiNW array and demonstrated its high potential as an active layer in solar cells.

  9. Spin Filtering in Epitaxial Spinel Films with Nanoscale Phase Separation.

    PubMed

    Li, Peng; Xia, Chuan; Li, Jun; Zhu, Zhiyong; Wen, Yan; Zhang, Qiang; Zhang, Junwei; Peng, Yong; Alshareef, Husam N; Zhang, Xixiang

    2017-05-23

    The coexistence of ferromagnetic metallic phase and antiferromagnetic insulating phase in nanoscaled inhomogeneous perovskite oxides accounts for the colossal magnetoresistance. Although the model of spin-polarized electron transport across antiphase boundaries has been commonly employed to account for large magnetoresistance (MR) in ferrites, the magnetic anomalies, the two magnetic phases and enhanced molecular moment, are still unresolved. We observed a sizable MR in epitaxial spinel films (NiCo2O4-δ) that is much larger than that commonly observed in spinel ferrites. Detailed analysis reveals that this MR can be attributed to phase separation, in which the perfect ferrimagnetic metallic phase and ferrimagnetic insulating phase coexist. The magnetic insulating phase plays an important role in spin filtering in these phase separated spinel oxides, leading to a sizable MR effect. A spin filtering model based on Zeeman effect and direct tunneling is developed to account for MR of the phase separated films.

  10. Strain phase separation: Formation of ferroelastic domain structures

    NASA Astrophysics Data System (ADS)

    Xue, Fei; Li, Yongjun; Gu, Yijia; Zhang, Jinxing; Chen, Long-Qing

    2016-12-01

    Phase decomposition is a well-known process leading to the formation of two-phase mixtures. Here we show that a strain imposed on a ferroelastic crystal promotes the formation of mixed phases and domains, i.e., strain phase separation with local strains determined by a common tangent construction on the free energy versus strain curves. It is demonstrated that a domain structure can be understood using the concepts of domain/phase rule, lever rule, and coherent and incoherent strain phase separation, in a complete analogy to phase decomposition. The proposed strain phase separation model is validated using phase-field simulations and experimental observations of PbTi O3 and BiFe O3 thin films as examples. The proposed model provides a simple tool to guide and design domain structures of ferroelastic systems.

  11. Pressure-induced phase transformation, reversible amorphization, and anomalous visible light response in organolead bromide perovskite

    DOE PAGES

    Wang, Yonggang; Lu, Xujie; Yang, Wenge; ...

    2015-08-18

    Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH3NH3PbBr3 (MAPbBr3), under hydrostatic pressure up to 34 GPa at room temperature: Two phase transformations below 2 GPa (from Pm3¯m to Im3¯, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr6 octahedra and destroying of long-range ordering of MA cations, respectively.more » The visible light response of MAPbBr3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Lastly, our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.« less

  12. Pressure-induced phase transformation, reversible amorphization, and anomalous visible light response in organolead bromide perovskite

    SciTech Connect

    Wang, Yonggang; Lu, Xujie; Yang, Wenge; Wen, Ting; Yang, Liuxiang; Ren, Xiangting; Wang, Lin; Lin, Zheshuai; Zhao, Yusheng

    2015-08-18

    Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH3NH3PbBr3 (MAPbBr3), under hydrostatic pressure up to 34 GPa at room temperature: Two phase transformations below 2 GPa (from Pm3¯m to Im3¯, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr6 octahedra and destroying of long-range ordering of MA cations, respectively. The visible light response of MAPbBr3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Lastly, our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.

  13. Possible Existence of Two Amorphous Phases of D-Mannitol Related by a First-Order Transition

    NASA Astrophysics Data System (ADS)

    Zhu, Men; Wang, Jun-Qiang; Perepezko, John; Yu, Lian

    We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above Tg (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase (Phase X). The enthalpy of Phase X is roughly halfway between those of the known amorphous and crystalline phases. The amorphous nature of Phase X is suggested by its absence of birefringence, transparency, broad X-ray diffraction, and broad Raman and NIR spectra. Phase X has greater molecular spacing, higher molecular order, fewer intra- and more inter-molecular hydrogen bonds than the normal liquid. On fast heating, Phase X transforms back to SCL near 330 K. Upon temperature cycling, it shows a glass-transition-like change of heat capacity. The presence of D-sorbitol enables a first-order liquid-liquid transition (LLT) from SCL to Phase X. This is the first report of polyamorphism at 1 atm for a pharmaceutical relevant substance. As amorphous solids are explored for many applications, polyamorphism could offer a tool to engineer the properties of materials. (Ref: M. Zhu et al., J. Chem. Phys. 2015, 142, 244504)

  14. Amorphous phase-segregated copoly(ether)esterurethane thermoset networks with oligo(propylene glycol) and oligo[(rac-lactide)-co-glycolide] segments: synthesis and characterization.

    PubMed

    Zotzmann, Jörg; Alteheld, Armin; Behl, Marc; Lendlein, Andreas

    2009-09-01

    Completely amorphous copoly(ether)ester networks based on oligo(propylene glycol) and oligo[(rac-dilactide)-co-glycolide] segments were synthesized by crosslinking star-shaped hydroxyl-telechelic cooligomers using an aliphatic low-molecular weight diisocyanate. Two different network architectures were applied exhibiting differences in the phase-separation behavior. For networks from oligo(propylene glycol)-block-oligo[(rac-lactide)-co-glycolide] triols (G(3)OPG-bl-OLG) only one glass transition was obtained. However, networks from a mixture of oligo(propylene glycol) triols (G(3)OPG) and oligo[(rac-lactide)-co-glycolide] tetrols (P(4)OLG) with a ratio of components in a certain range show two glass transition temperatures (T (g)) being attributed to two segregated amorphous phases. In this way a wide spectrum of mechanical properties can be realized and adjusted to the requirements of a specific application.

  15. Phase-separated silicon-tin nanocomposites for high capacity negative electrodes in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Xiao, Xingcheng; Wang, John S.; Liu, Ping; Sachdev, Anil K.; Verbrugge, Mark W.; Haddad, Daad; Balogh, Michael P.

    2012-09-01

    Both silicon and tin have a high specific capacity (3600 mAh g-1 for Li15Si4 and 992 mAh g-1 for Li22Sn5 respectively) and are among the most attractive materials for potential negative electrodes in lithium ion batteries. However, mechanical degradation induced by the large volume expansion during the cycling has limited their practical application. In this work, we developed a new class of Si-Sn nanocomposites with unique phase-separated nanostructure, where the amorphous Si nanoparticles are thermodynamically precipitated out from Si-Sn alloy and embedded within the Sn matrix. The phase separation-induced nanostructure provides the capability to mitigate the mechanical degradation, by preventing the nucleation and propagation of microcracks during lithiation. The nanocomposite electrode exhibits relative high capacity (1400 mAh g-1) and excellent cycling stability with the optimum composition and nanostructure.

  16. 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.

  17. Sequence-Specific Polyampholyte Phase Separation in Membraneless Organelles

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    Liquid-liquid phase separation of charge- and/or aromatic-enriched intrinsically disordered proteins (IDPs) is critical in the biological function of membraneless organelles. Much of the physics of this recent discovery remains to be elucidated. Here, we present a theory in the random phase approximation to account for electrostatic effects in polyampholyte phase separations, yielding predictions consistent with recent experiments on the IDP Ddx4. The theory is applicable to any charge pattern and thus provides a general analytical framework for studying sequence dependence of IDP phase separation.

  18. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

    NASA Astrophysics Data System (ADS)

    Lan, S.; Ren, Y.; Wei, X. Y.; Wang, B.; Gilbert, E. P.; Shibayama, T.; Watanabe, S.; Ohnuma, M.; Wang, X.-L.

    2017-03-01

    An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase, which forms the room-temperature glass phase on quenching. The outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat treatment.

  19. Gallium-enhanced phase contrast in atom probe tomography of nanocrystalline and amorphous Al-Mn alloys.

    PubMed

    Ruan, Shiyun; Torres, Karen L; Thompson, Gregory B; Schuh, Christopher A

    2011-07-01

    Over a narrow range of composition, electrodeposited Al-Mn alloys transition from a nanocrystalline structure to an amorphous one, passing through an intermediate dual-phase nanocrystal/amorphous structure. Although the structural change is significant, the chemical difference between the phases is subtle. In this study, the solute distribution in these alloys is revealed by developing a method to enhance phase contrast in atom probe tomography (APT). Standard APT data analysis techniques show that Mn distributes uniformly in single phase (nanocrystalline or amorphous) specimens, and despite some slight deviations from randomness, standard methods reveal no convincing evidence of Mn segregation in dual-phase samples either. However, implanted Ga ions deposited during sample preparation by focused ion-beam milling are found to act as chemical markers that preferentially occupy the amorphous phase. This additional information permits more robust identification of the phases and measurement of their compositions. As a result, a weak partitioning tendency of Mn into the amorphous phase (about 2 at%) is discerned in these alloys.

  20. Relation between bandgap and resistance drift in amorphous phase change materials.

    PubMed

    Rütten, Martin; Kaes, Matthias; Albert, Andreas; Wuttig, Matthias; Salinga, Martin

    2015-12-01

    Memory based on phase change materials is currently the most promising candidate for bridging the gap in access time between memory and storage in traditional memory hierarchy. However, multilevel storage is still hindered by the so-called resistance drift commonly related to structural relaxation of the amorphous phase. Here, we present the temporal evolution of infrared spectra measured on amorphous thin films of the three phase change materials Ag4In3Sb67Te26, GeTe and the most popular Ge2Sb2Te5. A widening of the bandgap upon annealing accompanied by a decrease of the optical dielectric constant ε∞ is observed for all three materials. Quantitative comparison with experimental data for the apparent activation energy of conduction reveals that the temporal evolution of bandgap and activation energy can be decoupled. The case of Ag4In3Sb67Te26, where the increase of activation energy is significantly smaller than the bandgap widening, demonstrates the possibility to identify new phase change materials with reduced resistance drift.

  1. Relation between bandgap and resistance drift in amorphous phase change materials

    PubMed Central

    Rütten, Martin; Kaes, Matthias; Albert, Andreas; Wuttig, Matthias; Salinga, Martin

    2015-01-01

    Memory based on phase change materials is currently the most promising candidate for bridging the gap in access time between memory and storage in traditional memory hierarchy. However, multilevel storage is still hindered by the so-called resistance drift commonly related to structural relaxation of the amorphous phase. Here, we present the temporal evolution of infrared spectra measured on amorphous thin films of the three phase change materials Ag4In3Sb67Te26, GeTe and the most popular Ge2Sb2Te5. A widening of the bandgap upon annealing accompanied by a decrease of the optical dielectric constant ε∞ is observed for all three materials. Quantitative comparison with experimental data for the apparent activation energy of conduction reveals that the temporal evolution of bandgap and activation energy can be decoupled. The case of Ag4In3Sb67Te26, where the increase of activation energy is significantly smaller than the bandgap widening, demonstrates the possibility to identify new phase change materials with reduced resistance drift. PMID:26621533

  2. Photopolymerization-induced crystallization and phase separation in poly(ethylene oxide)/triacrylate blends

    SciTech Connect

    Park, Soo Jeoung; Kyu, Thein

    2008-12-28

    The present article describes experimental and theoretical investigations of miscibility and crystallization behavior of blends of poly(ethylene oxide) (PEO) and triacrylate monomer (TA) using differential scanning calorimetry and optical microscopy. The PEO/TA blends manifested a single T{sub g} varying systematically with composition suggestive of a miscible character in their amorphous states. Moreover, there occurs melting point depression of PEO crystals with increasing TA. A phase diagram was subsequently established that exhibited a solid+liquid coexistence region bound by the liquidus and solidus lines, followed by an upper critical solution temperature (UCST) at a lower temperature. The emerging phase morphology was investigated to verify the coexistence regions. Upon photopolymerization in the isotropic melt above the melting point depression curve, both the UCST and the melting temperatures move upward and eventually surpass the reaction temperature, resulting in phase separation as well as crystallization of PEO driven by the changing supercooling, i.e., the thermodynamic driving force. Of particular interest is the interplay between photopolymerization-induced phase separation and crystallization, which eventually determines the final phase morphology of the PEO/TA blend such as crystalline lamellae, sheaf, or spherulites in isotropic liquid, phase separated domains, and viscous fingering liquids.

  3. Photopolymerization-induced crystallization and phase separation in poly(ethylene oxide)/triacrylate blends.

    PubMed

    Park, Soo Jeoung; Kyu, Thein

    2008-12-28

    The present article describes experimental and theoretical investigations of miscibility and crystallization behavior of blends of poly(ethylene oxide) (PEO) and triacrylate monomer (TA) using differential scanning calorimetry and optical microscopy. The PEO/TA blends manifested a single T(g) varying systematically with composition suggestive of a miscible character in their amorphous states. Moreover, there occurs melting point depression of PEO crystals with increasing TA. A phase diagram was subsequently established that exhibited a solid+liquid coexistence region bound by the liquidus and solidus lines, followed by an upper critical solution temperature (UCST) at a lower temperature. The emerging phase morphology was investigated to verify the coexistence regions. Upon photopolymerization in the isotropic melt above the melting point depression curve, both the UCST and the melting temperatures move upward and eventually surpass the reaction temperature, resulting in phase separation as well as crystallization of PEO driven by the changing supercooling, i.e., the thermodynamic driving force. Of particular interest is the interplay between photopolymerization-induced phase separation and crystallization, which eventually determines the final phase morphology of the PEO/TA blend such as crystalline lamellae, sheaf, or spherulites in isotropic liquid, phase separated domains, and viscous fingering liquids.

  4. Synthesis, conductivity and high-pressure phase transition of amorphous boron carbon nitride

    NASA Astrophysics Data System (ADS)

    Bai, Suo Zhu; Yao, Bin; Xing, Guo Zhong; Zhang, Ke; Su, Wen-Hui

    2007-06-01

    Amorphous BCN was prepared by chemical solid-state reaction between boracic acid (H 3BO 3) and melamine (C 3N 6H 6) in mass ratios of H 3BO 3 to C 3N 6H 6 of 1:2-1:4 and heat treatment at 1273 K under 10 -3 Pa. The amorphous B sbnd C sbnd N behave insulating property below 890 K, but semiconductor conductivity above 890 K and show different conductivity-temperature relationships in temperature ranges of 913-963 and 963-1083 K. The conductive activation energy was calculated to be 0.26-0.34 eV at 913-963 K and 1.02-1.10 eV at 963-1083 K, implying that the conduction mechanisms are different in the different temperature ranges. Annealed for 40 min at 1473 K under 4.0 GPa, the amorphous BCN with the chemical composition B 0.48C 0.29N 0.23 was prepared in the mass ratio of 1:3 crystallizes into single-phase hexagonal (h-BCN) compound with lattice constants of a=0.2506 nm and c=0.6652 nm. Raman scattering peaks were observed at 1330, 1364,1584 and 1617 cm -1 in the Raman spectrum (RS) of h-BCN, of which the peaks located at 1330 and 1617 cm -1 are assigned to characteristic peaks of the h-BCN.

  5. Addressing the Amorphous Content Issue in Quantitative Phase Analysis: The Certification of NIST Standard Reference Material 676a

    SciTech Connect

    J Cline; R Von Dreele; R Winburn; P Stephens; J Filliben

    2011-12-31

    A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Under the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.

  6. Effect of Si additions on thermal stability and the phase transition sequence of sputtered amorphous alumina thin films

    SciTech Connect

    Bolvardi, H.; Baben, M. to; Nahif, F.; Music, D. Schnabel, V.; Shaha, K. P.; Mráz, S.; Schneider, J. M.; Bednarcik, J.; Michalikova, J.

    2015-01-14

    Si-alloyed amorphous alumina coatings having a silicon concentration of 0 to 2.7 at. % were deposited by combinatorial reactive pulsed DC magnetron sputtering of Al and Al-Si (90-10 at. %) split segments in Ar/O{sub 2} atmosphere. The effect of Si alloying on thermal stability of the as-deposited amorphous alumina thin films and the phase formation sequence was evaluated by using differential scanning calorimetry and X-ray diffraction. The thermal stability window of the amorphous phase containing 2.7 at. % of Si was increased by more than 100 °C compared to that of the unalloyed phase. A similar retarding effect of Si alloying was also observed for the α-Al{sub 2}O{sub 3} formation temperature, which increased by more than 120 °C. While for the latter retardation, the evidence for the presence of SiO{sub 2} at the grain boundaries was presented previously, this obviously cannot explain the stability enhancement reported here for the amorphous phase. Based on density functional theory molecular dynamics simulations and synchrotron X-ray diffraction experiments for amorphous Al{sub 2}O{sub 3} with and without Si incorporation, we suggest that the experimentally identified enhanced thermal stability of amorphous alumina with addition of Si is due to the formation of shorter and stronger Si–O bonds as compared to Al–O bonds.

  7. Addressing the amorphous content issue in quantitative phase analysis: the certification of NIST standard reference material 676a.

    PubMed

    Cline, James P; Von Dreele, Robert B; Winburn, Ryan; Stephens, Peter W; Filliben, James J

    2011-07-01

    A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum (α-Al(2)O(3)) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Under the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% ± 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.

  8. Sound propagation in phase-separating fluids

    NASA Astrophysics Data System (ADS)

    Onuki, Akira

    1991-06-01

    We examine sound propagation in two-phase states of one- and two-component fluids by taking into account heat and mass transport between the two phases. For the sake of simplicity, detailed calculations are performed on near-critical fluids undergoing nucleation or spinodal decomposition, which exhibit very large acoustic anomalies at relatively low frequencies. As a universal relation the zero-frequency sound speed is reduced to 82% of the sound speed without domains in near-critical pure fluids. However, our predictions can be applied even to fluids far from criticality. One of our main findings is that, when droplets are sparsely distributed, sounds can induce latent-heat generation or absorption at the interfaces and produce long-range temperature gradients extending far from the droplets. The sounds are then anomalously attenuated at low frequencies, and the effect may be used to detect onset of nucleation. We also calculate a frequency-dependent adiabatic compressibility in two-phase states, which is valid even far from criticality and is applicable to bubbly fluids. It reproduces the effective-medium theory at relatively high frequencies and a Landau-Lifshitz result in the zero-frequency limit. The mechanism investigated is general and is not limited to fluids.

  9. SEC/reversed-phase separation of E. coli proteins.

    PubMed

    Apffell, Alex

    2010-05-01

    Although many chromatographic modes can be coupled for the multidimensional separation of a complex mixture, a very favorable combination is that of size-exclusion chromatography (SEC) and reversed-phase chromatography. The separation mechanisms are largely orthogonal and the mobile phases are compatible. The use of a retentive second dimension allows trapping of specific fractions from the SEC separation and transferring them to the reversed-phase separation. One of the advantages of multidimensional chromatography is that it is scalable in terms of automation. In a completely manual system, fractions eluting from a first dimension can be manually collected and injected into a second separation dimension. In an automated system, fraction transfer can be accomplished through automated valving. The following protocol illustrates this approach, with both a manual method and an external column switching method integrated into an automated high-performance liquid chromatography (HPLC) method. As an illustration, soluble proteins from Escherichia coli are separated.

  10. Template-assisted mineral formation via an amorphous liquid phase precursor route

    NASA Astrophysics Data System (ADS)

    Amos, Fairland F.

    The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was

  11. Mechanical enhancement through phase separation in a bicontinuous hydrogel network

    NASA Astrophysics Data System (ADS)

    Nixon, Ryan; Angelini, Thomas

    2015-03-01

    Bicontinous networks of phase separated polymers are often used in biomedical materials to control the spatial distribution of multiple surface functionalities. Here we describe a different use of phase separation, which leverages a balance of aggregating and swelling tendencies of the two separated components, producing a hydrogel that is highly stretchable and resilient after large extensions. In contrast to the typical one-component hydrogel, which is brittle and weak, the two-component micro-phase separated hydrogel recovers within just a few minutes after being stretched by several hundred percent, and fails at about 1000% strain. Our preliminary 3D reconstructions of the bi-continuous phases suggest that the gel's material properties arise from a system-spanning network of non-specific hydrophobic bonds that can be broken and re-formed under cycles of large strain, while elasticity is provided by the highly-solvated hydrogel that makes up the complementary phase.

  12. Phase separation as a possible means of nuclear compartmentalization.

    PubMed

    Aumiller, William M; Davis, Bradley W; Keating, Christine D

    2014-01-01

    The nucleus is perhaps the most familiar organelle within eukaryotic cells, serving as a compartment to house the genetic material. The nuclear volume is subdivided into a variety of functional and dynamic nuclear bodies not separated from the nucleoplasm by membranes. It has been hypothesized that aqueous phase separation brought about by macromolecular crowding may be in part responsible for these intranuclear compartments. This chapter discusses macromolecular solution chemistry with regard to several common types of phase separation in polymer solutions as well as to recent evidence that suggests that cytoplasmic and nuclear bodies may exist as liquid phases. We then examine the functional significance of phase separation and how it may serve as a means of compartmentalizing various nuclear activities, and describe recent studies that have used simple model systems to generate coexisting aqueous phase compartments, concentrate molecules within them, and perform localized biochemical reactions. © 2014 Elsevier Inc. All rights reserved.

  13. Phase transitions from semiconductive amorphous to conductive polycrystalline in indium silicon oxide thin films

    NASA Astrophysics Data System (ADS)

    Mitoma, Nobuhiko; Da, Bo; Yoshikawa, Hideki; Nabatame, Toshihide; Takahashi, Makoto; Ito, Kazuhiro; Kizu, Takio; Fujiwara, Akihiko; Tsukagoshi, Kazuhito

    2016-11-01

    The enhancement in electrical conductivity and optical transparency induced by a phase transition from amorphous to polycrystalline in lightly silicon-doped indium oxide (InSiO) thin films is studied. The phase transition caused by simple thermal annealing transforms the InSiO thin films from semiconductors to conductors. Silicon atoms form SiO4 tetrahedra in InSiO, which enhances the overlap of In 5s orbitals as a result of the distortion of InO6 octahedral networks. Desorption of weakly bonded oxygen releases electrons from deep subgap states and enhances the electrical conductivity and optical transparency of the films. Optical absorption and X-ray photoelectron spectroscopy measurements reveal that the phase transition causes a Fermi energy shift of ˜0.2 eV.

  14. Coupled dissolution-precipitation as a mechanism for amorphous-to-crystalline calcium carbonate phase transition

    NASA Astrophysics Data System (ADS)

    Rodriguez-Navarro, Carlos Manuel; Kudłacz, Krzysztof; Ruiz-Agudo, Encarnacion

    2014-05-01

    Growing evidence shows that several calcium carbonate biominerals form via an amorphous precursor phase. Such a biomineralization strategy could also be applicable for the biomimetic synthesis of novel functional materials. A crucial step in this process is the transformation of amorphous calcium carbonate (ACC) into calcite. However, controversy exists as to what is the actual mechanism of this transformation: Is it a solid-solid (solid state) or a dissolution/precipitation mechanism? Determining the transition mechanism is critical for example in interpreting the formation of oriented crystalline structures in biominerals (e.g., echinoderm spicles). We studied calcium carbonate precipitation and phase transitions according to the overall reaction Ca(OH)2 + CO2 = CaCO3+ H2O. Mineral phase transformations during this reaction were studied using transmission electron microscopy (TEM). Our TEM analysis showed that two different types of ACC are sequentially formed during this reaction. Type I ACC shows no well-defined short-range order, while Type II ACC shows a short-range order corresponding to calcite. Following e-beam irradiation, Type I ACC particles transform into randomly oriented CaO nanocrystals, while irradiation of Type II ACC leads to the formation of pseudomorphs made up of perfectly oriented aggregates of calcite nanocrystals. Moreover, calcite crystals formed in solution or in air (85 % relative humidity) after Type II ACC are also pseudomorphs made up of porous aggregates of preferentially oriented calcite nanocrystals. Our results give experimental evidence showing that the ACC to calcite transformation under relevant biomineralization conditions (low T and P), also applicable in the biomimetic synthesis of calcite, is a pseudomorphic dissolution-precipitation process. This mechanism involves the tightly interface-coupled dissolution of the precursor amorphous phase (with the crystalline phase protostructure) and concomitant deposition of the

  15. Phase Separators And Fountain-Effect Pumps For He 11

    NASA Technical Reports Server (NTRS)

    Whitehouse, Paul L.

    1989-01-01

    Fused-glass microchannel arrays for use as HE 11 phase separators and fountain-effect pumps. Microchannel devices for use in low-gravity storage and cooling systems containing superfluid helium. Phase separators and pumps take advantage of thermomechanical effect peculiar to He 11 in restricted spaces. By creating thermal gradient in porous plug, direction of flow reversed, turning phase separator into pump. However, addition of heat disadvantage. Thermal gradient created by using Peltier effect to transfer heat across array, removing heat from He 11 supply and overcoming undesirable addition of heat.

  16. Continuum Theory of Phase Separation Kinetics for Active Brownian Particles

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

    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.

  17. Phase Separators And Fountain-Effect Pumps For He 11

    NASA Technical Reports Server (NTRS)

    Whitehouse, Paul L.

    1989-01-01

    Fused-glass microchannel arrays for use as HE 11 phase separators and fountain-effect pumps. Microchannel devices for use in low-gravity storage and cooling systems containing superfluid helium. Phase separators and pumps take advantage of thermomechanical effect peculiar to He 11 in restricted spaces. By creating thermal gradient in porous plug, direction of flow reversed, turning phase separator into pump. However, addition of heat disadvantage. Thermal gradient created by using Peltier effect to transfer heat across array, removing heat from He 11 supply and overcoming undesirable addition of heat.

  18. Field-Induced Crystalline-to-Amorphous Phase Transformation on the Si Nano-Apex and the Achieving of Highly Reliable Si Nano-Cathodes

    PubMed Central

    Huang, Yifeng; Deng, Zexiang; Wang, Weiliang; Liang, Chaolun; She, Juncong; Deng, Shaozhi; Xu, Ningsheng

    2015-01-01

    Nano-scale vacuum channel transistors possess merits of higher cutoff frequency and greater gain power as compared with the conventional solid-state transistors. The improvement in cathode reliability is one of the major challenges to obtain high performance vacuum channel transistors. We report the experimental findings and the physical insight into the field induced crystalline-to-amorphous phase transformation on the surface of the Si nano-cathode. The crystalline Si tip apex deformed to amorphous structure at a low macroscopic field (0.6~1.65 V/nm) with an ultra-low emission current (1~10 pA). First-principle calculation suggests that the strong electrostatic force exerting on the electrons in the surface lattices would take the account for the field-induced atomic migration that result in an amorphization. The arsenic-dopant in the Si surface lattice would increase the inner stress as well as the electron density, leading to a lower amorphization field. Highly reliable Si nano-cathodes were obtained by employing diamond like carbon coating to enhance the electron emission and thus decrease the surface charge accumulation. The findings are crucial for developing highly reliable Si-based nano-scale vacuum channel transistors and have the significance for future Si nano-electronic devices with narrow separation. PMID:25994377

  19. Vortex phase separation in mesoscopic superconductors

    PubMed Central

    Iaroshenko, O.; Rybalko, V.; Vinokur, V. M.; Berlyand, L.

    2013-01-01

    We demonstrate that in mesoscopic type II superconductors with the lateral size commensurate with London penetration depth, the ground state of vortices pinned by homogeneously distributed columnar defects can form a hierarchical nested domain structure. Each domain is characterized by an average number of vortices trapped at a single pinning site within a given domain. Our study marks a radical departure from the current understanding of the ground state in disordered macroscopic systems and provides an insight into the interplay between disorder, vortex-vortex interaction, and confinement within finite system size. The observed vortex phase segregation implies the existence of the soliton solution for the vortex density in the finite superconductors and establishes a new class of nonlinear systems that exhibit the soliton phenomenon.

  20. Computer simulation study of metastable ice VII and amorphous phases obtained by its melting

    NASA Astrophysics Data System (ADS)

    Slovák, Jan; Tanaka, Hideki

    2005-05-01

    Molecular dynamics simulations of metastable ice VII and cubic ice Ic are carried out in order to examine (1) the ability of commonly used water interaction potentials to reproduce the properties of ices, and (2) the possibility of generating low-density amorphous (LDA) structures by heating ice VII, which is known to transform to LDA at ˜135K at normal pressure [S. Klotz, J. M. Besson, G. Hamel, R. J. Nelmes, J. S. Loveday, and W. G. Marshall, Nature (London) 398, 681 (1999)]. We test four simple empirical interaction potentials of water: TIP4P [W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein, J. Chem. Phys. 79, 926 (1983)], SPC/E [H. J. C. Berendsen, J. R. Grigera, and T. P. Straatsma, J. Phys. Chem. B 91, 6269 (1987)], TIP5P [M. W. Mahoney and W. L. Jorgensen, J. Chem. Phys. 112, 8910 (2000)], and ST2 [F. H. Stillinger and A. Rahman, J. Chem. Phys. 60, 1545 (1974)]. We have found that TIP5P ice VII melts at 210 K, TIP4P at 90 K, and SPC/E at 70 K. Only TIP5P water after transition has a structure similar to that of LDA. TIP4P and SPC/E have almost identical structures, dissimilar to any known water or amorphous phases, but upon heating both slowly evolve towards LDA-like structure. ST2 ice VII is remarkably stable up to 430 K. TIP4P and SPC/E predict correctly the cubic ice collapse into a high-density amorphous ice (HDA) at ˜1GPa whereas TIP5P remains stable up to ˜5GPa. The densities of the simulated ice phases differ significantly, depending on the potential used, and are generally higher than experimental values. The importance of proper treatment of long-range electrostatic interactions is also discussed.

  1. Computer simulation study of metastable ice VII and amorphous phases obtained by its melting.

    PubMed

    Slovák, Jan; Tanaka, Hideki

    2005-05-22

    Molecular dynamics simulations of metastable ice VII and cubic ice Ic are carried out in order to examine (1) the ability of commonly used water interaction potentials to reproduce the properties of ices, and (2) the possibility of generating low-density amorphous (LDA) structures by heating ice VII, which is known to transform to LDA at approximately 135 K at normal pressure [S. Klotz, J. M. Besson, G. Hamel, R. J. Nelmes, J. S. Loveday, and W. G. Marshall, Nature (London) 398, 681 (1999)]. We test four simple empirical interaction potentials of water: TIP4P [W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein, J. Chem. Phys. 79, 926 (1983)], SPC/E [H. J. C. Berendsen, J. R. Grigera, and T. P. Straatsma, J. Phys. Chem. B 91, 6269 (1987)], TIP5P [M. W. Mahoney and W. L. Jorgensen, J. Chem. Phys. 112, 8910 (2000)], and ST2 [F. H. Stillinger and A. Rahman, J. Chem. Phys. 60, 1545 (1974)]. We have found that TIP5P ice VII melts at 210 K, TIP4P at 90 K, and SPC/E at 70 K. Only TIP5P water after transition has a structure similar to that of LDA. TIP4P and SPC/E have almost identical structures, dissimilar to any known water or amorphous phases, but upon heating both slowly evolve towards LDA-like structure. ST2 ice VII is remarkably stable up to 430 K. TIP4P and SPC/E predict correctly the cubic ice collapse into a high-density amorphous ice (HDA) at approximately 1 GPa whereas TIP5P remains stable up to approximately 5 GPa. The densities of the simulated ice phases differ significantly, depending on the potential used, and are generally higher than experimental values. The importance of proper treatment of long-range electrostatic interactions is also discussed.

  2. 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.

  3. Phase separation in the isolation and purification of membrane proteins.

    PubMed

    Arnold, Thomas; Linke, Dirk

    2007-10-01

    Phase separation is a simple, efficient, and cheap method to purify and concentrate detergent-solubilized membrane proteins. In spite of this, phase separation is not widely used or even known among membrane protein scientists, and ready-to-use protocols are available for only relatively few detergent/membrane protein combinations. Here, we summarize the physical and chemical parameters that influence the phase separation behavior of detergents commonly used for membrane protein studies. Examples for the successful purification of membrane proteins using this method with different classes of detergents are provided. As the choice of the detergent is critical in many downstream applications (e.g., membrane protein crystallization or functional assays), we discuss how new phase separation protocols can be developed for a given detergent buffer system.

  4. Separation of Chloroplast Pigments Using Reverse Phase Chromatography.

    ERIC Educational Resources Information Center

    Reese, R. Neil

    1997-01-01

    Presents a protocol that uses reverse phase chromatography for the separation of chloroplast pigments. Provides a simple and relatively safe procedure for use in teaching laboratories. Discusses pigment extraction, chromatography, results, and advantages of the process. (JRH)

  5. Separation of Chloroplast Pigments Using Reverse Phase Chromatography.

    ERIC Educational Resources Information Center

    Reese, R. Neil

    1997-01-01

    Presents a protocol that uses reverse phase chromatography for the separation of chloroplast pigments. Provides a simple and relatively safe procedure for use in teaching laboratories. Discusses pigment extraction, chromatography, results, and advantages of the process. (JRH)

  6. Effect of amorphous phases during the hydraulic conversion of α-TCP into calcium-deficient hydroxyapatite.

    PubMed

    Hurle, Katrin; Neubauer, Juergen; Bohner, Marc; Doebelin, Nicola; Goetz-Neunhoeffer, Friedlinde

    2014-09-01

    Powders of α-tricalcium phosphate (α-TCP), which readily react with water to form calcium-deficient hydroxyapatite (CDHA), are frequently used in bone cements. As, for clinical applications, it is important to adjust the setting reaction of the cements to a reasonable reaction time, exact knowledge of the hydration mechanism is essential. It is known that prolonged milling results in partial amorphization of α-TCP powders and that dissolution of the amorphous phase significantly accelerates the hydration, but it is not clear yet when the amorphous phase reacts in comparison to the crystalline α-TCP. Therefore the aim of this study was to investigate the development of quantitative phase content of α-TCP samples during hydration. For this purpose, three α-TCP powders, containing 0, 16 and 71wt.% of amorphous phase (ATCP), were mixed with either deionized water or a 0.1M Na2HPO4 aqueous solution. The crystalline evolution of the paste was assessed quantitatively during the first 48h of hydration at 23°C by G-factor quantification. The present investigations demonstrate that ATCP reacted earlier than crystalline α-TCP. The results also suggest the formation of an X-ray amorphous phase during the hydraulic conversion formation of α-TCP into CDHA.

  7. The mobility of the amorphous phase in polyethylene as a determining factor for slow crack growth

    NASA Astrophysics Data System (ADS)

    Men, Y. F.; Rieger, J.; Enderle, H.-F.; Lilge, D.

    2004-12-01

    Polyethylene (PE) pipes generally exhibit a limited lifetime, which is considerably shorter than their chemical degradation period. Slow crack growth failure occurs when pipes are used in long-distance water or gas distribution though being exposed to a pressure lower than the corresponding yield stress. This slow crack growth failure is characterized by localized craze growth and craze fibril rupture. In the literature, the lifetime of PE pipes is often considered as being determined by the density of tie chains connecting adjacent crystalline lamellae. But this consideration cannot explain the excellent durability of the recent bimodal grade PE for pipe application. We show in this paper the importance of the craze fibril length as the determining factor for the pipe lifetime. The conclusions are drawn from stress analysis. It is found that longer craze fibrils sustain lower stress and are deformed to a lesser degree. The mobility of the amorphous phase is found to control the amount of material that can be “sucked” in by the craze fibrils and thus the length of the craze fibrils. The mobility of the amorphous phase can be monitored by dynamic mechanical analysis measurements. Excellent agreement between the mobility thus derived and lifetimes of PE materials as derived from FNCT (full notch creep test) is given, thus providing an effective means to estimate the lifetime of PE pipes by considering well-defined physical properties.

  8. Formation of nanocrystalline phases during thermal decomposition of amorphous Ni-P alloys by isothermal annealing.

    PubMed

    Révész, A; Lendvai, J; Cziráki, A; Liebermann, H H; Bakonyi, I

    2001-06-01

    The microstructure and the average grain size were investigated by x-ray diffraction and transmission electron microscopy for nanocrystalline (n) Ni-P alloys with 18, 19, and 22 at.% P. A detailed study of the nanocrystalline states obtained along different heat treatment routes has been performed: (1) a-->ni by isothermal annealing of the melt-quenched amorphous (a) Ni-P alloys; (2) ni-->nii by isothermal annealing of the nanocrystalline ni state; (3) ni-->nii by linear heating of the ni state. The heats evolved during the structural transformations were determined by differential scanning calorimetry. From these studies, a scheme of the structural transformations and their energetics was constructed, which also includes previous results on phases obtained by linear heating of the as-quenched amorphous state of the same alloys. Grain boundary energies also have been estimated. In some cases it was necessary to assume a variation of the specific grain boundary energy during the phase transformation to understand the enthalpy and microstructure changes during the different heat treatments.

  9. Investigating Structure and Dynamics of Proteins in Amorphous Phases Using Neutron Scattering.

    PubMed

    Castellanos, Maria Monica; McAuley, Arnold; Curtis, Joseph E

    2017-01-01

    In order to increase shelf life and minimize aggregation during storage, many biotherapeutic drugs are formulated and stored as either frozen solutions or lyophilized powders. However, characterizing amorphous solids can be challenging with the commonly available set of biophysical measurements used for proteins in liquid solutions. Therefore, some questions remain regarding the structure of the active pharmaceutical ingredient during freezing and drying of the drug product and the molecular role of excipients. Neutron scattering is a powerful technique to study structure and dynamics of a variety of systems in both solid and liquid phases. Moreover, neutron scattering experiments can generally be correlated with theory and molecular simulations to analyze experimental data. In this article, we focus on the use of neutron techniques to address problems of biotechnological interest. We describe the use of small-angle neutron scattering to study the solution structure of biological molecules and the packing arrangement in amorphous phases, that is, frozen glasses and freeze-dried protein powders. In addition, we discuss the use of neutron spectroscopy to measure the dynamics of glassy systems at different time and length scales. Overall, we expect that the present article will guide and prompt the use of neutron scattering to provide unique insights on many of the outstanding questions in biotechnology.

  10. Laser-driven formation of a high-pressure phase in amorphous silica.

    PubMed

    Salleo, Alberto; Taylor, Seth T; Martin, Michael C; Panero, Wendy R; Jeanloz, Raymond; Sands, Timothy; Génin, François Y

    2003-12-01

    Because of its simple composition, vast availability in pure form and ease of processing, vitreous silica is often used as a model to study the physics of amorphous solids. Research in amorphous silica is also motivated by its ubiquity in modern technology, a prominent example being as bulk material in transmissive and diffractive optics for high-power laser applications such as inertial confinement fusion (ICF). In these applications, stability under high-fluence laser irradiation is a key requirement, with optical breakdown occurring when the fluence of the beam is higher than the laser-induced damage threshold (LIDT) of the material. The optical strength of polished fused silica transmissive optics is limited by their surface LIDT. Surface optical breakdown is accompanied by densification, formation of point defects, cratering, material ejection, melting and cracking. Through a combination of electron diffraction and infrared reflectance measurements we show here that synthetic vitreous silica transforms partially into a defective form of the high-pressure stishovite phase under high-intensity (GW cm(-2)) laser irradiation. This phase transformation offers one suitable mechanism by which laser-induced damage grows catastrophically once initiated, thereby dramatically shortening the service lifetime of optics used for high-power photonics.

  11. Phase separation in the crust of accreting neutron stars.

    PubMed

    Horowitz, C J; Berry, D K; Brown, E F

    2007-06-01

    Nucleosynthesis, on the surface of accreting neutron stars, produces a range of chemical elements. We perform molecular dynamics simulations of crystallization to see how this complex composition forms new neutron star crust. We find chemical separation, with the liquid ocean phase greatly enriched in low atomic number elements compared to the solid crust. This phase separation should change many crust properties such as the thermal conductivity and shear modulus.

  12. Phase separation in the crust of accreting neutron stars

    SciTech Connect

    Horowitz, C. J.; Berry, D. K.; Brown, E. F.

    2007-06-15

    Nucleosynthesis, on the surface of accreting neutron stars, produces a range of chemical elements. We perform molecular dynamics simulations of crystallization to see how this complex composition forms new neutron star crust. We find chemical separation, with the liquid ocean phase greatly enriched in low atomic number elements compared to the solid crust. This phase separation should change many crust properties such as the thermal conductivity and shear modulus.

  13. Phase-Locked Semiconductor Lasers With Separate Contacts

    NASA Technical Reports Server (NTRS)

    Katz, Joseph; Yariv, Amnon; Margalit, Shlomo

    1988-01-01

    Individual current feeds enable better uniformity and flexible control. Separate contacts for lasers in array enable control of output radiation pattern and compensation of manufacturing nonuniformities among lasers. Concept of separate current control described for two-laser array in "Semiconductor Laser Phased Array" (NPO-15963).

  14. Characterization of Polymer Phase Separation of Reacting Systems

    NASA Astrophysics Data System (ADS)

    Yontz, D. J.; Hsu, S. L.; Gier, D.; Lidy, W.; Mazor, M.

    1997-03-01

    The degree of phase separation and size of the hard domains and soft domains that form in polyurethanes are highly dependent on the temperature at which phase separation occurs. This current study has focused on a polyurea urethane synthesized from toluene diisocyanate (TDI), water, and PPO. The temperature of this very exothermic system increases from room temperature to well over 100 ^circC in less than two minutes. This rise in temperature, especially during the first several minutes in which molecular weight buildup and phase separation compete, plays a significant role in the development of the final phase separated morphology. Samples prepared isothermally displayed a morphology that differed from that of the samples prepared with the inherent temperature profile. The evidence has shown that the phase separation process of this system cannot be predicted easily. Our experimental data have shown that competition between the rate of reaction and the phase separation rate is crucial to the production of this heterogeneous morphology. Infrared spectroscopy and atomic force microscopy analyses have proved to be instrumental in the characterization of the structures produced.

  15. 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.

  16. Mechanical Yield in Amorphous Solids: A First-Order Phase Transition

    NASA Astrophysics Data System (ADS)

    Jaiswal, Prabhat K.; Procaccia, Itamar; Rainone, Corrado; Singh, Murari

    2016-02-01

    Amorphous solids yield at a critical value of the strain (in strain-controlled experiments); for larger strains, the average stress can no longer increase—the system displays an elastoplastic steady state. A long-standing riddle in the materials community is what the difference is between the microscopic states of the material before and after yield. Explanations in the literature are material specific, but the universality of the phenomenon begs a universal answer. We argue here that there is no fundamental difference in the states of matter before and after yield, but the yield is a bona fide first-order phase transition between a highly restricted set of possible configurations residing in a small region of phase space to a vastly rich set of configurations which include many marginally stable ones. To show this, we employ an order parameter of universal applicability, independent of the microscopic interactions, that is successful in quantifying the transition in an unambiguous manner.

  17. The effect of Ta interface on the crystallization of amorphous phase change material thin films

    SciTech Connect

    Ghezzi, G. E.; Noé, P. Marra, M.; Sabbione, C.; Fillot, F.; Bernier, N.; Ferrand, J.; Maîtrejean, S.; Hippert, F.

    2014-06-02

    The crystallization of amorphous GeTe and Ge{sub 2}Sb{sub 2}Te{sub 5} phase change material films, with thickness between 10 and 100 nm, sandwiched between either Ta or SiO{sub 2} layers, was investigated by optical reflectivity. Ta cladding layers were found to increase the crystallization temperature, even for films as thick as 100 nm. X-Ray diffraction investigations of crystallized GeTe films showed a very weak texture in Ta cladded films, in contrast with the strong texture observed for SiO{sub 2} cladding layers. This study shows that crystallization mechanism of phase change materials can be highly impacted by interface effects, even for relatively thick films.

  18. Probe diffusion in phase-separated bicontinuous biopolymer gels.

    PubMed

    Wassén, Sophia; Bordes, Romain; Gebäck, Tobias; Bernin, Diana; Schuster, Erich; Lorén, Niklas; Hermansson, Anne-Marie

    2014-11-07

    Probe diffusion was determined in phase separated bicontinuous gels prepared by acid-induced gelation of the whey protein isolate-gellan gum system. The topological characterization of the phase-separated gel systems is achieved by confocal microscopy and the diffusion measurements are performed using pulsed field gradient (PFG) NMR and fluorescence recovery after photo-bleaching (FRAP). These two techniques gave complementary information about the mass transport at different time- and length scales, PFG NMR provided global diffusion rates in the gel systems, while FRAP enabled the measurements of diffusion in different phases of the phase-separated gels. The results revealed that the phase-separated gel with the largest characteristic wavelength had the fastest diffusion coefficient, while the gel with smaller microstructures had a slower probe diffusion rate. By using the diffusion data obtained by FRAP and the structural data from confocal microscopy, modelling through the lattice-Boltzmann framework was carried out to simulate the global diffusion and verify the validity of the experimental measurements. With this approach it was found that discrepancies between the two experimental techniques can be rationalized in terms of probe distribution between the different phases of the system. The combination of different techniques allowed the determination of diffusion in a phase-separated biopolymer gel and gave a clearer picture of this complex system. We also illustrate the difficulties that can arise if precautions are not taken to understand the system-probe interactions.

  19. Impact of polymers on the crystallization and phase transition kinetics of amorphous nifedipine during dissolution in aqueous media.

    PubMed

    Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

    2014-10-06

    The commercial and clinical success of amorphous solid dispersions (ASD) in overcoming the low bioavailability of poorly soluble molecules has generated momentum among pharmaceutical scientists to advance the fundamental understanding of these complex systems. A major limitation of these formulations stems from the propensity of amorphous solids to crystallize upon exposure to aqueous media. This study was specifically focused on developing analytical techniques to evaluate the impact of polymers on the crystallization behavior during dissolution, which is critical in designing effective amorphous formulations. In the study, the crystallization and polymorphic conversions of a model compound, nifedipine, were explored in the absence and presence of polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and HPMC-acetate succinate (HPMC-AS). A combination of analytical approaches including Raman spectroscopy, polarized light microscopy, and chemometric techniques such as multivariate curve resolution (MCR) were used to evaluate the kinetics of crystallization and polymorphic transitions as well as to identify the primary route of crystallization, i.e., whether crystallization took place in the dissolving solid matrix or from the supersaturated solutions generated during dissolution. Pure amorphous nifedipine, when exposed to aqueous media, was found to crystallize rapidly from the amorphous matrix, even when polymers were present in the dissolution medium. Matrix crystallization was avoided when amorphous solid dispersions were prepared, however, crystallization from the solution phase was rapid. MCR was found to be an excellent data processing technique to deconvolute the complex phase transition behavior of nifedipine.

  20. Thermal conductivity measurement of amorphous dielectric multilayers for phase-change memory power reduction

    SciTech Connect

    Fong, S. W. Wong, H.-S. P.; Sood, A.; Chen, L.; Kumari, N.; Gibson, G. A.; Asheghi, M.; Goodson, K. E.

    2016-07-07

    In this work, we investigate the temperature-dependent thermal conductivities of few nanometer thick alternating stacks of amorphous dielectrics, specifically SiO{sub 2}/Al{sub 2}O{sub 3} and SiO{sub 2}/Si{sub 3}N{sub 4}. Experiments using steady-state Joule-heating and electrical thermometry, while using a micro-miniature refrigerator over a wide temperature range (100–500 K), show that amorphous thin-film multilayer SiO{sub 2}/Si{sub 3}N{sub 4} and SiO{sub 2}/Al{sub 2}O{sub 3} exhibit through-plane room temperature effective thermal conductivities of about 1.14 and 0.48 W/(m × K), respectively. In the case of SiO{sub 2}/Al{sub 2}O{sub 3}, the reduced conductivity is attributed to lowered film density (7.03 → 5.44 × 10{sup 28 }m{sup –3} for SiO{sub 2} and 10.2 → 8.27 × 10{sup 28 }m{sup –3} for Al{sub 2}O{sub 3}) caused by atomic layer deposition of thin-films as well as a small, finite, and repeating thermal boundary resistance (TBR) of 1.5 m{sup 2} K/GW between dielectric layers. Molecular dynamics simulations reveal that vibrational mismatch between amorphous oxide layers is small, and that the TBR between layers is largely due to imperfect interfaces. Finally, the impact of using this multilayer dielectric in a dash-type phase-change memory device is studied using finite-element simulations.

  1. Effects of magnetomechanical vibrations and bending stresses on three-phase three-leg transformers with amorphous cores

    NASA Astrophysics Data System (ADS)

    Hsu, Chang-Hung; Chang, Yeong-Hwa; Lee, Chun-Yao; Yao, Chia-Shiang; He, Yan-Lou; Chu, Huei-Lung; Chang, Chia-Wen; Chan, Wei-Shou

    2012-04-01

    This paper explores the influence of bending stresses on the magnetic characteristics of three-phase transformers with amorphous cores. Different types of core structures, including C-cores and toroidal cores, and their magnetic properties are compared using VSM and XRD. The losses in the magnetic core of the three-phase transformer are analyzed using the finite element analysis for both design and measurement. In addition, experimental results indicated that amorphous-core transformers with rectangular corners had higher audible noise and vibration intensities. This is because the condensed distribution of magnetic flux lines in the corners of the core may create high magnetic inductions associated with high magnetostriction. Finally, experiments with three-phase amorphous-core transformers were performed to study the effects of magnetism and magnetostriction on their performance in terms of core loss, vibration, and audible noise.

  2. Separate Magnitude and Phase Regularization via Compressed Sensing

    PubMed Central

    Noll, Douglas C.; Nielsen, Jon-Fredrik; Fessler, Jeffrey A.

    2012-01-01

    Compressed sensing (CS) has been used for accelerating magnetic resonance imaging (MRI) acquisitions, but its use in applications with rapid spatial phase variations is challenging, e.g., proton resonance frequency shift (PRF-shift) thermometry and velocity mapping. Previously, an iterative MRI reconstruction with separate magnitude and phase regularization was proposed for applications where magnitude and phase maps are both of interest, but it requires fully sampled data and unwrapped phase maps. In this paper, CS is combined into this framework to reconstruct magnitude and phase images accurately from undersampled data. Moreover, new phase regularization terms are proposed to accommodate phase wrapping and to reconstruct images with encoded phase variations, e.g., PRF-shift thermometry and velocity mapping. The proposed method is demonstrated with simulated thermometry data and in-vivo velocity mapping data and compared to conventional phase corrected CS. PMID:22552571

  3. 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.

  4. 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. .

  5. Laser-induced phase separation of silicon carbide.

    PubMed

    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

    2016-11-30

    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.

  6. Laser-induced phase separation of silicon carbide

    NASA Astrophysics Data System (ADS)

    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

    2016-11-01

    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.

  7. 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

  8. Cytoskeletal pinning controls phase separation in multicomponent lipid membranes.

    PubMed

    Arumugam, Senthil; Petrov, Eugene P; Schwille, Petra

    2015-03-10

    We study the effect of a minimal cytoskeletal network formed on the surface of giant unilamellar vesicles by the prokaryotic tubulin homolog, FtsZ, on phase separation in freestanding lipid membranes. FtsZ has been modified to interact with the membrane through a membrane targeting sequence from the prokaryotic protein MinD. FtsZ with the attached membrane targeting sequence efficiently forms a highly interconnected network on membranes with a concentration-dependent mesh size, much similar to the eukaryotic cytoskeletal network underlying the plasma membrane. Using giant unilamellar vesicles formed from a quaternary lipid mixture, we demonstrate that the artificial membrane-associated cytoskeleton, on the one hand, suppresses large-scale phase separation below the phase transition temperature, and, on the other hand, preserves phase separation above the transition temperature. Our experimental observations support the ideas put forward in our previous simulation study: In particular, the picket fence effect on phase separation may explain why micrometer-scale membrane domains are observed in isolated, cytoskeleton-free giant plasma membrane vesicles, but not in intact cell membranes. The experimentally observed suppression of large-scale phase separation much below the transition temperatures also serves as an argument in favor of the cryoprotective role of the cytoskeleton. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  9. Anomalous small-angle X-ray scattering of nanoporous two-phase atomistic models for amorphous silicon–germanium alloys

    SciTech Connect

    Chehaidar, A.

    2015-09-15

    The present work deals with a detailed analysis of the anomalous small-angle X-ray scattering in amorphous silicon–germanium alloy using the simulation technique. We envisage the nanoporous two-phase alloy model consisting in a mixture of Ge-rich and Ge-poor domains and voids at the nanoscale. By substituting Ge atoms for Si atoms in nanoporous amorphous silicon network, compositionally heterogeneous alloys are generated with various composition-contrasts between the two phases. After relaxing the as-generated structure, we compute its radial distribution function, and then we deduce by the Fourier transform technique its anomalous X-ray scattering pattern. Using a smoothing procedure, the computed X-ray scattering patterns are corrected for the termination errors due to the finite size of the model, allowing so a rigorous quantitative analysis of the anomalous small-angle scattering. Our simulation shows that, as expected, the anomalous small-angle X-ray scattering technique is a tool of choice for characterizing compositional heterogeneities coexisting with structural inhomogeneities in an amorphous alloy. Furthermore, the sizes of the compositional nanoheterogeneities, as measured by anomalous small-angle X-ray scattering technique, are X-ray energy independent. A quantitative analysis of the separated reduced anomalous small-angle X-ray scattering, as defined in this work, provided a good estimate of their size.

  10. Study on Solid-Phase Crystallization of Amorphized Vanadium-Doped ZnO Thin Films

    NASA Astrophysics Data System (ADS)

    Watanabe, Akihiro; Chiba, Hiroshi; Kawashima, Tomoyuki; Washio, Katsuyoshi

    2016-04-01

    The effects of post-annealing and film thickness on the solid-phase crystallization (SPC) of amorphized vanadium-doped ZnO (VZO) thin films were investigated. The 2-500-nm-thick VZO (V of about 4 at.%) thin films were deposited on a c-face sapphire substrate at room temperature by RF magnetron sputtering and subsequently were annealed at an annealing temperature (T A) from 700°C to 900°C in a nitrogen atmosphere. From in-plane x-ray diffraction (XRD) measurements, the as-deposited VZO film had a faint in-plane orientation at the initial stage of deposition. However, the ZnO(100) XRD intensity weakened with increasing film thickness and no diffraction peak was seen over 35-nm thick. That is, the pseudo-amorphous film was fabricated. By annealing the 100-nm-thick VZO film over 700°C, the sixfold symmetry appeared. The ZnO(100) XRD intensity increased sharply at a T A of 800°C and was saturated at a higher T A. The c axis orientation reached a peak at a T A of 800°C according to the ZnO(002) XRD intensity. Concerning the effect of film thickness in the case of T A = 800°C, both the in-plane and c axis orientation improved up to 100-nm thick and deteriorated over it. At a T A ≥ 850°C or film thickness ≥200 nm, where the c axis orientation was deteriorated, the secondary phase-like Zn3V2O8 was formed. As a result, it is found that the careful selection of the T A and film thickness is necessary to avoid the formation of secondary phase-like Zn3V2O8 to fabricate the high-quality buffer layer via SPC.

  11. Quasi-amorphous inorganic thin films: non-crystalline polar phases.

    PubMed

    Wachtel, Ellen; Lubomirsky, Igor

    2010-06-18

    Quasi-amorphous thin films of BaTiO3, SrTiO3, and BaZrO3 are the only known examples of inorganic, non-crystalline, polar materials. The conditions under which they are formed and the origin of their polarity set these materials apart from other classes of inorganic materials. The most important feature of the quasi-amorphous phase is that the polarity is the result of the orientational ordering of local bonding units but without any detectable spatial periodicity. This mechanism is reminiscent of that observed in ferroelectric polymers and permits compounds that do not have polar crystalline polymorphs, such as SrTiO3 and BaZrO3, to form polar non-crystalline solids. In the present report, we provide an overview of the essential features of these materials including preparation, structure, and chemical composition. The report also reviews our current level of understanding and offers some guidelines for further development and application of non-crystalline inorganic polar materials.

  12. Thermal crystallization of sputter-deposited amorphous Ge films: Competition of diamond cubic and hexagonal phases

    NASA Astrophysics Data System (ADS)

    Okugawa, M.; Nakamura, R.; Ishimaru, M.; Yasuda, H.; Numakura, H.

    2016-12-01

    Following our previous studies on crystallization induced by electron irradiation, we have investigated the crystallization of sputter-deposited amorphous germanium films by heat treatments. On continuous heating, samples aged for 3 days and 4 months at room temperature crystallized at 500°C to form coarse spherical particles of a hexagonal structure, of about 100 nm in diameter, whereas samples aged for 7 months turned to homogeneous nanograins of the diamond cubic structure at 600°C. When the films aged for 4 months at room temperature were annealed at 350°C for 2 h and then heated, they crystallized at 550°C to form a mixture of the two microstructures, and those annealed at 350°C and further at 500°C for 1 h crystallized at 600°C mostly to nanograins. Crystallization by electron irradiation at 350°C to 4-month-aged samples has also been studied. With increasing annealing time at 350°C, coarse particles of a hexagonal structure ceased to appear, and were replaced by fine nanograins of the diamond cubic structure. These observations can be understood in terms of structural instability of sputter-deposited amorphous films. Medium-range ordered clusters must initially be present in the films and serve as nuclei of the metastable hexagonal phase. They are unstable, however, and are eliminated by annealing, resulting in the reduction in size and number of coarse particles with a metastable structure.

  13. Nanoscale control over phase separation in conjugated polymer blends using mesoporous silica spheres.

    PubMed

    Kelly, Timothy L; Yano, Kazuhisa; Wolf, Michael O

    2010-01-05

    A method of preparing blended conjugated polymer microparticles using mesoporous silica spheres is described. Poly(3,4-ethylenedioxythiophene) (PEDOT) was blended with poly(furfuryl alcohol) (PFA) by a sequential infiltration-polymerization approach. The materials were evaluated by both scanning and transmission electron microscopy and are shown to retain the overall spherical structure of the silica template. The filling of the mesopores and the polymer distribution within individual particles were determined by a combination of energy-dispersive X-ray microanalysis, X-ray photoelectron spectroscopy, and nitrogen adsorption. The results suggest that when PEDOT is added to the silica host, followed by PFA, the phase separation of the two immiscible polymers is constrained by the dimensions of the silica mesopores, ensuring nanoscale contact between the two phases. The silica template can be removed by etching with 25% hydrofluoric acid, leaving behind a blended polymer microparticle. The etched microparticles exhibit macroporous morphologies different from that of pure PEDOT particles prepared by a similar route. The blended microparticles also appear to undergo limited phase separation; no evidence for distinct polymer domains was observed. Conductivity measurements indicate that the blended particles are above the percolation threshold and support the conclusion that the phase domains are extremely small. Importantly, when PFA is added to the host first, followed by PEDOT, there is a striking difference to the final composition and morphology of the particles. This reversal of the blending order results in a more amorphous, phase-separated material. These results demonstrate the preparation of conjugated polymer blends with engineered nanoscale phase separation and may allow for future improvements in organic device architecture and performance.

  14. Atomic scale insight into the amorphous structure of Cu doped GeTe phase-change material

    SciTech Connect

    Zhang, Linchuan; Sa, Baisheng; Zhou, Jian; Sun, Zhimei; Song, Zhitang

    2014-10-21

    GeTe shows promising application as a recording material for phase-change nonvolatile memory due to its fast crystallization speed and extraordinary amorphous stability. To further improve the performance of GeTe, various transition metals, such as copper, have been doped in GeTe in recent works. However, the effect of the doped transition metals on the stability of amorphous GeTe is not known. Here, we shed light on this problem for the system of Cu doped GeTe by means of ab initio molecular dynamics calculations. Our results show that the doped Cu atoms tend to agglomerate in amorphous GeTe. Further, base on analyzing the pair correlation functions, coordination numbers and bond angle distributions, remarkable changes in the local structure of amorphous GeTe induced by Cu are obviously seen. The present work may provide some clues for understanding the effect of early transition metals on the local structure of amorphous phase-change compounds, and hence should be helpful for optimizing the structure and performance of phase-change materials by doping transition metals.

  15. Characterizing the Phyllosilicates and Amorphous Phases Found by MSL Using Laboratory XRD and EGA Measurements of Natural and Synthetic Materials

    NASA Technical Reports Server (NTRS)

    Rampe, Elizabeth B.; Morris, Richard V.; Chipera, Steve; Bish, David L.; Bristow, Thomas; Archer, Paul Douglas; Blake, David; Achilles, Cherie; Ming, Douglas W.; Vaniman, David; hide

    2013-01-01

    The Curiosity Rover landed on the Peace Vallis alluvial fan in Gale crater on August 5, 2012. A primary mission science objective is to search for past habitable environments, and, in particular, to assess the role of past water. Identifying the minerals and mineraloids that result from aqueous alteration at Gale crater is essential for understanding past aqueous processes at the MSL landing site and hence for interpreting the site's potential habitability. X-ray diffraction (XRD) data from the CheMin instrument and evolved gas analyses (EGA) from the SAM instrument have helped the MSL science team identify phases that resulted from aqueous processes: phyllosilicates and amorphous phases were measure in two drill samples (John Klein and Cumberland) obtained from the Sheepbed Member, Yellowknife Bay Fm., which is believed to represent a fluvial-lacustrine environment. A third set of analyses was obtained from scoop samples from the Rocknest sand shadow. Chemical data from the APXS instrument have helped constrain the chemical compositions of these secondary phases and suggest that the phyllosilicate component is Mg-enriched and the amorphous component is Fe-enriched, relatively Si-poor, and S- and H-bearing. To refine the phyllosilicate and amorphous components in the samples measured by MSL, we measured XRD and EGA data for a variety of relevant natural terrestrial phyllosilicates and synthetic mineraloids in laboratory testbeds of the CheMin and SAM instruments. Specifically, Mg-saturated smectites and vermiculites were measured with XRD at low relative humidity to understand the behavior of the 001 reflections under Mars-like conditions. Our laboratory XRD measurements suggest that interlayer cation composition affects the hydration state of swelling clays at low RH and, thus, the 001 peak positions. XRD patterns of synthetic amorphous materials, including allophane, ferrihydrite, and hisingerite were used in full-pattern fitting (FULLPAT) models to help

  16. Amine templated zinc phosphates phases for membrane separations

    SciTech Connect

    Nenoff, T.M.; Chavez, A.V.; Thoma, S.G.; Provencio, P.; Harrison, W.T.A.; Phillips, M.L.F.

    1998-08-01

    This research is focused on developing inorganic molecular sieve membranes for light gas separations such as hydrogen recovery and natural gas purification, and organic molecular separations, such as chiral enantiomers. The authors focus on zinc phosphates because of the ease in crystallization of new phases and the wide range of pore sizes and shapes obtained. With hybrid systems of zinc phosphate crystalline phases templated by amine molecules, the authors are interested in better understanding the association of the template molecules to the inorganic phase, and how the organic transfers its size, shape, and (in some cases) chirality to the bulk. Furthermore, the new porous phases can also be synthesized as thin films on metal oxide substrates. These films allow one to make membranes from organic/inorganic hybrid systems, suitable for diffusion experiments. Characterization techniques for both the bulk phases and the thin films include powder X-ray diffraction, TGA, Scanning Electron Micrograph (SEM) and Electron Dispersive Spectrometry (EDS).

  17. Phase separation of lanthanum hydride under high pressure

    NASA Astrophysics Data System (ADS)

    Machida, A.; Watanuki, T.; Kawana, D.; Aoki, K.

    2011-02-01

    Structural change of lanthanum dihydride LaH2.3, which has a face-centered-cubic (fcc) metal lattice with tetrahedral interstitial sites fully occupied with hydrogen atoms and partially occupied octahedral sites, has been investigated at high pressures up to 20 GPa at ambient temperature by synchrotron radiation x-ray diffraction. Additional Bragg reflections appear just on higher angle sides of the original ones at ~11 GPa and their peak intensities increase gradually on further compression. The coexistence state of two fcc metal lattices thus observed above 11 GPa is interpreted in terms of phase separation or disproportionation reaction from the dihydride toward a solid solution and trihydride states, in both of which the octahedral interstitial sites are partially occupied with hydrogen atoms. A gradual distortion from the cubic to a tetragonal lattice is observed prior to the phase separation. The coexistence phase goes back to the dihydride fcc phase via the lattice distorted phase with decreasing pressure.

  18. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

    PubMed Central

    Lan, S.; Ren, Y.; Wei, X. Y.; Wang, B.; Gilbert, E. P.; Shibayama, T.; Watanabe, S.; Ohnuma, M.; Wang, X. -L.

    2017-01-01

    An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase, which forms the room-temperature glass phase on quenching. The outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat treatment. PMID:28303882

  19. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

    DOE PAGES

    Lan, S.; Ren, Y.; Wei, X. Y.; ...

    2017-03-17

    An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in-situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clustersmore » over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase which forms the room-temperature glass phase upon quenching. Finally, the outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat-treatment.« less

  20. Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses.

    PubMed

    Lan, S; Ren, Y; Wei, X Y; Wang, B; Gilbert, E P; Shibayama, T; Watanabe, S; Ohnuma, M; Wang, X-L

    2017-03-17

    An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase, which forms the room-temperature glass phase on quenching. The outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat treatment.

  1. Exploiting the Phenomenon of Liquid-Liquid Phase Separation for Enhanced and Sustained Membrane Transport of a Poorly Water-Soluble Drug.

    PubMed

    Indulkar, Anura S; Gao, Yi; Raina, Shweta A; Zhang, Geoff G Z; Taylor, Lynne S

    2016-06-06

    Recent studies on aqueous supersaturated lipophilic drug solutions prepared by methods including antisolvent addition, pH swing, or dissolution of amorphous solid dispersions (ASDs) have demonstrated that when crystallization is slow, these systems undergo liquid-liquid phase separation (LLPS) when the concentration of the drug in the medium exceeds its amorphous solubility. Following LLPS, a metastable equilibrium is formed where the concentration of drug in the continuous phase corresponds to the amorphous solubility while the dispersed phase is composed of a nanosized drug-rich phase. It has been reasoned that the drug-rich phase may act as a reservoir, enabling the rate of passive transport of the drug across a membrane to be maintained at the maximum value for an extended period of time. Herein, using clotrimazole as a model drug, and a flow-through diffusion cell, the reservoir effect is demonstrated. Supersaturated clotrimazole solutions at concentrations below the amorphous solubility show a linear relationship between the maximum flux and the initial concentration. Once the concentration exceeds the amorphous solubility, the maximum flux achieved reaches a plateau. However, the duration for which the high flux persists was found to be highly dependent on the number of drug-rich nanodroplets present in the donor compartment. Macroscopic amorphous particles of clotrimazole did not lead to the same reservoir effect observed with the nanodroplets formed through the process of LLPS. A first-principles mathematical model was developed which was able to fit the experimental receiver concentration-time profiles for concentration regimes both below and above amorphous solubility, providing support for the contention that the nanodroplet phase does not directly diffuse across the membrane but, instead, rapidly replenishes the drug in the aqueous phase that has been removed by transport across the membrane. This study provides important insight into the properties of

  2. Distribution of nanoscale nuclei in the amorphous dome of a phase change random access memory

    SciTech Connect

    Lee, Bong-Sub Darmawikarta, Kristof; Abelson, John R.; Raoux, Simone; Shih, Yen-Hao; Zhu, Yu

    2014-02-17

    The nanoscale crystal nuclei in an amorphous Ge{sub 2}Sb{sub 2}Te{sub 5} bit in a phase change memory device were evaluated by fluctuation transmission electron microscopy. The quench time in the device (∼10 ns) afforded more and larger nuclei in the melt-quenched state than in the as-deposited state. However, nuclei were even more numerous and larger in a test structure with a longer quench time (∼100 ns), verifying the prediction of nucleation theory that slower cooling produces more nuclei. It also demonstrates that the thermal design of devices will strongly influence the population of nuclei, and thus the speed and data retention characteristics.

  3. CFA Films in Amorphous Substrate: Structural Phase Induction and Magnetization Dynamics

    NASA Astrophysics Data System (ADS)

    Correa, M. A.; Bohn, F.; Escobar, V. M.

    We report a systematic study of the structural and quasi-static magnetic properties, as well as of the dynamic magnetic response through MI effect, in Co2FeAl and MgO//Co2FeAl single layers and a MgO//Co2FeAl/Ag/Co2FeAl trilayered film, all grown onto an amorphous substrate. We present a new route to induce the crystalline structure in the Co2FeAl alloy and verify that changes in the structural phase of this material leads to remarkable modifications of the magnetic anisotropy and, consequently, dynamic magnetic behavior. Considering the electrical and magnetic properties of the Co2FeAl, our results open new possibilities for technological applications of this full-Heusler alloy in rigid and flexible spintronic devices.

  4. Phase separation of equilibrium polymers of proteins in living cells.

    PubMed

    Sear, Richard P

    2008-01-01

    A number of proteins polymerise reversibly in living cells. The equilibrium polymers are functional: if mutant proteins are made that cannot polymerise, then these proteins cannot perform their biological functions. Furthermore, these polymers of proteins appear to phase separate inside the cell. The dynamics of one of these polymerising, phase separating proteins has been studied via fluorescence recovery after photobleaching (FRAP) by Bienz and coworkers. Here, their data is compared with the results of quantitative modelling to gain a better understanding of the dynamics of this protein inside a cell. The protein is called Dishevelled; it is a protein essential to the development of all animals and the name originates in the disruption of hair formation in a mutant version of this protein. It is not known how polymerisation and phase separation enable Dishevelled to perform its biological function but here we propose and discuss two possibilities. The first is that the cell is exploiting the inherently sharp, switch-like nature of a phase transition to respond in a switch-like way to a external signal. The second is that phase separation dynamically creates a compartment (the more concentrated phase) into which other proteins partition.

  5. Continuous flow system for controlling phases separation near λ transition

    SciTech Connect

    Chorowski, M.; Poliński, J.; Kempiński, W.; Trybuła, Z.; Łoś, Sz.; Chołast, K.; Kociemba, A.

    2014-01-29

    As demands on 3He are increasing and conventional 3He production through tritium decay is decreasing, alternative 3He production methods are becoming economically viable. One such possibility is to use entropy filters for extraction of the 3He isotope from natural gas. According to the phase diagram of the 3He, its solidification is impossible by only lowering of the temperature. Hence during the cooling process at stable pressure we can reach λ-point and pass to the special phase - He II. The total density of HeII is a sum of the two phases: normal the superfluid ones. It is possible to separate these two phases with an entropy filter - the barrier for the classically-behaving normal phase. This barrier can also be used to separate the two main isotopes of He: 4He and 3He, because at temperatures close to the 4He-λ-point the 3He isotope is part of the normal phase. The paper presents continuous flow schemes of different separation methods of 3He from helium commodity coming from natural gas cryogenic processing. An overall thermodynamic efficiency of the 3He/4He separation process is presented. A simplified model of continuous flow HeI -HeII recuperative heat exchanger is given. Ceramic and carbon porous plugs have been tested in entropy filter applications.

  6. Amorphization of Al[sub 6]Mn phase in an Al-14 a/o Mn alloy during low energy helium ion bombardment

    SciTech Connect

    Nair, K.G.M.; Krishan, K. . Materials Science Division); Vijayalakshmi, M. . Metallurgy Division)

    1993-10-01

    Amorphization of ordered intermetallic compounds has been observed during ion, electron and neutron irradiations. Investigations have been carried out in a number of systems. It has been generally observed that intermetallic compounds with a narrow range of homogeneity (line compounds) amorphize on irradiation. The present paper reports the observation of irradiation-induced amorphization in the Al[sub 6]Mn phase in an Al-14 a/o Mn alloy. The dose and energy dependence of the amorphization process are discussed. The present studies suggest that the defects produced during irradiation rather than the implanted atoms (helium) play a major role in the crystalline to amorphous transition.

  7. Ultrafast optical response of the amorphous and crystalline states of the phase change material Ge2Sb2Te5

    NASA Astrophysics Data System (ADS)

    Miller, T. A.; Rudé, M.; Pruneri, V.; Wall, S.

    2016-07-01

    We examine the ultrafast optical response of the crystalline and amorphous phases of the phase change material Ge2Sb2Te5 (GST) below the phase transformation threshold. Simultaneous measurement of the transmissivity and reflectivity of thin film samples yields the time-dependent evolution of the dielectric function for both phases. We then identify how lattice motion and electronic excitation manifest in the dielectric response. The dielectric response of both phases is large but markedly different. At 800 nm, the changes in amorphous GST are well described by the Drude response of the generated photocarriers, whereas the crystalline phase is better described by the depopulation of resonant bonds. We find that the generated coherent phonons have a greater influence in the amorphous phase than the crystalline phase. Furthermore, coherent phonons do not influence resonant bonding. For fluences up to 50% of the transformation threshold, the structure does not exhibit bond softening in either phase, enabling large changes of the optical properties without structural modification.

  8. Gas Phase Chiral Separations By Ion Mobility Spectrometry

    PubMed Central

    Dwivedi, Prabha; Wu, Ching; Hill, Herbert H.

    2013-01-01

    This manuscript introduces the concept of Chiral Ion Mobility Spectrometry (CIMS) and presents examples demonstrating the gas phase separation of enantiomers of a wide range of racemates including pharmaceuticals, amino acids and carbohydrates. CIMS is similar to traditional ion mobility spectrometry (IMS), where gas phase ions, when subjected to a potential gradient are separated at atmospheric pressure due to differences in their shapes and sizes. In addition to size and shape, CIMS separates ions based on their stereospecific interaction with a chiral gas. In order to achieve chiral discrimination by CIMS, an asymmetric environment was provided by doping the drift gas with a volatile chiral reagent. In this study S-(+)-2-butanol was used as a chiral modifier to demonstrate enantiomeric separations of atenolol, serine, methionine, threonine, methyl-α-glucopyranoside, glucose, penicillamine, valinol, phenylalanine, and tryptophan from their respective racemic mixtures. PMID:17165808

  9. Phase separation during radiation crosslinking of unsaturated polyester resin

    NASA Astrophysics Data System (ADS)

    Pucić, Irina; Ranogajec, Franjo

    2003-06-01

    Phase separation during radiation-initiated crosslinking of unsaturated polyester resin was studied. Residual reactivity of liquid phases and gels of partially cured samples was determined by DSC. Uncured resin and liquid phases showed double reaction exotherm, gels had a single maximum that corresponded to higher-temperature maximum of liquid parts. The lower-temperature process was attributed to styrene-polyester copolymerization. At higher temperatures, polyester unsaturations that remained unreacted due to microgel formation homopolymerized. FTIR revealed different composition of phases. In thicker samples, reaction heat influenced microgel formation causing delayed appearance of gel and faster increase in conversion.

  10. Possible existence of two amorphous phases of d-mannitol related by a first-order transition

    NASA Astrophysics Data System (ADS)

    Zhu, Men; Wang, Jun-Qiang; Perepezko, John H.; Yu, Lian

    2015-06-01

    We report that the common polyalcohol d-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature Tg (284 K), the supercooled liquid (SCL) of d-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near Tg + 50 K, enabling a determination of their equilibrium temperature. The presence of d-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from d-mannitol's SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near Tg with substantial enthalpy decrease toward the crystalline phases; the processes in water and d-mannitol both strengthen the hydrogen bonds. In contrast to TPP, d-mannitol's Phase X forms more rapidly and can transform back to the SCL. These features make d-mannitol a valuable new model for understanding polyamorphism.

  11. Possible existence of two amorphous phases of D-mannitol related by a first-order transition

    SciTech Connect

    Zhu, Men; Yu, Lian; Wang, Jun-Qiang; Perepezko, John H.

    2015-06-28

    We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature T{sub g} (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near T{sub g} + 50 K, enabling a determination of their equilibrium temperature. The presence of D-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from D-mannitol’s SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near T{sub g} with substantial enthalpy decrease toward the crystalline phases; the processes in water and D-mannitol both strengthen the hydrogen bonds. In contrast to TPP, D-mannitol’s Phase X forms more rapidly and can transform back to the SCL. These features make D-mannitol a valuable new model for understanding polyamorphism.

  12. X-Ray Amorphous Phases in Antarctica Dry Valley Soils: Insight into Aqueous Alteration Processes on Mars?

    NASA Technical Reports Server (NTRS)

    Ming, D. W.; Morris, R. V.; Rampe, E. B.; Golden, D. C.; Quinn, J. E.

    2015-01-01

    The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 weight percentage) of X-ray amorphous materials in a windblown deposit (Rocknest) and in a sedimentary mudstone (Cumberland and John Klein) in Gale crater, Mars. On Earth, X-ray amorphous components are common in soils and sediments, but usually not as abundant as detected in Gale crater. One hypothesis for the abundant X-ray amorphous materials on Mars is limited interaction of liquid water with surface materials, kinetically inhibiting maturation to more crystalline phases. The objective of this study was to characterize the chemistry and mineralogy of soils formed in the Antarctica Dry Valleys, one of the driest locations on Earth. Two soils were characterized from different elevations, including a low elevation, coastal, subxerous soil in Taylor Valley and a high elevation, ultraxerous soil in University Valley. A variety of techniques were used to characterize materials from each soil horizon, including Rietveld analysis of X-ray diffraction data. For Taylor Valley soil, the X-ray amorphous component ranged from about 4 weight percentage in the upper horizon to as high as 15 weight percentage in the lowest horizon just above the permafrost layer. Transmission electron microscopy indicated that the presence of short-range ordered (SRO) smectite was the most likely candidate for the X-ray amorphous materials in the Taylor Valley soils. The SRO smectite is likely an aqueous alteration product of mica inherited from granitic materials during glaciation of Taylor Valley. The drier University Valley soils had lower X-ray amorphous contents of about 5 weight percentage in the lowest horizon. The X-ray amorphous materials in University Valley are attributed to nanoparticles of TiO2 and possibly amorphous SiO2. The high abundance of X-ray amorphous materials in Taylor Valley is surprising for one of the driest places on Earth. These materials

  13. X-ray Amorphous Phases in Antarctica Dry Valley Soils: Insight into Aqueous Alteration Processes on Mars?

    NASA Astrophysics Data System (ADS)

    Ming, D. W.; Morris, R. V.; Rampe, E. B.; Quinn, J. E.; Graff, T. G.

    2015-12-01

    The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 wt. %) of X-ray amorphous materials in a windblown deposit (Rocknest) and in a sedimentary mudstone (Cumberland and John Klein) in Gale crater. On Earth, X-ray amorphous components are common in soils and sediments, but usually not as abundant as detected in Gale crater. One hypothesis for the abundant X-ray amorphous materials on Mars is limited interaction of liquid water with surface materials, kinetically inhibiting maturation to more crystalline phases. The objective of this study was to characterize the chemistry and mineralogy of soils formed in the Antarctica Dry Valleys, one of the driest locations on Earth. Two soils were characterized from different elevations, including a low elevation, coastal, subxerous soil in Taylor Valley and a high elevation, ultraxerous soil in University Valley. A variety of techniques were used to characterize materials from each soil horizon, including Rietveld analysis of X-ray diffraction data. For Taylor Valley soil, the X-ray amorphous component ranged from about 4 wt. % in the upper horizon to as high as 15 wt. % in the lowest horizon just above the permafrost layer. Transmission electron microscopy indicated that the presence of short-range ordered (SRO) smectite was the most likely candidate for the X-ray amorphous materials in the Taylor Valley soils. The SRO smectite is likely an aqueous alteration product of mica inherited from granitic materials during glaciation of Taylor Valley. The drier University Valley soil had lower X-ray amorphous contents of about 5 wt. % througout the profile. The X-ray amorphous materials in University Valley are attributed to nanoparticles of TiO2 and possibly amorphous SiO2. The high abundance of X-ray amorphous materials in Taylor Valley is surprising for one of the driest places on Earth. These materials may have been physically and chemical altered during

  14. Stabilization of organic matter in soils: role of amorphous mineral phases

    NASA Astrophysics Data System (ADS)

    Zewde Tamrat, Wuhib; Rose, Jérôme; Levard, Clément; Chaurand, Perrine; Basile-Doelsch, Isabelle

    2016-04-01

    Soil organic matter (SOM) globally contributes the largest portion of continental carbon stock. One major issue concerning this large C pool includes its instability by mineralization and erosion due to land use. The main hypothesis of this work is that physicochemical stabilization of SOM is mainly driven by interactions of organic compounds, not with mineral surfaces as classically considered, but with amorphous polymers continuously formed by the alteration of soil minerals(1-3). Our objective is to understand how nano-organomineral complexes (nCOMx) are structured at the nanoscale, assess mechanisms of their formation, and quantify the effects of their occurrence on SOM turnovers. Due to inherent high complexity of natural samples, our methodology is based on the formation of nCOMx from both synthetic systems and natural mineral-weathered components. For the mineral component, biotite (from Bancroft, Canada) was selected. For the organic component, 3,4-Dihydroxy-L-phenylalanine, an amino acid with hydroxyl (pKa=9.95), carboxyl (pKa=2,58), amino (pKa=9,24) and an aromatic functions was chosen. The methodology aimed at developing conditions that generate biotite dissolution and nCOMx precipitation. The second step of the experiment consisted of the precipitation of nCOMx by slowly increasing pH over 3 to 12 hours of hydrolysis. Three final pH conditions were tested (4.2, 5 and 7) with Metal/Carbon ratios of 0.01, 0.1, 1, 10 and 'No Carbon'. The first results of dissolution rates and congruency, AFM imaging, ICPMS, HR-TEM and XRD as well as XAS characterizations (transmission and florescence mode at the Fe K-edge) of nCOMx will be presented. Experiments and analysis techniques were designed to study these synthetic phases with regard to Si, Al, Fe and OM proportions to increase the OM proportion (as in natural soil phases) and also increase the stability of the OM phase (as in increased residence time of OM in the soil). We will focus particularly on the Fe state

  15. Shape Deformation of Ternary Vesicles Coupled with Phase Separation

    NASA Astrophysics Data System (ADS)

    Yanagisawa, Miho; Imai, Masayuki; Taniguchi, Takashi

    2008-04-01

    We report an experimental study on shape deformations of ternary vesicles undergoing phase separation under an osmotic pressure difference. The phase separation on various shape vesicles causes unique shape-deformation branches. In the domain coarsening stage, prolate, discocyte, and starfish vesicles show a shape convergence to discocytes, whereas a pearling instability is observed in tube vesicles. In late stages, the domains start to bud towards the inside or outside of the vesicle depending on the excess area. We discuss the deformation branches based on the membrane elasticity model.

  16. Phase separation in thin films: Effect of temperature gradients

    NASA Astrophysics Data System (ADS)

    Jaiswal, Prabhat K.; Puri, Sanjay; Binder, Kurt

    2013-09-01

    We study the phase-separation kinetics of a binary (AB) mixture confined in a thin film of thickness D with a temperature gradient. Starting from a Kawasaki-exchange kinetic Ising model, we use a master-equation approach to systematically derive an extension of the Cahn-Hilliard model for this system. We study the effect of temperature gradients perpendicular to the film with “neutral” (no preference for either A or B) surfaces. We highlight the rich phenomenology and pattern dynamics which arises from the interplay of phase separation and the temperature gradient.

  17. Use of X-ray tomography to map crystalline and amorphous phases in frozen biomaterials.

    PubMed

    Bischof, J C; Mahr, B; Choi, J H; Behling, M; Mewes, D

    2007-02-01

    The outcome of both cryopreservation and cryosurgical freezing applications is influenced by the concentration and type of the cryoprotective agent (CPA) or the cryodestructive agent (i.e., the chemical adjuvants referred to here as CDA) added prior to freezing. It also depends on the amount and type of crystalline, amorphous and/or eutectic phases formed during freezing which can differentially affect viability. This work describes the use of X-ray computer tomography (CT) for non-invasive, indirect determination of the phase, solute concentration and temperature within biomaterials (CPA, CDA loaded solutions and tissues) by X-ray attenuation before and after freezing. Specifically, this work focuses on establishing the feasibility of CT (100-420 kV acceleration voltage) to accurately measure the concentration of glycerol or salt as model CPA and CDAs in unfrozen solutions and tissues at 20 degrees C, or the phase in frozen solutions and tissue systems at -78.5 and -196 degrees C. The solutions are composed of water with physiological concentrations of NaCl (0.88% wt/wt) and DMEM (Dulbecco's Modified Eagle's Medium) with added glycerol (0-8 M). The tissue system is chosen as 3 mm thick porcine liver slices as well as 2 cm diameter cores which were either imaged fresh (3-4 h cold ischemia) or after loading with DMEM based glycerol solutions (0-8 M) for times ranging from hours to 7 days at 4 degrees C. The X-ray attenuation is reported in Hounsfield units (HU), a clinical measurement which normalizes X-ray attenuation values by the difference between those of water and air. NaCl solutions from 0 to 23.3% wt/wt (i.e. water to eutectic concentration) were found to linearly correspond to HU in a range from 0 to 155. At -196 degrees C the variation was from -80 to 95 HU while at -78.5 degrees C all readings were roughly 10 HU lower. At 20 degrees C NaCl and DMEM solutions with 0-8 M glycerol loading show a linear variation from 0 to 145 HU. After freezing to -78

  18. Phase separation of polystyrene/poly(vinylmethylether)/organoclay nanocomposites.

    PubMed

    El Mabrouk, Khalil; Bousmina, Mosto

    2006-02-01

    The effect of addition of organically modified montmorillonite (OMMT) on the phase separation of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blend was examined. Using two types of OMMT modified with two different kinds of surfactants, the effect of organic modification on nanocomposites was investigated by focusing on three major aspects: phase transition, morphological study, and melt rheological behavior both below and above the critical transition temperature. X-ray diffraction (XRD) patterns revealed the formation of intercalated nanocomposites and transmission electron micrographic (TEM) observations showed that the ordering of silicate layers in blend matrix is well matched with the XRD patterns. The addition of clay was found to affect both the mechanism of phase separation and the final morphology. Such effects resulted in uncommon rheological behavior of the blend both below and above the critical transition temperature. Surface phase separation of thin films for virgin blend and nanocomposites was also examined by atomic force microscopy (AFM). Morphology resulting after phase separation was found to be dependent on the nature and the amount of OMMT added to the polymer blend.

  19. Phase Separation kinetics in an Fe-Cr-Al alloy

    SciTech Connect

    Capdevila, C.; Miller, Michael K; Chao, J.

    2012-01-01

    The {alpha}-{alpha}{prime} phase separation kinetics in a commercial Fe-20 wt.% Cr-6 wt.% Al oxide dispersion-strengthened PM 2000{trademark} steel have been characterized with the complementary techniques atom probe tomography and thermoelectric power measurements during isothermal aging at 673, 708, and 748 K for times up to 3600 h. A progressive decrease in the Al content of the Cr-rich {alpha}{prime} phase was observed at 708 and 748 K with increasing time, but no partitioning was observed at 673 K. The variation in the volume fraction of the {alpha}{prime} phase well inside the coarsening regime, along with the Avrami exponent 1.2 and activation energy 264 kJ mol{sup -1}, obtained after fitting the experimental results to an Austin-Rickett type equation, indicates that phase separation in PM 2000{trademark} is a transient coarsening process with overlapping nucleation, growth, and coarsening stages.

  20. Phase separation in biological membranes: integration of theory and experiment.

    PubMed

    Elson, Elliot L; Fried, Eliot; Dolbow, John E; Genin, Guy M

    2010-01-01

    Lipid bilayer model membranes that contain a single lipid species can undergo transitions between ordered and disordered phases, and membranes that contain a mixture of lipid species can undergo phase separations. Studies of these transformations are of interest for what they can tell us about the interaction energies of lipid molecules of different species and conformations. Nanoscopic phases (<200 nm) can provide a model for membrane rafts, specialized membrane domains enriched in cholesterol and sphingomyelin, which are believed to have essential biological functions in cell membranes. Crucial questions are whether lipid nanodomains can exist in stable equilibrium in membranes and what is the distribution of their sizes and lifetimes in membranes of different composition. Theoretical methods have supplied much information on these questions, but better experimental methods are needed to detect and characterize nanodomains under normal membrane conditions. This review summarizes linkages between theoretical and experimental studies of phase separation in lipid bilayer model membranes.

  1. Phase separation in biological membranes: integration of theory and experiment

    PubMed Central

    Elson, Elliot L.; Fried, Eliot; Dolbow, John E.; Genin, Guy M.

    2013-01-01

    Lipid bilayer model membranes can undergo transitions between ordered and disordered phases, and membranes that contain a mixture of lipid species can undergo phase separations. Studies of these transformations are of interest for what they can tell us about the interaction energies of lipid molecules of different species and conformations. Nanoscopic phases can provide a model for membrane rafts, which have important biological functions in cell membranes. Important questions are whether lipid nanodomains can exist in stable equilibrium in membranes and what is the distribution of their sizes in membranes of different composition. It is also important to know the lifetimes of nanodomains. Theoretical methods have supplied much important information on these questions, but better experimental methods are needed to detect and characterize nanodomains under normal membrane conditions. This review summarizes linkages between theoretical and experimental studies of phase separation in lipid bilayer model membranes. PMID:20192775

  2. Investigation of Phase Mixing in Amorphous Solid Dispersions of AMG 517 in HPMC-AS Using DSC, Solid-State NMR, and Solution Calorimetry.

    PubMed

    Calahan, Julie L; Azali, Stephanie C; Munson, Eric J; Nagapudi, Karthik

    2015-11-02

    Intimate phase mixing between the drug and the polymer is considered a prerequisite to achieve good physical stability for amorphous solid dispersions. In this article, spray dried amorphous dispersions (ASDs) of AMG 517 and HPMC-as were studied by differential scanning calorimetry (DSC), solid-state NMR (SSNMR), and solution calorimetry. DSC analysis showed a weakly asymmetric (ΔTg ≈ 13.5) system with a single glass transition for blends of different compositions indicating phase mixing. The Tg-composition data was modeled using the BKCV equation to accommodate the observed negative deviation from ideality. Proton spin-lattice relaxation times in the laboratory and rotating frames ((1)H T1 and T1ρ), as measured by SSNMR, were consistent with the observation that the components of the dispersion were in intimate contact over a 10-20 nm length scale. Based on the heat of mixing calculated from solution calorimetry and the entropy of mixing calculated from the Flory-Huggins theory, the free energy of mixing was calculated. The free energy of mixing was found to be positive for all ASDs, indicating that the drug and polymer are thermodynamically predisposed to phase separation at 25 °C. This suggests that miscibility measured by DSC and SSNMR is achieved kinetically as the result of intimate mixing between drug and polymer during the spray drying process. This kinetic phase mixing is responsible for the physical stability of the ASD.

  3. Nanocrystals in compression: unexpected structural phase transition and amorphization due to surface impurities

    NASA Astrophysics Data System (ADS)

    Liu, Gang; Kong, Lingping; Yan, Jinyuan; Liu, Zhenxian; Zhang, Hengzhong; Lei, Pei; Xu, Tao; Mao, Ho-Kwang; Chen, Bin

    2016-06-01

    We report an unprecedented surface doping-driven anomaly in the compression behaviors of nanocrystals demonstrating that the change of surface chemistry can lead to an interior bulk structure change in nanoparticles. In the synchrotron-based X-ray diffraction experiments, titania nanocrystals with low concentration yttrium dopants at the surface are found to be less compressible than undoped titania nanocrystals. More surprisingly, an unexpected TiO2(ii) phase (α-PbO2 type) is induced and obvious anisotropy is observed in the compression of yttrium-doped TiO2, in sharp contrast to the compression behavior of undoped TiO2. In addition, the undoped brookite nanocrystals remain with the same structure up to 30 GPa, whereas the yttrium-doped brookite amorphizes above 20 GPa. The abnormal structural evolution observed in yttrium-doped TiO2 does not agree with the reported phase stability of nano titania polymorphs, thus suggesting that the physical properties of the interior of nanocrystals can be controlled by the surface, providing an unconventional and new degree of freedom in search for nanocrystals with novel tunable properties that can trigger applications in multiple areas of industry and provoke more related basic science research.We report an unprecedented surface doping-driven anomaly in the compression behaviors of nanocrystals demonstrating that the change of surface chemistry can lead to an interior bulk structure change in nanoparticles. In the synchrotron-based X-ray diffraction experiments, titania nanocrystals with low concentration yttrium dopants at the surface are found to be less compressible than undoped titania nanocrystals. More surprisingly, an unexpected TiO2(ii) phase (α-PbO2 type) is induced and obvious anisotropy is observed in the compression of yttrium-doped TiO2, in sharp contrast to the compression behavior of undoped TiO2. In addition, the undoped brookite nanocrystals remain with the same structure up to 30 GPa, whereas the yttrium

  4. DUAL PHASE MEMBRANE FOR HIGH TEMPERATURE CO2 SEPARATION

    SciTech Connect

    Jerry Y.S. Lin

    2002-12-01

    This project is aimed at synthesis of a new inorganic dual-phase carbonate membrane for high temperature CO{sub 2} separation. Metal-carbonate dual-phase membranes were prepared by the direct infiltration method and the synthesis conditions were optimized. The dual-phase membranes are gas-tight with helium permeance about six orders of magnitude lower than that for the metal support. Efforts were made to test seals for permeation and separation experiments for dual-phase membrane at the intermediate temperature range (about 500 C) under oxidizing atmosphere. An effective new permeation cell with a metal seal was designed, fabricated and tested. The permeation setup provided leak-free sealing for the dual-phase membranes under the desired operation conditions. Though the reliable data showing high permeance for carbon dioxide with oxygen for the prepared metal-carbonate dual phase membrane has not been measured, the research efforts in improving membrane synthesis and setting up a new permeation cell with suitable seal have made it closer for one to demonstrate good dual-phase membranes for high temperature carbon dioxide separation. Research efforts were also directed towards preparation of a new ceramic-carbonate dual-phase membrane. Porous lanthanum cobaltite (LC) perovskite type oxide ceramic support with oxidation resistance better than the metal support and high electronic conductivity (1300-1500 S/cm in 400-600 C), was prepared and studied as an alternative support for the dual-phase carbonate membranes. The LC powder was found not reactive with the carbonate at 600 C. The porous LC disks have helium permeance and pore diameter smaller than the metal support but larger than the common {alpha}-alumina support. These results show promise to use the LC support for preparation of oxidation resistant dual-phase carbonate membranes.

  5. Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

    DOE PAGES

    Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

    2015-12-01

    Amorphous MoSx is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS2 in composition and chemical state. However, structural changes in the MoSx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoSx catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmental TEM. For the first time,more » we directly observe the formation of crystalline domains in the MoSx catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoSx catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H2 generation.« less

  6. Anomalous phase separation behavior of gel-derived soda-silica glasses

    NASA Technical Reports Server (NTRS)

    Neilson, G. F.; Weinberg, M. C.

    1982-01-01

    The effects of retained bound hydroxyl groups on amorphous immiscibility behavior and on the kinetics of phase separation were studied in glasses containing from 10 to 19 percent sodium oxide preparaed by the gel process. Differences in behavior as functions of preliminary thermal treatment of the gel precursor and of melting conditions were studied, employing IR spectroscopy, SAXS and WAXD to monitor the variation in glass microstructure. Both the initial gel treatment and the OH concentration in the prepared glasses were found to affect the immiscibility temperatures, and the magnitude of the maximum temperature increase was also a function of the sodium oxide concentration. It is suggested that the variation in thermodynamic behavior may be caused by the structural arrangement attained by the OH groups during the gel condensation process, which in turn affects the extent of hydrogen bonding to nonbridging oxygen ions.

  7. Anomalous phase separation behavior of gel-derived soda-silica glasses

    NASA Technical Reports Server (NTRS)

    Neilson, G. F.; Weinberg, M. C.

    1982-01-01

    The effects of retained bound hydroxyl groups on amorphous immiscibility behavior and on the kinetics of phase separation were studied in glasses containing from 10 to 19 percent sodium oxide preparaed by the gel process. Differences in behavior as functions of preliminary thermal treatment of the gel precursor and of melting conditions were studied, employing IR spectroscopy, SAXS and WAXD to monitor the variation in glass microstructure. Both the initial gel treatment and the OH concentration in the prepared glasses were found to affect the immiscibility temperatures, and the magnitude of the maximum temperature increase was also a function of the sodium oxide concentration. It is suggested that the variation in thermodynamic behavior may be caused by the structural arrangement attained by the OH groups during the gel condensation process, which in turn affects the extent of hydrogen bonding to nonbridging oxygen ions.

  8. Ruthenium Behavior at Phase Separation of Borosilicate Glass-12259

    SciTech Connect

    Enokida, Youichi; Sawada, Kayo

    2012-07-01

    The Rokkasho reprocessing plant (RRP) located in Aomori, Japan, vitrifies high level waste (HLW) into a borosilicate glass. The HLW is generated from the reprocessing of spent fuel and contains ruthenium (Ru) and other platinum group metals (PGMs). Based on the recent consequences after a huge earthquake that occurred in Japan, a hypothetical blackout was postulated for the RRP to address additional safety analysis requirements. During a prolonged blackout, the borosilicate glass could phase separate due to cooling of the glass in the melter. The Ru present in the glass matrix could migrate into separate phases and impact the durability of the borosilicate glass. The durability of the glass is important for quality assurance and performance assessment of the vitrified HLW. A fundamental study was performed at an independent university to understand the impact of a prolonged blackout. Simulated HLW glasses were prepared for the RRP, and the Ru behavior in phase separated glasses was studied. The simulated HLW glasses contained nonradioactive elements and PGMs. The glass compositions were then altered to enhance the formation of the phase-separated glasses when subjected to thermal treatment at 700 deg. C for 24 hours. The synthesized simulated glasses contained 1.1 % Ru by weight as ruthenium dioxide (RuO{sub 2}). A portion of the RuO{sub 2} formed needle-shaped crystals in the glass specimens. After the thermal treatment, the glass specimen had separated into two phases. One of the two phases was a B{sub 2}O{sub 3} rich phase, and the other phase was a SiO{sub 2} rich phase. The majority of the chemical species in the B{sub 2}O{sub 3} rich phase was leached away with the Material Characterization Center-3 (MCC-3) protocol standardized by the Pacific Northwest National Laboratory using an aqueous low-concentrated nitric acid solution, but the leaching of the Ru fraction was very limited; less than 1% of the original Ru content. The Ru leaching was much less than

  9. Potential energy landscape of the apparent first-order phase transition between low-density and high-density amorphous ice

    NASA Astrophysics Data System (ADS)

    Giovambattista, Nicolas; Sciortino, Francesco; Starr, Francis W.; Poole, Peter H.

    2016-12-01

    The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics to describe supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different from the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition is qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order phase transition between out-of-equilibrium states. Finally, we compare the PEL properties explored during the LDA-HDA transformations in ST2 water with those reported previously for SPC/E water, for which the LDA-HDA transformations are rather smooth. This comparison illuminates the previous work showing that, at accessible computer times scales, a liquid-liquid phase transition occurs in the case of ST2 water, but not for SPC/E water.

  10. Potential energy landscape of the apparent first-order phase transition between low-density and high-density amorphous ice.

    PubMed

    Giovambattista, Nicolas; Sciortino, Francesco; Starr, Francis W; Poole, Peter H

    2016-12-14

    The potential energy landscape (PEL) formalism is a valuable approach within statistical mechanics to describe supercooled liquids and glasses. Here we use the PEL formalism and computer simulations to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) at different temperatures. We employ the ST2 water model for which the LDA-HDA transformations are remarkably sharp, similar to what is observed in experiments, and reminiscent of a first-order phase transition. Our results are consistent with the view that LDA and HDA configurations are associated with two distinct regions (megabasins) of the PEL that are separated by a potential energy barrier. At higher temperature, we find that low-density liquid (LDL) configurations are located in the same megabasin as LDA, and that high-density liquid (HDL) configurations are located in the same megabasin as HDA. We show that the pressure-induced LDL-HDL and LDA-HDA transformations occur along paths that interconnect these two megabasins, but that the path followed by the liquid is different from the path followed by the amorphous solid. At higher pressure, we also study the liquid-to-ice-VII first-order phase transition, and find that the behavior of the PEL properties across this transition is qualitatively similar to the changes found during the LDA-HDA transformation. This similarity supports the interpretation that the LDA-HDA transformation is a first-order phase transition between out-of-equilibrium states. Finally, we compare the PEL properties explored during the LDA-HDA transformations in ST2 water with those reported previously for SPC/E water, for which the LDA-HDA transformations are rather smooth. This comparison illuminates the previous work showing that, at accessible computer times scales, a liquid-liquid phase transition occurs in the case of ST2 water, but not for SPC/E water.

  11. Modeling Human Population Separation History Using Physically Phased Genomes.

    PubMed

    Song, Shiya; Sliwerska, Elzbieta; Emery, Sarah; Kidd, Jeffrey M

    2017-01-01

    Phased haplotype sequences are a key component in many population genetic analyses since variation in haplotypes reflects the action of recombination, selection, and changes in population size. In humans, haplotypes are typically estimated from unphased sequence or genotyping data using statistical models applied to large reference panels. To assess the importance of correct haplotype phase on population history inference, we performed fosmid pool sequencing and resolved phased haplotypes of five individuals from diverse African populations (including Yoruba, Esan, Gambia, Maasai, and Mende). We physically phased 98% of heterozygous SNPs into haplotype-resolved blocks, obtaining a block N50 of 1 Mbp. We combined these data with additional phased genomes from San, Mbuti, Gujarati, and Centre de'Etude du Polymorphism Humain European populations and analyzed population size and separation history using the pairwise sequentially Markovian coalescent and multiple sequentially Markovian coalescent models. We find that statistically phased haplotypes yield a more recent split-time estimation compared with experimentally phased haplotypes. To better interpret patterns of cross-population coalescence, we implemented an approximate Bayesian computation approach to estimate population split times and migration rates by fitting the distribution of coalescent times inferred between two haplotypes, one from each population, to a standard isolation-with-migration model. We inferred that the separation between hunter-gatherer populations and other populations happened ∼120-140 KYA, with gene flow continuing until 30-40 KYA; separation between west-African and out-of-African populations happened ∼70-80 KYA; while the separation between Maasai and out-of-African populations happened ∼50 KYA. Copyright © 2017 by the Genetics Society of America.

  12. Modeling Human Population Separation History Using Physically Phased Genomes

    PubMed Central

    Song, Shiya; Sliwerska, Elzbieta; Emery, Sarah; Kidd, Jeffrey M.

    2017-01-01

    Phased haplotype sequences are a key component in many population genetic analyses since variation in haplotypes reflects the action of recombination, selection, and changes in population size. In humans, haplotypes are typically estimated from unphased sequence or genotyping data using statistical models applied to large reference panels. To assess the importance of correct haplotype phase on population history inference, we performed fosmid pool sequencing and resolved phased haplotypes of five individuals from diverse African populations (including Yoruba, Esan, Gambia, Maasai, and Mende). We physically phased 98% of heterozygous SNPs into haplotype-resolved blocks, obtaining a block N50 of 1 Mbp. We combined these data with additional phased genomes from San, Mbuti, Gujarati, and Centre de’Etude du Polymorphism Humain European populations and analyzed population size and separation history using the pairwise sequentially Markovian coalescent and multiple sequentially Markovian coalescent models. We find that statistically phased haplotypes yield a more recent split-time estimation compared with experimentally phased haplotypes. To better interpret patterns of cross-population coalescence, we implemented an approximate Bayesian computation approach to estimate population split times and migration rates by fitting the distribution of coalescent times inferred between two haplotypes, one from each population, to a standard isolation-with-migration model. We inferred that the separation between hunter-gatherer populations and other populations happened ∼120–140 KYA, with gene flow continuing until 30–40 KYA; separation between west-African and out-of-African populations happened ∼70–80 KYA; while the separation between Maasai and out-of-African populations happened ∼50 KYA. PMID:28049708

  13. Thermally Triggered Phase Separation of Organic Electrolyte-Cellulose Solutions.

    PubMed

    de Oliveira, Heitor F N; Clough, Matthew T; Rinaldi, Roberto

    2016-12-08

    Organic electrolyte solutions (OES)-binary mixtures of an ionic liquid (IL) with a neutral polar aprotic co-solvent-are being recognized as excellent candidate solvents for the dissolution, derivatization, and sustainable processing of cellulose. These solutions exhibit the beneficially combined properties of rapid-to-instantaneous cellulose dissolution, raised thermal stability, and reduced viscosity, compared to cellulose solutions in the parent ILs. Herein, we report the reversible, thermally triggered phase separation of cellulose solutions in 1-ethyl-3-methylimidazolium acetate with 1,3-dimethyl-2-imidazolidinone. In these solutions, cellulose drives the process of phase separation, resulting in a lower, IL-rich layer in which the biopolymer is segregated. In turn, the upper phase is enriched in the neutral co-solvent. We show that the temperature of phase separation can be fine-tuned by modification of mole fractions of IL, co-solvent, and cellulose. This finding holds promise for the design of strategies for separation and solvent recycling in cellulose chemistry. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Phase separation in transparent liquid-liquid miscibility gap systems

    NASA Technical Reports Server (NTRS)

    Gelles, S. H.; Bhat, B. N.; Laub, R. J.

    1979-01-01

    A program to be carried out on transparent liquid-phase miscibility gap materials was developed for the purpose of acquiring additional insight into the separation process occurring in these systems. The transparency feature allows the reaction to be viewed directly through light scattering and holographic methods.

  15. Assemblages: Functional units formed by cellular phase separation

    PubMed Central

    Wright, Peter E.

    2014-01-01

    The partitioning of intracellular space beyond membrane-bound organelles can be achieved with collections of proteins that are multivalent or contain low-complexity, intrinsically disordered regions. These proteins can undergo a physical phase change to form functional granules or other entities within the cytoplasm or nucleoplasm that collectively we term “assemblage.” Intrinsically disordered proteins (IDPs) play an important role in forming a subset of cellular assemblages by promoting phase separation. Recent work points to an involvement of assemblages in disease states, indicating that intrinsic disorder and phase transitions should be considered in the development of therapeutics. PMID:25179628

  16. Diagnostic immunoassay by solid phase separation for digoxin

    SciTech Connect

    Grenier, F.C.; Pry, T.A.; Kolaczkowski, L.

    1988-11-29

    A method is described for conducting a diagnostic immunoassay for digoxin, comprising: (a) forming a reaction mixture of a test sample with a molar excess of labeled anti-digoxin antibodies whereby the labeled antibodies are capable of forming complex with digoxin present in the sample; (b) contacting the reaction mixture with a solid phase material having immobilized thereon a compound; (c) separating the solid phase material from the reaction mixture; and (d) determining the presence of digoxin in the test sample by measuring the amount of complex present in the liquid phase.

  17. Demixing kinetics of phase separated polymer solutions in microgravity

    NASA Technical Reports Server (NTRS)

    Brooks, D. E.; Bamberger, S. B.; Harris, J. M.; Vanalstine, J.; Snyder, R. S.

    1988-01-01

    Phase separated solutions of two neutral polymers in buffer provide a useful and versatile medium for the partition separation of biological cells. However, the efficiency of such separations is orders of magnitude lower than the thermodynamic limit. To test the hypothesis that this inefficiency is at least partially due to the convection and sedimentation that occur during the gravity driven demixing that follows introduction of cells to the systems, a series of experiments were begun aimed at performing cell partition in a low g environment. Demixing of isopycnic three polymer solvent systems was studied, experiments were performed on KC-135 aircraft and one shuttle middeck experiment was completed. Analysis of the results of these experiments and comparisons with the predictions of scaling relations for the dependence of phase domain size on time, derived for a number of possible demixing mechanisms, are presented.

  18. First-order transition in confined water between high-density liquid and low-density amorphous phases.

    PubMed

    Koga, K; Tanaka, H; Zeng, X C

    2000-11-30

    Supercooled water and amorphous ice have a rich metastable phase behaviour. In addition to transitions between high- and low-density amorphous solids, and between high- and low-density liquids, a fragile-to-strong liquid transition has recently been proposed, and supported by evidence from the behaviour of deeply supercooled bilayer water confined in hydrophilic slit pores. Here we report evidence from molecular dynamics simulations for another type of first-order phase transition--a liquid-to-bilayer amorphous transition--above the freezing temperature of bulk water at atmospheric pressure. This transition occurs only when water is confined in a hydrophobic slit pore with a width of less than one nanometre. On cooling, the confined water, which has an imperfect random hydrogen-bonded network, transforms into a bilayer amorphous phase with a perfect network (owing to the formation of various hydrogen-bonded polygons) but no long-range order. The transition shares some characteristics with those observed in tetrahedrally coordinated substances such as liquid silicon, liquid carbon and liquid phosphorus.

  19. Metallic and semiconducting carbon nanotubes separation using an aqueous two-phase separation technique: a review

    NASA Astrophysics Data System (ADS)

    Tang, Malcolm S. Y.; Ng, Eng-Poh; Juan, Joon Ching; Ooi, Chien Wei; Ling, Tau Chuan; Woon, Kai Lin; Loke Show, Pau

    2016-08-01

    It is known that carbon nanotubes show desirable physical and chemical properties with a wide array of potential applications. Nonetheless, their potential has been hampered by the difficulties in acquiring high purity, chiral-specific tubes. Considerable advancement has been made in terms of the purification of carbon nanotubes, for instance chemical oxidation, physical separation, and myriad combinations of physical and chemical methods. The aqueous two-phase separation technique has recently been demonstrated to be able to sort carbon nanotubes based on their chirality. The technique requires low cost polymers and salt, and is able to sort the tubes based on their diameter as well as metallicity. In this review, we aim to provide a review that could stimulate innovative thought on the progress of a carbon nanotubes sorting method using the aqueous two-phase separation method, and present possible future work and an outlook that could enhance the methodology.

  20. Novel 3-hydroxypropyl bonded phase by direct hydrosilylation of allyl alcohol on amorphous hydride silica

    PubMed Central

    Gómez, Jorge E.; Navarro, Fabián H.; Sandoval, Junior E.

    2015-01-01

    A novel 3-hydroxypropyl (propanol) bonded silica phase has been prepared by hydrosilylation of allyl alcohol on a hydride silica intermediate, in the presence of platinum (0)-divinyltetramethyldisiloxane (Karstedt's catalyst). The regio-selectivity of this synthetic approach had been correctly predicted by previous reports involving octakis(dimethylsiloxy)octasilsesquioxane (Q8M8H) and hydrogen silsesquioxane (T8H8), as molecular analogs of hydride amorphous silica. Thus, C-silylation predominated (~ 94%) over O-silylation, and high surface coverages of propanol groups (5±1 µmol/m2) were typically obtained in this work. The propanol-bonded phase was characterized by spectroscopic (IR and solid state NMR on silica microparticles), contact angle (on fused-silica wafers) and CE (on fused-silica tubes) techniques. CE studies of the migration behavior of pyridine, caffeine, tris(2,2’-bipyridine)Ru(II) chloride and lysozyme on propanol-modified capillaries were carried out. The adsorption properties of these select silanol-sensitive solutes were compared to those on the unmodified and hydride-modified tubes. It was found that hydrolysis of the SiH species underlying the immobilized propanol moieties leads mainly to strong ion-exchange based interactions with the basic solutes at pH 4, particularly with lysozyme. Interestingly, and in agreement with water contact angle and electroosmotic mobility figures, the silanol-probe interactions on the buffer-exposed (hydrolyzed) hydride surface are quite different from those of the original unmodified tube. PMID:24934906

  1. Analysis of Phase Separation in Czochralski Grown Single Crystal Ilmenite

    NASA Technical Reports Server (NTRS)

    Wilkins, R.; Powell, Kirk St. A.; Loregnard, Kieron R.; Lin, Sy-Chyi; Muthusami, Jayakumar; Zhou, Feng; Pandey, R. K.; Brown, Geoff; Hawley, M. E.

    1998-01-01

    Ilmenite (FeTiOs) is a wide bandgap semiconductor with an energy gap of 2.58 eV. Ilmenite has properties suited for radiation tolerant applications, as well as a variety of other electronic applications. Single crystal ilmenite has been grown from the melt using the Czochralski method. Growth conditions have a profound effect on the microstructure of the samples. Here we present data from a variety of analytical techniques which indicate that some grown crystals exhibit distinct phase separation during growth. This phase separation is apparent for both post-growth annealed and unannealed samples. Under optical microscopy, there appear two distinct areas forming a matrix with an array of dots on order of 5 pm diameter. While appearing bright in the optical micrograph, atomic force microscope (AFM) shows the dots to be shallow pits on the surface. Magnetic force microscope (MFM) shows the dots to be magnetic. Phase identification via electron microprobe analysis (EMPA) indicates two major phases in the unannealed samples and four in the annealed samples, where the dots appear to be almost pure iron. This is consistent with micrographs taken with a scanning probe microscope used in the magnetic force mode. Samples that do not exhibit the phase separation have little or no discernible magnetic structure detectable by the MFM.

  2. Binary mixtures of polyhedral nanoparticles: from phase separation to superstructures

    NASA Astrophysics Data System (ADS)

    Khadilkar, Mihir; Agarwal, Umang; Escobedo, Fernando

    2014-03-01

    Polyhedral nanoparticles have emerged as important model systems for both fundamental studies of entropic self-assembly as well as material design. The mixing of more than one shape provides a promising strategy towards achieving a greater variety of structures and properties. We explore this with the study of the phase behavior of binary mixtures of hard convex polyhedra having similar sizes but different shapes. Choosing representative particle shapes from those readily synthesizable, we find that the phase behavior of such mixtures is dependent on the interplay of mixing and packing entropy, which can give rise to miscible or phase-separated states. While expectedly many of the binary systems studied exhibit phase separation at high pressures due to the incompatible pure-component crystal structures, our study shows that the essential qualitative trends in miscibility and phase separation can be correlated to properties of the pure components, such as the relative values of the order-disorder transition pressure of each component. However, the relative size ratios and the presence of mesophases for the pure-component systems are also critical in aiding the formation of fully miscible blends of novel plastic crystalline superstructures.

  3. Analysis of Phase Separation in Czochralski Grown Single Crystal Ilmenite

    NASA Technical Reports Server (NTRS)

    Wilkins, R.; Powell, Kirk St. A.; Loregnard, Kieron R.; Lin, Sy-Chyi; Muthusami, Jayakumar; Zhou, Feng; Pandey, R. K.; Brown, Geoff; Hawley, M. E.

    1998-01-01

    Ilmenite (FeTiOs) is a wide bandgap semiconductor with an energy gap of 2.58 eV. Ilmenite has properties suited for radiation tolerant applications, as well as a variety of other electronic applications. Single crystal ilmenite has been grown from the melt using the Czochralski method. Growth conditions have a profound effect on the microstructure of the samples. Here we present data from a variety of analytical techniques which indicate that some grown crystals exhibit distinct phase separation during growth. This phase separation is apparent for both post-growth annealed and unannealed samples. Under optical microscopy, there appear two distinct areas forming a matrix with an array of dots on order of 5 pm diameter. While appearing bright in the optical micrograph, atomic force microscope (AFM) shows the dots to be shallow pits on the surface. Magnetic force microscope (MFM) shows the dots to be magnetic. Phase identification via electron microprobe analysis (EMPA) indicates two major phases in the unannealed samples and four in the annealed samples, where the dots appear to be almost pure iron. This is consistent with micrographs taken with a scanning probe microscope used in the magnetic force mode. Samples that do not exhibit the phase separation have little or no discernible magnetic structure detectable by the MFM.

  4. Amorphous and nanocrystalline phase formation in highly-driven Al-based binary alloys

    SciTech Connect

    Kalay, Yunus Eren

    2009-01-01

    Remarkable advances have been made since rapid solidification was first introduced to the field of materials science and technology. New types of materials such as amorphous alloys and nanostructure materials have been developed as a result of rapid solidification techniques. While these advances are, in many respects, ground breaking, much remains to be discerned concerning the fundamental relationships that exist between a liquid and a rapidly solidified solid. The scope of the current dissertation involves an extensive set of experimental, analytical, and computational studies designed to increase the overall understanding of morphological selection, phase competition, and structural hierarchy that occurs under far-from equilibrium conditions. High pressure gas atomization and Cu-block melt-spinning are the two different rapid solidification techniques applied in this study. The research is mainly focused on Al-Si and Al-Sm alloy systems. Silicon and samarium produce different, yet favorable, systems for exploration when alloyed with aluminum under far-from equilibrium conditions. One of the main differences comes from the positions of their respective T0 curves, which makes Al-Si a good candidate for solubility extension while the plunging T0 line in Al-Sm promotes glass formation. The rapidly solidified gas-atomized Al-Si powders within a composition range of 15 to 50 wt% Si are examined using scanning and transmission electron microscopy. The non-equilibrium partitioning and morphological selection observed by examining powders at different size classes are described via a microstructure map. The interface velocities and the amount of undercooling present in the powders are estimated from measured eutectic spacings based on Jackson-Hunt (JH) and Trivedi-Magnin-Kurz (TMK) models, which permit a direct comparison of theoretical predictions. For an average particle size of 10 {micro}m with a Peclet number of ~0.2, JH and TMK deviate from

  5. Formation and stability of metastable structures and amorphous phases in PU-V, PU-TA, and PU-YB systems with positive heats of mixing

    NASA Astrophysics Data System (ADS)

    Rizzo, H. F.; Zocco, T.; Massalski, T. B.; Nastasi, M.; Echeverria, A.

    1994-08-01

    The triode sputtering technique with a “split-target” arrangement was used to obtain metastable crystalline and amorphous phases in the Pu-V, Pu-Ta, and Pu-Yb systems. The proposed phase diagrams for these systems all exhibit liquid immiscibility. The heats of mixing are estimated to be highly positive, and the atomic radii of the component atoms differ by at least 10 pct. Extended amorphous and body-centered cubic (bcc) solid-solution regions were observed in the Pu-V and Pu-Ta systems. The corresponding lattice parameters appear to follow in each case an assumed Vegard’s Law extension. In the Pu-Yb system, no amorphous phase was obtained, but an extended face-centered cubic (fcc) solid-solution region (24 to 78 at. pct Yb) was observed with a large positive deviation of the lattice parameter (˜9 pct at 40 at. pct Yb) from a linear Vegard’s Law between the pure fcc components. The observed ranges of amorphous and metastable solid-solution phases have been interpreted in terms of predicated heats of formation for these phases using Miedema’s thermodynamic approximations that include chemical, elastic, and structural contributions. The effect of the high deposition rates on the formation of amorphous and metastable phases has also been considered. Thermal annealing of Pu-Ta amorphous alloys brings about a rapid diffusion of Pu to the free surface of the amorphous phase without crystallization of the remaining Ta-rich amorphous phase. Microhardness measurements indicate that amorphous Pu-V and Pu-Ta alloys are softer than the crystalline bcc solid-solution alloys in the same composition range. Several similarities in the formation of mixed phase regions (amorphous and solid solutions), microhardness, and resistance to decomposition on heating were noted between the Pu-Ta and Pu-V systems and the Cu-W system studied previously.

  6. Structural and thermoelastic properties of crystalline and amorphous TiSi2 phases by tight-binding molecular dynamics

    NASA Astrophysics Data System (ADS)

    Iannuzzi, M.; Miglio, Leo; Celino, M.

    2000-06-01

    We have characterized by total-energy calculations and molecular-dynamics simulations the two crystalline phases (C54 and C49) of TiSi2 in a wide range of temperatures. We have also produced and analyzed the amorphous and the liquid phases. Structural and thermoelastic properties are calculated and reported for all the phases. The molecular-dynamics simulations are based on an original set of parameters for the interatomic potential in the framework of the tight-binding approach. The intrinsic difference between the C54 and C49 phases is addressed and discussed by looking at the structural and the electronic properties.

  7. Relation between the High Density Phase and the Very-High Density Phase of Amorphous Solid Water

    NASA Astrophysics Data System (ADS)

    Giovambattista, Nicolas; Stanley, H. Eugene; Sciortino, Francesco

    2005-03-01

    It has been suggested that high-density amorphous (HDA) ice is a structurally arrested form of high-density liquid (HDL) water, while low-density amorphous ice is a structurally arrested form of low-density liquid (LDL) water. Recent experiments and simulations have been interpreted to support the possibility of a second distinct high-density structural state, named very high-density amorphous (VHDA) ice, questioning the LDL-HDL hypothesis. We test this interpretation using extensive computer simulations and find that VHDA is a more stable form of HDA and that, in fact, VHDA should be considered as the amorphous ice of the quenched HDL.

  8. Impact of amorphous precursor phases on magnesium isotope signatures of Mg-calcite

    NASA Astrophysics Data System (ADS)

    Mavromatis, Vasileios; Purgstaller, Bettina; Dietzel, Martin; Buhl, Dieter; Immenhauser, Adrian; Schott, Jacques

    2017-04-01

    Various marine calcifiers form exoskeletons via an amorphous calcium carbonate (ACC) precursor phase and magnesium plays an important role in the temporary stabilization of this metastable phase. Thus, the use of Mg isotope ratios of marine biogenic carbonates as a proxy to reconstruct past seawater chemistry calls for a detailed understanding of the mechanisms controlling Mg isotope signatures during the formation and transformation of ACC to the final crystalline carbonate mineral. For this purpose we have investigated the Mg isotope fractionation between (Ca,Mg)CO3 solids and aqueous fluids at 25 °C and pH = 8.3 during (i) the direct precipitation of crystalline Mg-calcite and (ii) the formation of Mg-rich ACC (Mg-ACC) and its transformation to Mg-calcite. The outcome documents that the small Mg isotope fractionation between Mg-ACC and reactive fluid (ΔMg26ACC-fluid = - 1.0 ± 0.1 ‰) is not preserved during the transformation of the ACCs into Mg-calcite. Following a pronounced isotopic shift accompanying the transformation of Mg-ACC into Mg-calcite, Δ26Mgcalcite-fluid progressively decreases with reaction progress from ∼ - 3.0 ‰ to - 3.6 ‰, reflecting both the approach of isotopic equilibrium and the increase of calcite Mg content (to near 20 mol % Mg). In contrast the crystalline Mg-calcite precipitated directly from the reacting fluid, i.e. lacking a discernable formation of an amorphous precursor, exhibits only small temporal variations in Δ26Mgcalcite-fluid which overall is affected by the precipitation kinetics. The values found in this study at the onset of Mg-ACC precipitation for Mg isotope fractionation between Mg-ACC and the fluid (ΔMg26ACC-fluid = - 1.0 ‰) and between Mg-ACC and Mg2+(aq) (Δ(aq) 26 Mg ACC-Mg2+ = + 2.0 ‰) are consistent with the formation of a hydrated Ca nanoporous solid accommodating Mg bicarbonate/carbonate species in combination with hydrated magnesium. This material crossed by percolating channels filled with the

  9. An overview of multidimensional liquid phase separations in food analysis.

    PubMed

    Franco, Maraíssa Silva; Padovan, Rodrigo Nogueira; Fumes, Bruno Henrique; Lanças, Fernando Mauro

    2016-07-01

    Food safety is a priority public health concern that demands analytical methods capable to detect low concentration level of contaminants (e.g. pesticides and antibiotics) in different food matrices. Due to the high complexity of these matrices, a sample preparation step is in most cases mandatory to achieve satisfactory results being usually tedious, lengthy, and prone to the introduction of errors. For this reason, many research groups have focused efforts on the development of online systems capable to do the cleanup, concentration, and separation steps at once through multidimensional separation techniques (MDS). Among several possible setups, the most popular are the multidimensional chromatographic techniques (MDC) that consist in combining more than one mobile and/or stationary phase to provide a satisfactory separation. In the present review, we selected a variety of multidimensional separation systems used for food contaminant analysis in order to discuss the instrumentation aspects, the concept of orthogonality, column approaches used in these systems, and new materials that can be used in these columns. Selected classes of contaminants present in food matrices are introduced and discussed as example of the potential applications of multidimensional liquid phase separation techniques in food safety. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Early stage phase separation in pharmaceutical solid dispersion thin films under high humidity: improved spatial understanding using probe-based thermal and spectroscopic nanocharacterization methods.

    PubMed

    Qi, Sheng; Moffat, Jonathan G; Yang, Ziyi

    2013-03-04

    Phase separation in pharmaceutical solid dispersion thin films under high humidity is still poorly understood on the submicrometer scale. This study investigated the phase separation of a model solid dispersion thin film, felodipine-PVP K29/32, prepared by spin-coating and analyzed using probe-based methods including atomic force microscopy, nanothermal analysis, and photothermal infrared microspectroscopy. The combined use of these techniques revealed that the phase separation process occurring in the thin films under high humidity is different from that in dry conditions reported previously. The initial stage of phase separation is primarily initiated in the bulk of the films as amorphous drug domains. Drug migration toward the surface of the solid dispersion film was then observed to occur under exposure to increased humidity. PVP cannot prevent phase separation of felodipine under high humidity but can minimize the crystallization of amorphous felodipine domains in the solid dispersion thin films. This study demonstrates the unique abilities of these nanocharacterization methods for studying, in three dimensions, the phase separation of thin films for pharmaceutical applications.

  11. Effect of carbon and nitrogen doping on the structure of amorphous GeTe phase change material

    NASA Astrophysics Data System (ADS)

    Raty, Jean-Yves; Ghezzi, Giada; Maitrejean, Sylvain; Noé, Pierre; Roule, Anne; Bichara, Christophe; Hippert, Françoise

    2012-02-01

    Carbon and Nitrogen-doped GeTe are promising materials for use in phase change memories since the addition of C or N increases the stability of the amorphous phase. By combining ab initio molecular dynamics and X-ray scattering experiments, we show that carbon deeply modifies the structure of the amorphous phase through long carbon chains, tetrahedral and triangular units centred on carbon. A clear signature of these units is the appearance of an additional interatomic distance around 3.3 A in the pair correlation function. Besides, the first Ge-Ge and Ge-Te distances are almost not affected by doping. The implications for the vibrational and thermal properties are finally discussed.

  12. Phase separation dynamics during Myxococcus xanthus fruiting body formation

    NASA Astrophysics Data System (ADS)

    Liu, Guannan; Bahar, Fatmagul; Patch, Adam; Thutupalli, Shashi; Yllanes, David; Marchetti, M. Cristina; Welch, Roy; Shaevitz, Joshua

    Many living systems take advantage of collective behavior for group survival. We use the soil-dwelling bacterium Myxococcus xanthus as a model to study out-of-equilibrium phase separation during fruiting body formation. M. xanthus cells have the ability to glide on solid surfaces and reverse their direction periodically. When starved, M. xanthus cells aggregate together and form structures called fruiting bodies, inside of which cells sporulate to survive stressful conditions. We show that at high cell density the formation of fruiting bodies is a phase separation process. From experimental data that combines single-cell tracking, population-scale imaging, mutants, and drug applications, we construct the phase diagram of M. xanthus in the space of Péclet number and cell density. When wild type cells are starved, we find that they actively increase their Péclet number by modulating gliding speed and reversal frequency which induces a phase separation from a gas-like state to an aggregated fruiting body state.

  13. Phase separation in solutions with specific and nonspecific interactions

    SciTech Connect

    Jacobs, William M.; Frenkel, Daan; Oxtoby, David W.

    2014-05-28

    Protein solutions, which tend to be thermodynamically stable under physiological conditions, can demix into protein-enriched and protein-depleted phases when stressed. Using a lattice-gas model of proteins with both isotropic and specific, directional interactions, we calculate the critical conditions for phase separation for model proteins with up to four patches via Monte Carlo simulations and statistical associating fluid theory. Given a fixed specific interaction strength, the critical value of the isotropic energy, which accounts for dispersion forces and nonspecific interactions, measures the stability of the solution with respect to nonspecific interactions. Phase separation is suppressed by the formation of protein complexes, which effectively passivate the strongly associating sites on the monomers. Nevertheless, we find that protein models with three or more patches can form extended aggregates that phase separate despite the assembly of passivated complexes, even in the absence of nonspecific interactions. We present a unified view of the critical behavior of model fluids with anisotropic interactions, and we discuss the implications of these results for the thermodynamic stability of protein solutions.

  14. Diffusion-driven phase separation of deeply quenched mixtures

    NASA Astrophysics Data System (ADS)

    Vladimirova, Natalia; Malagoli, Andrea; Mauri, Roberto

    1998-12-01

    In this work, we study the phase separation of deeply quenched mixtures in which the diffusion coefficient depends on the local composition field φ. In one dimension (1D), the system evolves until it reaches a spatially periodic steady state, with a period that, for instant quenching, coincides with the wavelength of the mode of maximum growth of the linear stability analysis. Similar results are obtained also when the temperature of the system is the solution of the heat equation, but in this case the period of the periodic steady-state solution increases as the heat diffusivity decreases. In 2D the concentration profile, after reaching a periodic configuration similar to the 1D steady state, continues to evolve, forming single-phase domains separated by sharp interfaces, which then thicken as the system tries to minimize its interfacial area. When the quench takes place across, or near, the critical point, the drops merge to form filaments which later coarsen and grow. However, when the quench takes place far from the critical point and near the metastable region of the phase diagram, the length of these filaments decreases as the system becomes a collection of nucleating drops. The composition field within and without these microdomains appears to be nonuniform and time-dependent even after the formation of sharp interfaces, thereby contradicting the commonly accepted assumption of local equilibrium at the late stage of the phase separation process. These results do not depend on the amount and the form of the random noise, while they are strongly influenced by the conditions of the system at the boundaries, as the morphology of phase separation becomes anisotropic and acquires a preferential direction when these conditions are not uniform.

  15. 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.

  16. Enantiomeric phase separation in a lattice gas model: Guggenheim approximation

    NASA Astrophysics Data System (ADS)

    Huckaby, Dale A.; Shinmi, Masato; Ausloos, Marcel; Clippe, Paulette

    1986-05-01

    We consider a lattice gas in which the two enantiomeric forms of a tetrahedral molecule, consisting of a central carbon atom bonded to four different groups A, B, G, and H, are adsorbed onto a triangular lattice, such that the carbon atom is above a lattice site, the three bonds to A, B, and G point toward neighboring lattice sites, and the bond to H points perpendicular to and away from the plane of the lattice. For a certain choice of intermolecular interactions, such as may exist between the zwitterion forms of an amino acid, the phase diagram was investigated using a Guggenheim approximation with two order parameters. Enantiomeric phase separation into two symmetric condensed phases occurs at low temperatures. These condensed phases become a single racemic condensed phase at a critical line, and they are in equilibrium with a racemic gas phase along a line of triple points. These two lines coincide at a critical endpoint. The racemic condensed and gas phases are in equilibrium along a two phase coexistence line which begins at the critical endpoint and ends at a critical point. No tricritical point was found in the model for the special choice of interactions studied.

  17. Growth and Morphology of Phase Separating Supercritical Fluids

    NASA Technical Reports Server (NTRS)

    Hegseth, John; Beysens, Daniel; Perrot, Francoise; Nikolayev, Vadim; Garrabos, Yves

    1996-01-01

    The scientific objective is to study the relation between the morphology and the growth kinetics of domains during phase separation. We know from previous experiments performed near the critical point of pure fluids and binary liquids that there are two simple growth laws at late times. The 'fast' growth appears when the volumes of the phases are nearly equal and the droplet pattern is interconnected. In this case the size of the droplets grows linearly in time. The 'slow' growth appears when the pattern of droplets embedded in the majority phase is disconnected. In this case the size of the droplets increases in proportion to time to the power 1/3. The volume fraction of the minority phase is a good candidate to determine this change of behavior. All previous attempts to vary the volume fraction in a single experimental cell have failed because of the extreme experimental difficulties.

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

    PubMed

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

    2011-03-14

    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.

  19. Phase separation of polymer thin films and some applications

    NASA Astrophysics Data System (ADS)

    Zhu, Shaoming

    Phase separation of polymer thin film is a common issue in polymer thin film application. The existence of surface and surfactant are understood to play an important role in thin film final topography. In chapter two, the configuration of polymer blend thin film phase separation on cobalt substrate with PMMA phase forming column structure, and PS phase encapsulating the PMMA phase was used as resist mask to transfer the topographical feature to cobalt thin film. Isolated near spherical single and multi domain magnetic islands were obtained. The island made using this method had a broad single domain range from below 1000 to 5000A. In chapter three, when the polymer blend thin film was in bilayer configuration and diblock copolymer was added on the top layer, we found the confinement can increase the mixing of two homopolymers in highly incompatible polymer blends. By affecting the formation of micelles, the copolymers are forced to the interface between the two homopolymer phases where they reduce the interfacial tension to zero and form a microemulsion. Our findings have two important implications: first, they elucidate the role entropy plays in determining the phase behaviour of confined polymer blends and second, they offer a simple pathway to create thin film coatings with precisely controlled properties and surfaces. In chapter four, the kinetics process of microemulsion formation in confinement configuration has been analyzed. The microemulsion formation proceeded at initial stage by capillary wave, then it followed the growth regime t1/3 and lnt, then followed a more slow growth regime (lnt).56 or (lnt).60 till finally reached equilibrium, when the structure was frozen. In chapter five, we study the evolution of the morphologies of polymer blend thin films on silicon, cobalt, and gold substrates. In asymmetrical system, the substrate surface energy determined the wetting degree of the substrate preferring phases. In chapter six, we present a novel method for

  20. Thermal conductivity at the amorphous-nanocrystalline phase transition in beech wood biocarbon

    NASA Astrophysics Data System (ADS)

    Parfen'eva, L. S.; Orlova, T. S.; Smirnov, B. I.; Smirnov, I. A.; Misiorek, H.; Jezowski, A.; Ramirez-Rico, J.

    2014-05-01

    High-porosity samples of beech wood biocarbon (BE-C) were prepared by pyrolysis at carbonization temperatures T carb = 650, 1300, and 1600°C, and their resistivity ρ and thermal conductivity κ were studied in the 5-300 and 80-300 K temperature intervals. The experimental results obtained were evaluated by invoking X-ray diffraction data and information on the temperature dependences ρ( T) and κ( T) for BE-C samples prepared at T carb = 800, 1000, and 2400°C, which were collected by the authors earlier. An analysis of the κ( T carb) behavior led to the conclusion that the samples under study undergo an amorphous-nanocrystalline phase transition in the interval 800°C < T carb < 1000°C. Evaluation of the electronic component of the thermal conductivity revealed that the Lorentz number of the sample prepared at T carb = 2400°C exceeds by far the classical Sommerfeld value, which is characteristic of metals and highly degenerate semiconductors.

  1. Local Structure in Ab Initio Liquid Water: Signatures of Amorphous Phases

    NASA Astrophysics Data System (ADS)

    Santra, Biswajit; Distasio, Robert A., Jr.; Martelli, Fausto; Car, Roberto

    Within the framework of density functional theory, the inclusion of exact exchange and non-local van der Waals/dispersion interactions is crucial for predicting a microscopic structure of ambient liquid water that quantitatively agrees with experiment. In this work, we have used the local structure index (LSI) order parameter to analyze the local structure in such highly accurate ab initio liquid water. At ambient conditions, the LSI probability distribution, P(I), was unimodal with most water molecules characterized by more disordered high-density-like local environments. With thermal excitations removed, the resultant bimodal P(I) in the inherent potential energy surface (IPES) exhibited a 3:1 ratio between high- and low-density-like molecules, with the latter forming small connected clusters amid the predominant population. By considering the spatial correlations and hydrogen bond network topologies among water molecules with the same LSI identities, we demonstrate that the signatures of the experimentally observed low- and high-density amorphous phases of ice are present in the IPES of ambient liquid water This work was supported by the DOE: DE-SC0008626, DE-SC0005180.

  2. Effect of Alkali Ions on the Amorphous to Crystalline Phase Transition of Silica

    NASA Astrophysics Data System (ADS)

    Venezia, A. M.; La Parola, V.; Longo, A.; Martorana, A.

    2001-11-01

    The effect of the addition of alkali ions to commercial amorphous silica, generally used as support for heterogeneous catalysts, has been investigated from the point of view of morphological and structural changes. Samples of alkali-doped silica were prepared by impregnation and subsequent calcination at various temperatures. The structural effect of Li, Na, K, and Cs was determined by use of techniques such as wide-angle (WAXS) and small-angle X-ray scattering (SAXS). The WAXS diffractograms, analyzed with the Rietveld method using the GSAS program, allowed qualitative and quantitative identification of the fraction of the different silica polymorphs like quartz, tridymite, and cristobalite. SAXS measurements, using the classical method based on Porod's law, yielded the total surface area of the systems. The calculated areas were compared with the surface areas determined by the nitrogen adsorption technique using the analytical method of Brunauer-Emmett-Teller. The results are explained in terms of sizes of the alkali ions and cell volume of the different crystalline phases.

  3. Radiation-induced defects in dense phases of crystalline and amorphous SiO sub 2

    SciTech Connect

    Devine, R.A.B. ); Hubner, K.

    1989-10-01

    We have studied electron-spin resonance in unirradiated and irradiated samples of naturally occurring stishovite. An unidentified central resonance ({ital g}{similar to}2.0030) with weak hyperfine lines is observed with a density 6{times}10{sup 14} per gram in unirradiated samples. Irradiation induces two sets of hyperfine lines, one sharp (1 gauss peak to peak) and one broad (14 gauss peak to peak) with hyperfine parameters {ital A}{sub {parallel}}=590 gauss, {ital A}{sub {perpendicular}}=457 gauss (sharp) and {ital A}{sub {parallel}}=525{sub {minus}15}{sup +0} gauss, {ital A}{sub {perpendicular}}=503{sub {minus}0}{sup +75} gauss, (broad). The latter set is consistent with {ital E}{sub 1}{sup {prime}} centers in densified, amorphous SiO{sub 2} with {rho}{ge}3.2 gm cm{sup {minus}3} whilst we identify the former with {ital E}{sub 1}{sup {prime}} defects in crystalline Stishovite. The hyperfine parameters for the crystalline phase cannot be interpreted simply in terms of the usual {ital s}-{ital p} electron model.

  4. Construction and Validation of Binary Phase Diagram for Amorphous Solid Dispersion Using Flory-Huggins Theory.

    PubMed

    Bansal, Krishna; Baghel, Uttam Singh; Thakral, Seema

    2016-04-01

    Drug-polymer miscibility is one of the fundamental prerequisite for the successful design and development of amorphous solid dispersion formulation. The purpose of the present work is to provide an example of the theoretical estimation of drug-polymer miscibility and solubility on the basis of Flory-Huggins (F-H) theory and experimental validation of the phase diagram. The F-H interaction parameter, χ d-p, of model system, aceclofenac and Soluplus, was estimated by two methods: by melting point depression of drug in presence of different polymer fractions and by Hildebrand and Scott solubility parameter calculations. The simplified relationship between the F-H interaction parameter and temperature was established. This enabled us to generate free energy of mixing (ΔG mix) curves for varying drug-polymer compositions at different temperatures and finally the spinodal curve. The predicted behavior of the binary system was evaluated through X-ray diffraction, differential scanning calorimetry, and in vitro dissolution studies. The results suggest possibility of employing interaction parameter as preliminary tool for the estimation of drug-polymer miscibility.

  5. Phase separation of metallic hydrogen-helium alloys

    NASA Technical Reports Server (NTRS)

    Straus, D. M.; Ashcroft, N. W.; Beck, H.

    1977-01-01

    Calculations are presented for the thermodynamic functions and phase-separation boundaries of solid metallic hydrogen-helium alloys at temperatures between zero and 19,000 K and at pressures between 15 and 90 Mbar. Expressions for the band-structure energy of a randomly disordered alloy (including third order in the electron-ion interaction) are derived and evaluated. Short- and long-range orders are included by the quasi-chemical method, and lattice dynamics in the virtual-crystal harmonic approximation. It is concluded that at temperatures below 4000 K, there is essentially complete phase separation of hydrogen-helium alloys and that a miscibility gap remains at the highest temperatures and pressures considered. The relevance of these results to models of the deep interior of Jupiter is briefly discussed.

  6. Critical properties and phase separation in lattice Boltzmann fluid mixtures.

    PubMed

    Martys, N S; Douglas, J F

    2001-03-01

    Basic equilibrium properties of lattice Boltzmann (LB) fluid mixtures (coexistence curve, surface tension, interfacial profile, correlation length) are calculated to characterize the critical phenomena occurring in these model liquids and to establish a reduced variable description allowing a comparison with real fluid mixtures. We observe mean-field critical exponents and amplitudes so that the LB model may be useful for modeling high molecular weight polymer blends and other fluid mixtures approximated over a wide temperature range by mean-field theory. We also briefly consider phase separation under quiescent and shearing conditions and point out the strong influence of interacting boundaries on the qualitative form of the late-stage phase-separation morphology.

  7. Phase separation of metallic hydrogen-helium alloys

    NASA Technical Reports Server (NTRS)

    Straus, D. M.; Ashcroft, N. W.; Beck, H.

    1976-01-01

    Calculations are presented for the thermodynamic functions and phase separation boundaries of solid metallic hydrogen helium alloys at temperatures between 0 K and 19,000 K and at pressures between 15 and 90 megabars. Expressions for the band structure energy of a randomly disordered alloy (including third order in the electron ion interaction) are derived and evaluated. Short and long range order are included by the quasi-chemical method, and lattice dynamics in the virtual crystal harmonic approximation. We conclude that at temperatures below 4,000 K there is complete phase separation of hydrogen helium alloys, and that a miscibility gap remains at the highest temperatures and pressures considered. The relevance of these results to models of the deep interior of Jupiter is briefly discussed.

  8. Fibril Formation and Phase Separation in Aqueous Cellulose Ethers

    NASA Astrophysics Data System (ADS)

    Maxwell, Amanda; Schmidt, Peter; McAllister, John; Lott, Joseph; Bates, Frank; Lodge, Timothy

    Aqueous solutions of many cellulose ethers are known to undergo thermoreversible gelation and phase separation upon heating to form turbid hydrogels, but the mechanism and resulting structures have not been well understood. Turbidity, light scattering and small-angle neutron scattering (SANS) are used to show that hydroxypropyl methylcellulose (HPMC) chains are dissolved in water below 50 °C and undergo phase separation at higher temperatures. At 70 °C, at sufficiently high concentrations in water, HPMC orders into fibrillar structures with a well-defined radius of 18 +/- 2 nm, as characterized by cryogenic transmission electron microscopy and SANS. The HPMC fibril structure is independent of concentration and heating rate. However, HPMC fibrils do not form a percolating network as readily as is seen in methylcellulose, resulting in a lower hot-gel modulus, as demonstrated by rheology.

  9. GPU accelerated numerical simulations of viscoelastic phase separation model.

    PubMed

    Yang, Keda; Su, Jiaye; Guo, Hongxia

    2012-07-05

    We introduce a complete implementation of viscoelastic model for numerical simulations of the phase separation kinetics in dynamic asymmetry systems such as polymer blends and polymer solutions on a graphics processing unit (GPU) by CUDA language and discuss algorithms and optimizations in details. From studies of a polymer solution, we show that the GPU-based implementation can predict correctly the accepted results and provide about 190 times speedup over a single central processing unit (CPU). Further accuracy analysis demonstrates that both the single and the double precision calculations on the GPU are sufficient to produce high-quality results in numerical simulations of viscoelastic model. Therefore, the GPU-based viscoelastic model is very promising for studying many phase separation processes of experimental and theoretical interests that often take place on the large length and time scales and are not easily addressed by a conventional implementation running on a single CPU.

  10. Correlated lateral phase separations in stacks of lipid membranes

    NASA Astrophysics Data System (ADS)

    Hoshino, Takuma; Komura, Shigeyuki; Andelman, David

    2015-12-01

    Motivated by the experimental study of Tayebi et al. [Nat. Mater. 11, 1074 (2012)] on phase separation of stacked multi-component lipid bilayers, we propose a model composed of stacked two-dimensional Ising spins. We study both its static and dynamical features using Monte Carlo simulations with Kawasaki spin exchange dynamics that conserves the order parameter. We show that at thermodynamical equilibrium, due to strong inter-layer correlations, the system forms a continuous columnar structure for any finite interaction across adjacent layers. Furthermore, the phase separation shows a faster dynamics as the inter-layer interaction is increased. This temporal behavior is mainly due to an effective deeper temperature quench because of the larger value of the critical temperature, Tc, for larger inter-layer interaction. When the temperature ratio, T/Tc, is kept fixed, the temporal growth exponent does not increase and even slightly decreases as a function of the increased inter-layer interaction.

  11. Correlated lateral phase separations in stacks of lipid membranes.

    PubMed

    Hoshino, Takuma; Komura, Shigeyuki; Andelman, David

    2015-12-28

    Motivated by the experimental study of Tayebi et al. [Nat. Mater. 11, 1074 (2012)] on phase separation of stacked multi-component lipid bilayers, we propose a model composed of stacked two-dimensional Ising spins. We study both its static and dynamical features using Monte Carlo simulations with Kawasaki spin exchange dynamics that conserves the order parameter. We show that at thermodynamical equilibrium, due to strong inter-layer correlations, the system forms a continuous columnar structure for any finite interaction across adjacent layers. Furthermore, the phase separation shows a faster dynamics as the inter-layer interaction is increased. This temporal behavior is mainly due to an effective deeper temperature quench because of the larger value of the critical temperature, Tc, for larger inter-layer interaction. When the temperature ratio, T/Tc, is kept fixed, the temporal growth exponent does not increase and even slightly decreases as a function of the increased inter-layer interaction.

  12. Kinetics of motility-induced phase separation and swim pressure

    NASA Astrophysics Data System (ADS)

    Patch, Adam; Yllanes, David; Marchetti, M. Cristina

    2017-01-01

    Active Brownian particles (ABPs) represent a minimal model of active matter consisting of self-propelled spheres with purely repulsive interactions and rotational noise. Here we examine the pressure of ABPs in two dimensions in both closed boxes and systems with periodic boundary conditions and show that its nonmonotonic behavior with density is a general property of ABPs and is not the result of finite-size effects. We correlate the time evolution of the mean pressure towards its steady-state value with the kinetics of motility-induced phase separation. For parameter values corresponding to phase-separated steady states, we identify two dynamical regimes. The pressure grows monotonically in time during the initial regime of rapid cluster formation, overshooting its steady-state value and then quickly relaxing to it, and remains constant during the subsequent slower period of cluster coalescence and coarsening. The overshoot is a distinctive feature of active systems.

  13. Transport Selectivity of Nuclear Pores, Phase Separation, and Membraneless Organelles.

    PubMed

    Schmidt, H Broder; Görlich, Dirk

    2016-01-01

    Nuclear pore complexes (NPCs) provide a selective passageway for receptor-mediated active transport between nucleus and cytoplasm, while maintaining the distinct molecular compositions of both compartments at large. In this review we discuss how NPCs gain a remarkable sorting selectivity from non-globular FG domains and their phase separation into dense polymer meshworks. The resulting sieve-like FG hydrogels are effective barriers to normal macromolecules but are at the same time highly permeable to shuttling nuclear transport receptors, which bind to FG motifs as well as to their designated cargoes. Phase separation driven by disordered protein domains was recently also recognized as being pivotal to the formation of membraneless organelles, making it an important emerging principle in cell biology. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Tc anisotropy and phase separation in strained Vanadium Dioxide films

    NASA Astrophysics Data System (ADS)

    Liu, Mengkun; Wagner, Martin; Abreu, Elsa; Kittiwatanakul, Salinporn; McLeod, Alexander; Goldflam, Michael; Fei, Zhe; Dai, Siyuan; Fogler, Michael; Lu, Jiwei; Wolf, Stuart; Averitt, Richard; Basov, D. N.

    2013-03-01

    We report Infrared near field study on strain induced transition temperature (Tc) anisotropy in vanadium dioxide (VO2) films via direct visualization of a spontaneous structural and electronic phase separation. The films are epitaxially grown on [110]R or [100]R TiO2 substrates and exhibit large uniaxial strain. By mapping the film topography with AFM and electronic percolation with Infrared scattering scanning near-field optical microscopy, a temperature dependent electron-lattice correlation can be clearly observed. Our work sheds a new light onto the nature of the Tc anomaly in metal-insulator transition and leads to the possibility of controlling the material's properties through strain induced phase separation.

  15. Lattice-gas models of phase separation: interfaces, phase transitions, and multiphase flow

    SciTech Connect

    Rothman, D.H. ); Zaleski, S. )

    1994-10-01

    Momentum-conserving lattice gases are simple, discrete, microscopic models of fluids. This review describes their hydrodynamics, with particular attention given to the derivation of macroscopic constitutive equations from microscopic dynamics. Lattice-gas models of phase separation receive special emphasis. The current understanding of phase transitions in these momentum-conserving models is reviewed; included in this discussion is a summary of the dynamical properties of interfaces. Because the phase-separation models are microscopically time irreversible, interesting questions are raised about their relationship to real fluid mixtures. Simulation of certain complex-fluid problems, such as multiphase flow through porous media and the interaction of phase transitions with hydrodynamics, is illustrated.

  16. Separation of granulocytes from whole blood by leukoadhesion, phase 1

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Capillary glass tubes are investigated for the separation and retrieval of large quantities of viable granulocytes and monocytes from whole blood on a continuous basis from a single donor. This effort represented the feasibility demonstration of a three phase program for development of a capillary tube cell separation device. The activity included the analysis and parametric laboratory testing with subscale models required to design a prototype device. Capillary tubes 40 cm long with a nominal 0.030 cm internal diameter yielded the highest total process efficiency. Recovery efficiencies as high as 89% of the adhering cell population were obtained. Granulocyte phagocytosis of latex particles indicated approximately 90% viability. Monocytes recovered from the separation column retained their capability to stimulate human bone marrow colony growth, as demonstrated in an in vitro cell culture assay.

  17. Rationale for two phase polymer system microgravity separation experiments

    NASA Technical Reports Server (NTRS)

    Brooks, D. E.; Bamberger, S. B.; Harris, J. M.; Vanalstine, J.

    1984-01-01

    The two-phase systems that result when aqueous solutions of dextran and poly(ethylene glycol) are mixed at concentrations above a few percent are discussed. They provide useful media for the partition and isolation of macromolecules and cell subpopulations. By manipulating their composition, separations based on a variety of molecular and surface properties are achieved, including membrane hydrophobic properties, cell surface charge, and membrane antigenicity. Work on the mechanism of cell partition shows there is a randomizing, nonthermal energy present which reduces separation resolution. This stochastic energy is probably associated with hydrodynamic interactions present during separation. Because such factors should be markedly reduced in microgravity, a series of shuttle experiments to indicate approaches to increasing the resolution of the procedure are planned.

  18. The Potential of Amorphous Solid Secondary Organic Aerosol to Form Mixed-Phase and Cirrus Clouds

    NASA Astrophysics Data System (ADS)

    Knopf, D. A.; Wang, B.; Lambe, A. T.; Massoli, P.; Onasch, T. B.; Davidovits, P.; Worsnop, D. R.

    2012-12-01

    Atmospheric ice formation by heterogeneous nucleation, which results in cirrus and mixed-phase cloud formation, is one of the least understood processes affecting the global radiation budget, the hydrological cycle, and water vapor distribution. It is commonly assumed that inorganic particles such as mineral dust and solid ammonium sulfate represent important atmospheric ice nuclei (IN). However, a growing body of evidence suggests that secondary organic aerosols (SOA), which are ubiquitous in the atmosphere, exist in a solid (glassy) state. This implies that SOA may also play a role in ice cloud formation by acting as IN, but has not previously been experimentally verified. Here, we report observations of water uptake and ice nucleation via condensation, immersion, and deposition modes initiated by amorphous SOA particles at temperatures from T = 200 - 250 K and relative humidity (RH) from subsaturation conditions up to water saturation. SOA particles with oxygen-to-carbon (O/C) ratios ranging from 0.3 to 1.0 are generated from gas-phase OH oxidation of naphthalene in a flow reactor. At T > 230 K, water uptake at subsaturation conditions is correlated with SOA oxidation level (O/C ratio). This initial water uptake is followed by a moisture-induced phase transition and subsequent immersion freezing. At T < 230 K, the SOA forms ice via deposition nucleation at RH with respect to ice 10-15% below the homogeneous ice nucleation limit, with no apparent dependence on oxidation level. The SOA glass transition temperature (Tg) is estimated as a function of RH, temperature, and SOA oxidation level from corresponding measurements of particle density, hygroscopicity, and bounced fraction, the latter indicating particle phase state. Above Tg, water uptake and immersion freezing is observed when the particles are liquid or semi-solid. Below Tg, deposition ice nucleation is observed when the particles are solid. The data show that particle phase and viscosity govern the

  19. Separating homeologs by phasing in the tetraploid wheat transcriptome

    PubMed Central

    2013-01-01

    Background The high level of identity among duplicated homoeologous genomes in tetraploid pasta wheat presents substantial challenges for de novo transcriptome assembly. To solve this problem, we develop a specialized bioinformatics workflow that optimizes transcriptome assembly and separation of merged homoeologs. To evaluate our strategy, we sequence and assemble the transcriptome of one of the diploid ancestors of pasta wheat, and compare both assemblies with a benchmark set of 13,472 full-length, non-redundant bread wheat cDNAs. Results A total of 489 million 100 bp paired-end reads from tetraploid wheat assemble in 140,118 contigs, including 96% of the benchmark cDNAs. We used a comparative genomics approach to annotate 66,633 open reading frames. The multiple k-mer assembly strategy increases the proportion of cDNAs assembled full-length in a single contig by 22% relative to the best single k-mer size. Homoeologs are separated using a post-assembly pipeline that includes polymorphism identification, phasing of SNPs, read sorting, and re-assembly of phased reads. Using a reference set of genes, we determine that 98.7% of SNPs analyzed are correctly separated by phasing. Conclusions Our study shows that de novo transcriptome assembly of tetraploid wheat benefit from multiple k-mer assembly strategies more than diploid wheat. Our results also demonstrate that phasing approaches originally designed for heterozygous diploid organisms can be used to separate the close homoeologous genomes of tetraploid wheat. The predicted tetraploid wheat proteome and gene models provide a valuable tool for the wheat research community and for those interested in comparative genomic studies. PMID:23800085

  20. Macroscopic phase separation in high-temperature superconductors

    PubMed Central

    Wen, Hai-Hu

    2000-01-01

    High-temperature superconductivity is recovered by introducing extra holes to the Cu-O planes, which initially are insulating with antiferromagnetism. In this paper I present data to show the macroscopic electronic phase separation that is caused by either mobile doping or electronic instability in the overdoped region. My results clearly demonstrate that the electronic inhomogeneity is probably a general feature of high-temperature superconductors. PMID:11027323

  1. Theory of amorphous ices

    PubMed Central

    Limmer, David T.; Chandler, David

    2014-01-01

    We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens. PMID:24858957

  2. Phase separation in LuFeO{sub 3} films

    SciTech Connect

    Cao, Shi E-mail: caoshi86@gmail.com; Sinha, Kishan; Dowben, Peter A.; Xu, Xiaoshan E-mail: caoshi86@gmail.com; Zhang, Xiaozhe; Wang, Wenbin; Wang, Jian

    2016-05-16

    The structural transition at about 1000 °C, from the hexagonal to the orthorhombic phase of LuFeO{sub 3}, has been investigated in thin films of LuFeO{sub 3}. Separation of the two structural phases of LuFeO{sub 3} occurs on a length scale of micrometer, as visualized in real space using X-ray photoemission electron microscopy. The results are consistent with X-ray diffraction and atomic force microscopy obtained from LuFeO{sub 3} thin films undergoing the irreversible structural transition from the hexagonal to the orthorhombic phase of LuFeO{sub 3}, at elevated temperatures. The sharp phase boundaries between the structural phases are observed to align with the crystal planes of the hexagonal LuFeO{sub 3} phase. The coexistence of different structural domains indicates that the irreversible structural transition, from the hexagonal to the orthorhombic phase in LuFeO{sub 3}, is a first order transition, for epitaxial hexagonal LuFeO{sub 3} films grown on Al{sub 2}O{sub 3}.

  3. Phase separated microstructure and dynamics of polyurethane elastomers under strain

    NASA Astrophysics Data System (ADS)

    Iacob, Ciprian; Padsalgikar, Ajay; Runt, James

    The molecular mobility of polyurethane elastomers is of the utmost importance in establishing physical properties for uses ranging from automotive tires and shoe soles to more sophisticated aerospace and biomedical applications. In many of these applications, chain dynamics as well as mechanical properties under external stresses/strains are critical for determining ultimate performance. In order to develop a more complete understanding of their mechanical response, we explored the effect of uniaxial strain on the phase separated microstructure and molecular dynamics of the elastomers. We utilize X-ray scattering to investigate soft segment and hard domain orientation, and broadband dielectric spectroscopy for interrogation of the dynamics. Uniaxial deformation is found to significantly perturb the phase-separated microstructure and chain orientation, and results in a considerable slowing down of the dynamics of the elastomers. Attenuated total reflectance Fourier transform infrared spectroscopy measurements of the polyurethanes under uniaxial deformation are also employed and the results are quantitatively correlated with mechanical tensile tests and the degree of phase separation from small-angle X-ray scattering measurements.

  4. Novel Resistive Switching Behavior in Phase Separated Manganites

    NASA Astrophysics Data System (ADS)

    Guo, Hangwen; Ward, T. Zac; Sun, Dali; Snijders, Paul C.; Gai, Zheng; Shen, Jian

    2011-03-01

    Electronic phase separation plays a key role in many novel phenomena in complex materials. Manganites are a prime example of this class of materials and have recently come under increase scrutiny for possible application in resistive random-access memory (RRAM) technology. Here, we will discuss our recent work on spatially confined La5/8-xPrxCa3/8MnO3. We have discovered that it is possible to drive single electronic domain formation/annihilation through electric field pulsing. By measuring the I-V curve, we find such resistive switching is different from normal RRAM mechanisms in manganites and is closely related to the nature of electronic phase separation. These findings open these systems to a new understanding of the nature of electronic phase separation and begin the development of manganites for future applications in RRAM devices. Research sponsored by the Division of Materials Sciences and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy.

  5. An amorphous phase formation at palladium / silicon oxide (Pd/SiO{sub x}) interface through electron irradiation - electronic excitation process

    SciTech Connect

    Nagase, Takeshi; Yamashita, Ryo; Yabuuchi, Atsushi; Lee, Jung-Goo

    2015-11-15

    A Pd-Si amorphous phase was formed at a palladium/silicon oxide (Pd/SiO{sub x}) interface at room temperature by electron irradiation at acceleration voltages ranging between 25 kV and 200 kV. Solid-state amorphization was stimulated without the electron knock-on effects. The total dose required for the solid-state amorphization decreases with decreasing acceleration voltage. This is the first report on electron irradiation induced metallic amorphous formation caused by the electronic excitation at metal/silicon oxide interface.

  6. On the photoinduced phase transition from the amorphous to crystalline phase in (GeTe) n (Sb2Te3) m

    NASA Astrophysics Data System (ADS)

    Yakubenya, Sergei M.; Mishchenko, Andrey S.

    2017-01-01

    We suggest a phenomenological description of the photo-conversion in Ge-Sb-Te phase-change memory alloys from amorphous to crystalline tetrahedral phase. Suggested mechanism explains why both photo-excitation and high enough temperatures T > 160 °C are required for the transition from the amorphous to metastable crystalline phase. High energy position of chemical potential at elevated temperatures facilitates light induced creation of stable nucleons of the crystalline phase which are unstable at lower T. Then, light driven population of nucleons leads to accumulation of holes on neighboring Te and Ge ions and locks the photo-conversion transition by pushing Ge ions into the interstitial position to minimize the Coulomb repulsion energy.

  7. Novel 3-hydroxypropyl-bonded phase by direct hydrosilylation of allyl alcohol on amorphous hydride silica.

    PubMed

    Gómez, Jorge E; Navarro, Fabián H; Sandoval, Junior E

    2014-09-01

    A novel 3-hydroxypropyl (propanol)-bonded silica phase has been prepared by hydrosilylation of allyl alcohol on a hydride silica intermediate, in the presence of platinum (0)-divinyltetramethyldisiloxane (Karstedt's catalyst). The regio-selectivity of this synthetic approach had been correctly predicted by previous reports involving octakis(dimethylsiloxy)octasilsesquioxane (Q8 M8 (H) ) and hydrogen silsesquioxane (T8 H8 ), as molecular analogs of hydride amorphous silica. Thus, C-silylation predominated (∼94%) over O-silylation, and high surface coverages of propanol groups (5 ± 1 μmol/m(2) ) were typically obtained in this work. The propanol-bonded phase was characterized by spectroscopic (infrared (IR) and solid-state NMR on silica microparticles), contact angle (on fused-silica wafers) and CE (on fused-silica tubes) techniques. CE studies of the migration behavior of pyridine, caffeine, Tris(2,2'-bipyridine)Ru(II) chloride and lysozyme on propanol-modified capillaries were carried out. The adsorption properties of these select silanol-sensitive solutes were compared to those on the unmodified and hydride-modified tubes. It was found that hydrolysis of the SiH species underlying the immobilized propanol moieties leads mainly to strong ion-exchange-based interactions with the basic solutes at pH 4, particularly with lysozyme. Interestingly, and in agreement with water contact angle and electroosmotic mobility figures, the silanol-probe interactions on the buffer-exposed (hydrolyzed) hydride surface are quite different from those of the original unmodified tube. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. High-field electrical transport in amorphous phase-change materials

    NASA Astrophysics Data System (ADS)

    Kaes, Matthias; Le Gallo, Manuel; Sebastian, Abu; Salinga, Martin; Krebs, Daniel

    2015-10-01

    Electrical transport in chalcogenide-based phase change materials is an active area of research owing to the prominent role played by these materials in the field of information technology. Here, we present transport measurements (IV curves) obtained on line-cells of as-deposited amorphous phase change materials (Ge2Sb2Te5, GeTe, Ag4In3Sb66Te27) over a wide voltage and temperature range (300 K to 160 K). The well defined geometry of our devices enables a description of the transport behavior in terms of conductivity vs. electric field. At higher temperatures (300 K ≥ T ≥ 220 K) and low to intermediate fields (F < 20 V/μm), the data can be described within the framework of a previously developed model, which is based on multiple trapping transport together with 3D Poole-Frenkel emission from a two-center Coulomb potential. Based on this model, we observe a temperature dependence of the inter-trap distance, which we can relate to a temperature dependence in the occupation of the defect creating the Coulomb potential governing Poole-Frenkel emission. At higher fields and lower temperatures, the dependency of the IV curve on the electric field can be described by ln(I/I0) = (F/Fc)2. By combining this contribution with that of the Poole-Frenkel emission, we can show that the slope at high fields, Fc, is independent of temperature. We argue that models based on direct tunneling or thermally assisted tunneling from a single defect into the valence band cannot explain the observed behavior quantitatively.

  9. An IR investigation of solid amorphous ethanol - Spectra, properties, and phase changes.

    PubMed

    Hudson, Reggie L

    2017-12-05

    Mid- and far-infrared spectra of condensed ethanol (CH3CH2OH) at 10-160K are presented, with a special focus on amorphous ethanol, the form of greatest astrochemical interest, and with special attention given to changes at 155-160K. Infrared spectra of amorphous and crystalline forms are shown. The refractive index at 670nm of amorphous ethanol at 16K is reported, along with three IR band strengths and a density. A comparison is made to recent work on the isoelectronic compound ethanethiol (CH3CH2SH), and several astrochemical applications are suggested for future study. Published by Elsevier B.V.

  10. An IR Investigation of Solid Amorphous Ethanol-Spectra, Properties, and Phase Changes

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.

    2017-01-01

    Mid- and far-infrared spectra of condensed ethanol (CH3CH2OH) at 10-160 K are presented, with a special focus on amorphous ethanol, the form of greatest astrochemical interest, and with special attention given to changes at 155-160 K. Infrared spectra of amorphous and crystalline forms are shown. The refractive index at 670 nm of amorphous ethanol at 16 K is reported, along with three IR band strengths and a density. A comparison is made to recent work on the isoelectronic compound ethanethiol (CH3CH2SH), and several astrochemical applications are suggested for future study.

  11. Evaluation of phase separator number in hydrodesulfurization (HDS) unit

    NASA Astrophysics Data System (ADS)

    Jayanti, A. D.; Indarto, A.

    2016-11-01

    The removal process of acid gases such as H2S in natural gas processing industry is required in order to meet sales gas specification. Hydrodesulfurization (HDS)is one of the processes in the refinery that is dedicated to reduce sulphur.InHDS unit, phase separator plays important role to remove H2S from hydrocarbons, operated at a certain pressure and temperature. Optimization of the number of separator performed on the system is then evaluated to understand the performance and economics. From the evaluation, it shows that all systems were able to meet the specifications of H2S in the desired product. However, one separator system resulted the highest capital and operational costs. The process of H2S removal with two separator systems showed the best performance in terms of both energy efficiency with the lowest capital and operating cost. The two separator system is then recommended as a reference in the HDS unit to process the removal of H2S from natural gas.

  12. Biogenic Fish-gut Calcium Carbonate is a Stable Amorphous Phase in the Gilt-head Seabream, Sparus aurata

    PubMed Central

    Foran, Elizabeth; Weiner, Steve; Fine, Maoz

    2013-01-01

    The main source of calcium carbonate (CaCO3) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO3 are also produced in fish intestines. The precipitation of CaCO3 assists fish in intestinal water absorption and aids in whole body Ca2+ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg2+, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration. PMID:23609008

  13. Phase separation in artificial vesicles driven by light and curvature

    NASA Astrophysics Data System (ADS)

    Rinaldin, Melissa; Pomp, Wim; Schmidt, Thomas; Giomi, Luca; Kraft, Daniela; Physics of Life Processes Team; Soft; Bio Mechanics Collaboration; Self-Assembly in Soft Matter Systems Collaboration

    The role of phase-demixing in living cells, leading to the lipid-raft hypothesis, has been extensively studied. Lipid domains of higher lipid chain order are proposed to regulate protein spatial organization. Giant Unilamellar Vesicles provide an artificial model to study phase separation. So far temperature was used to initiate the process. Here we introduce a new methodology based on the induction of phase separation by light. To this aim, the composition of the lipid membrane is varied by photo-oxidation of lipids. The control of the process gained by using light allowed us to observe vesicle shape fluctuations during phase-demixing. The presence of fluctuations near the critical mixing point resembles features of a critical process. We quantitatively analyze these fluctuations using a 2d elastic model, from which we can estimate the material parameters such as bending rigidity and surface tension, demonstrating the non-equilibrium critical behaviour. Finally, I will describe recent attempts toward tuning the membrane composition by controlling the vesicle curvature.

  14. Phase separation in model lipid membranes: physics and biophysics

    NASA Astrophysics Data System (ADS)

    Gordon, Vernita; Beales, Paul; Deserno, Markus; Andrew, Caroline; Zhao, Zhijun; Egelhaaf, Stefan; Poon, Wilson

    2007-03-01

    Lipids are biological amphiphiles that, in aqueous solution, self-assemble into a variety of structures, including bilayer membranes that form hollow vesicles. In membranes with two or more constituents, lipids are well-mixed when the temperature is sufficiently high. As the temperature is lowered, systems undergo ordering transitions, membranes phase-separate laterally, and the resulting domains pattern vesicles. Here we demonstrate different aspects of this patterning that are important both for basic science and for their technological potentials: the packings of lipids in ordered-phase domains determine the domains' morphologies and inclusivities; adherent regions of membranes favour the growth of ordered-phase domains; rapid phase separation forms many small stripe domains that pattern vesicles with a `baseball' texture. These phenomena demonstrate basic physics and also have strong potential for exploitation to achieve vesicles with controllable patterns and properties. Lipid structures such as vesicles are attractive candidates for such technological development because they are intrinsicly biocompatible and because technologies using liposomes for controlled delivery and release are already widespread and under active development.

  15. Uphill diffusion and phase separation in partially miscible multicomponent mixtures

    NASA Astrophysics Data System (ADS)

    He, Ping; Raghavan, Ashwin; Ghoniem, Ahmed

    2015-11-01

    The partially miscible multicomponent mixtures, which are frequently encountered in green chemistry processes, often exhibit complicated behaviors, and are critical to the production rate, energy efficiency, and pollution controls. Recent studies have been mainly focused on phase behaviors. However, the coupled phase equilibrium and transport process, which may be the answer to phase separations observed in experiments, is not well researched. Here, we present a numerical and theoretical study on coupled mixing of heavy oil and supercritical water, and the results of our state-of-art modeling agree with experimental measurements. We find that due to the non-ideal diffusion driving force, (1) strong uphill diffusion of heavy oil fractions occurs, (2) a new heavy oil phase is separated starting from the plait point, and heavy fractions become highly concentrated, and (3) water diffusion initially overshoots in oil, and is expelled lately. Finally, we conclude our analysis applicable to different molecules and conditions. The authors thank Saudi Aramco for supporting this work (contract number 6600023444).

  16. First-principles computation of mantle materials in crystalline and amorphous phases

    NASA Astrophysics Data System (ADS)

    Karki, Bijaya B.

    2015-03-01

    First-principles methods based on density functional theory are used extensively in the investigation of the behavior and properties of mantle materials over broad ranges of pressure, temperature, and composition that are relevant. A review of computational results reported during the last couple of decades shows that essentially all properties including structure, phase transition, equation of state, thermodynamics, elasticity, alloying, conductivity, defects, interfaces, diffusivity, viscosity, and melting have been calculated from first principles. Using MgO, the second most abundant oxide of Earth's mantle, as a primary example and considering many other mantle materials in their crystalline and amorphous phases, we have found that most properties are strongly pressure dependent, sometimes varying non-monotonically and anomalously, with the effects of temperature being systematically suppressed with compression. The overall agreement with the available experimental data is excellent; it is remarkable that the early-calculated results such as shear wave velocities of two key phases, MgO and MgSiO3 perovskite, were subsequently reproduced by experimentation covering almost the entire mantle pressure regime. As covered in some detail, the defect formation and migration enthalpies of key mantle materials increase with pressure. The predicted trend is that partial MgO Schottky defects are energetically most favorable in Mg-silicates but their formation enthalpies are high. So, the diffusion in the mantle is likely to be in the extrinsic regime. Preliminary results on MgO and forsterite hint that the grain boundaries can accommodate point defects (including impurities) and enhance diffusion rates at all pressures. The structures are highly distorted in the close vicinity of the defects and at the interface with excess space. Recent simulations of MgO-SiO2 binary and other silicate melts have found that the melt self-diffusion and viscosity vary by several orders of

  17. Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

    SciTech Connect

    Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; Park, Joonsuk; Koh, Ai Leen; Abild-Pedersen, Frank; Jaramillo, Thomas F.; Sinclair, Robert

    2015-12-01

    Amorphous MoSx is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS2 in composition and chemical state. However, structural changes in the MoSx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoSx catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmental TEM. For the first time, we directly observe the formation of crystalline domains in the MoSx catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoSx catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H2 generation.

  18. Thermodynamics of the motility-induced phase separation

    NASA Astrophysics Data System (ADS)

    Solon, Alexandre; Stenhammar, Joachim; Cates, Michael; Tailleur, Julien

    Self-propelled particles are known to accumulate in regions of space where their velocity is lowered. In addition, if their velocity diminishes when the local density increases (for example due to crowding effects), a positive feedback loop leads to the now well-established motility-induced phase separation (MIPS) between a dense immotile phase and a dilute motile phase. Understanding the phase equilibrium of MIPS is still a matter of debate. Although, depending on the models used to study the transition, a chemical potential or a pressure can be defined, these quantities do not play their usual thermodynamic role. In particular, the usual common tangent or equal-area constructions fail in these systems. Indeed, we will show that describing the phase equilibrium of MIPS necessitates generalized thermodynamics that include non-equilibrium contributions. This approach allows us to predict correctly the phase diagram of MIPS and to gain insight into the thermodynamics of active systems. It also sheds light on the (in)equivalence of statistical ensembles for these systems, paving the way for more efficient computational studies.

  19. Morphology of Liquid-Liquid Phase Separated Aerosols.

    PubMed

    Qiu, Yuqing; Molinero, Valeria

    2015-08-26

    The morphology of liquid-liquid phase separated aerosols has a strong impact on their rate of gas and water uptake, and the type and rate of heterogeneous reactions in the atmosphere. However, it is extremely challenging to experimentally distinguish different morphologies (core-shell or partial wetting) of aerosols and to quantify the extent of wetting between the two phases. The aim of this work is to quantitatively predict the morphology of liquid-liquid aerosols from fundamental physical properties of the aerosol phases. We determine the equilibrium structure of liquid-liquid phase separated aerosols through free energy minimization and predict that the contact angle between the two liquids in the aerosol depends on the composition but not the amount of each phase. We demonstrate that for aerosols of diameter larger than ∼100 nm, the equilibrium contact angle can be accurately predicted from the surface tensions of each liquid with the vapor and between the two liquids through an expression that is identical to Young's equation. The internal structure of smaller, ultrafine aerosols depends also on the value of the line tension between the two liquids and the vapor. The thermodynamic model accurately predicts the experimental morphology, core-shell or partial wetting, of all aerosols for which surface tensions are provided in the literature, and provides contact angles that cannot be accurately determined with state of the art experimental methods. We find that the contact angle of model atmospheric aerosols is rarely higher than 30°. We validate the thermodynamic predictions through molecular simulations of nonane-water droplets, and use the simulation data to compute line tension values that are in good agreement with theory and the analysis from experimental data in water-nonane droplets. Our finding of a simple analytical equation to compute the contact angle of liquid-liquid droplets should have broad application for the prediction of the morphology of

  20. Enhanced Oxygen Evolution Reaction Electrocatalysis via Electrodeposited Amorphous α-Phase Nickel-Cobalt Hydroxide Nanodendrite Forests.

    PubMed

    Balram, Anirudh; Zhang, Hanfei; Santhanagopalan, Sunand

    2017-08-30

    We demonstrate an electrodeposition method to rapidly grow novel three-dimensional nanodendrite forests of amorphous α-phase mixed nickel-cobalt hydroxides on stainless steel foil toward high performance electrocatalysis of the oxygen evolution reaction (OER). The proposed hydrogen bubble-templated, diffusion-limited deposition process leads to the unprecedented dendritic growth of vertically aligned amorphous metal hydroxides, induced by the controlled electrolysis of the tuned water content in the primarily alcohol-based deposition solution. The hierarchical nature of these binder-free, amorphous metal hydroxide deposits leads to their superhydrophilic nature and underwater superaerophobic behavior. The combination of all of these qualities leads to exemplary catalytic performance. When directly grown on planar stainless steel substrates, these nanoforests show high OER activity with overpotentials as low as ∼255 mV to produce a current density of 10 mA cm(-2) over 10 000 accelerated stability test cycles. This work demonstrates a novel fabrication technique that can simultaneously achieve a dendritic hierarchical structure, vertical alignment, superaerophobicity, amorphous crystal structure, and intimate contact with the substrate that leads to high catalytic activity with excellent durability.

  1. Separation of peptides on superficially porous particle based macrocyclic glycopeptide liquid chromatography stationary phases: consideration of fast separations.

    PubMed

    Wimalasinghe, Rasangi M; Breitbach, Zachary S; Lee, Jauh T; Armstrong, Daniel W

    2017-03-01

    Macrocyclic glycopeptide based liquid chromatography stationary phases are known for their highly selective peptide separations. Fast and ultrafast (t R < 1 min) high-efficiency separations were achieved with superficially porous particle (SPP)-based stationary phases. Separations of pharmaceutically important classes of peptides such as enkephalins and bradykinins have been achieved in less than 5 min in isocratic elution modes. Selectivity for peptides structurally similar to one another was increased with use of teicoplanin-based stationary phases compared with commercial C18 stationary phases. Ultrafast isocratic separations of structurally related peptides were achieved with teicoplanin- and vancomycin-based short SPP columns. Acidic mobile phases produced better separations. Ammonium formate was the optimal mobile phase buffer additive. Use of an appropriate combination of a macrocyclic glycopeptide stationary phase and a mobile phase permits faster and more electrospray ionization mass spectrometry compatible isocratic separations than previous gradient approaches. The tryptic peptide separation characteristics of the teicoplanin stationary phase are demonstrated. Additionally, compared with commercial C18 stationary phases, teicoplanin showed tryptic peptide separations with different selectivities. Graphical Abstract Ultrafast separation of enkephalin peptide epimers.

  2. Gas-Liquid Two-Phase Flow Distribution Using Phase Separation Method

    NASA Astrophysics Data System (ADS)

    Zhang, B. D.; Liu, D.; Wang, D.

    2010-03-01

    A method for gas-liquid two-phase flow distribution is proposed in this study, which can be called the phase separation method. The advantage of the new method is that it converts two-phase flow distribution into single-phase distribution, which overcomes the problem of phase splitting in the distribution process of two-phase flow radically, and an equal quality distribution is guaranteed. At first, separate the mixture of gas and liquid into single or near single phase fluids by enhancing phase splitting in distributor, then distribute the single gas and liquid flow respectively as required, finally recombine each couple of gas and liquid stream respectively to form a two phase stream exiting a branch. Experiments were conducted in an air-water multiphase flow test loop. The flow pattern in the experiments included stratified flow, wave flow, slug flow and a part of annular flow. The experimental results show that the phase separation method and apparatus could be feasible to make an equal quality distribution and the deviation of stream quality among the branches is less than 1.6%.

  3. Quadruple-junction lattice coherency and phase separation in a binary-phase system

    PubMed Central

    Chung, Sung-Yoon; Choi, Si-Young; Kim, Jin-Gyu; Kim, Young-Min

    2015-01-01

    If each phase has an identical crystal structure and small misfit in the lattice parameters in a binary-phase crystalline system, coherent phase boundaries usually form during separation. Although there have been numerous studies on the effect of coherency elastic energy, no attempt has been made to demonstrate how the phase-separation behaviour varies when multiple interfaces meet at a junction. Here we show that a comprehensively different phase-separation morphology is induced, to release the high coherency strain confined to quadruple junctions. High-temperature in-situ transmission electron microscopy reveals that phase boundaries with a new crystallographic orientation emerge over twinned crystals to provide strain relaxation at quadruple junctions. The high coherency strain and the formation of different phase boundaries can be understood in terms of the force equilibrium between interface tensions at a junction point. Visualizing the quadruple points at atomic resolution, our observations emphasize the impact of multiple junctions on the morphology evolution during phase separation. PMID:26346223

  4. Macroscopic Phase Separation, Modulated Phases, and Microemulsions: A Unified Picture of Rafts

    PubMed Central

    Shlomovitz, Roie; Maibaum, Lutz; Schick, M.

    2014-01-01

    We simulate a simple phenomenological model describing phase behavior in a multicomponent membrane, a model capable of producing macroscopic phase separation, modulated phases, and microemulsions, all of which have been discussed in terms of raft phenomena. We show that one effect of thermal fluctuations on the mean-field phase diagram is that it permits a direct transition between either one of the coexisting liquid phases to a microemulsion. This implies that one system exhibiting phase separation can be related to a similar system exhibiting the heterogeneities characteristic of a microemulsion. The two systems could differ in their average membrane composition or in the relative compositions of their exoplasmic and cytoplasmic leaves. The model provides a unified description of these raft-associated phenomena. PMID:24806930

  5. Silk fibroin gelation via non-solvent induced phase separation.

    PubMed

    Kasoju, Naresh; Hawkins, Nicholas; Pop-Georgievski, Ognen; Kubies, Dana; Vollrath, Fritz

    2016-03-01

    Tissue engineering benefits from novel materials with precisely tunable physical, chemical and mechanical properties over a broad range. Here we report a practical approach to prepare Bombyx mori silk fibroin hydrogels using the principle of non-solvent induced phase separation (NIPS). A combination of reconstituted silk fibroin (RSF) and methanol (non-solvent), with a final concentration of 2.5% w/v and 12.5% v/v respectively, maintained at 22 °C temperature turned into a hydrogel within 10 hours. Freeze-drying of this gel gave a foam with a porosity of 88%, a water uptake capacity of 89% and a swelling index of 8.6. The gelation kinetics and the loss tangent of the gels were investigated by rheometry. The changes in the morphology of the porous foams were visualized by SEM. The changes in RSF chemical composition and the relative fraction of its secondary structural elements were analyzed by ATR-FTIR along with Fourier self-deconvolution. And, the changes in the glass transition temperature, specific heat capacity and the relative fraction of crystallinity of RSF were determined by TM-DSC. Data suggested that RSF-water-methanol behaved as a polymer-solvent-non-solvent ternary phase system, wherein the demixing of the water-methanol phases altered the thermodynamic equilibrium of RSF-water phases and resulted in the desolvation and eventual separation of the RSF phase. Systematic analysis revealed that both gelation time and the properties of hydrogels and porous foams could be controlled by the ratios of RSF and non-solvent concentration as well as by the type of non-solvent and incubation temperature. Due to the unique properties we envisage that the herein prepared NIPS induced RSF hydrogels and porous foams can possibly be used for the encapsulation of cells and/or for the controlled release of both hydrophilic and hydrophobic drugs.

  6. Phase Separation of Model Segmented Poly(Carbonate Urethanes)

    NASA Astrophysics Data System (ADS)

    Hernandez, Rebeca; Hung, Elena; Runt, James

    2006-03-01

    The present paper focuses on the phase separated morphology and segment demixing of model poly(carbonate urethanes) [PCU] with hard segment contents ranging from 30 -- 65% and soft segments composed of 1,6 poly(hexamethylene carbonate) [MW = 1K]. Hard segments were formed from 4,4'-methylenediphenyl diisocyanate and 1,4 butanediol. This family of materials represents a recent approach in the development of polyurethanes with improved long-term biostability, and is under clinical investigation in a number of biomedical devices. Only a single glass transition temperature was observed for each copolymer, increasing in temperature with increasing hard segment content. However, loss spectra from dynamic mechanical analysis showed clear evidence of two mixed phases. The results of small-angle X-ray scattering and tapping mode AFM experiments were consistent with these observations and will be discussed. Finally, these results will be compared with initial findings on phase separation in another family of polyurethane copolymers of current interest as blood-contact materials in biomedical devices having mixed poly(dimethylsiloxane) -- poly(hexamethyleneoxide) soft segments.

  7. Phase separation in polymer solutions near the critical point

    NASA Astrophysics Data System (ADS)

    Cherayil, Binny J.

    1991-08-01

    The Edwards path-integral description of chain statistics is used to derive an effective φ4 field theory of polymer solutions that is applicable near the temperature of critical phase separation Tc. The present formalism, an extension of the mean-field approach discussed in paper I [R. E. Goldstein and B. J. Cherayil, J. Chem. Phys. 90, 7448 (1989)], makes use of standard results from the theory of continuous phase transitions to account for the effects of previously neglected density fluctuations, and to obtain thereby, among other results, estimates for the temperature and molecular weight-scaling exponents of the coexistence curve in the vicinity of Tc. The critical monomer volume fraction ρc of the solution is shown to scale as the osmotic second virial coefficient below the theta point, providing a rigorous approach to the calculation of the molecular weight dependence of ρc. Experimental data on the phase separation of solutions of polystyrene in methylcyclohexane are shown to lie on a single universal curve when expressed in terms of the scaling variables suggested by the present analysis.

  8. Hierarchical scaffolds via combined macro- and micro-phase separation.

    PubMed

    George, Peter A; Quinn, Katie; Cooper-White, Justin J

    2010-02-01

    Recent advances in biomaterial surface engineering have shown that surface biomechanical, spatial and topographical properties can elicit control over fundamental biological processes such as cell shape, proliferation, differentiation and apoptosis. Along these lines, we have very recently shown that the self-assembly of block copolymers into thin films can be used as an extremely labile method to precisely position cellular adhesion molecules, at nanometre lateral spacings, to effect control over cell attachment and morphology. Here, we extend our work in 2-dimensional block copolymer films into the production of 3-dimensional porous block copolymer scaffolds. The reported method combines macro-scale temperature induced phase separation and micro-phase separation of block copolymers to produce highly porous scaffolds with surfaces comprised of nano-scale self-assembled block copolymer domains, representing a significant advance in currently available scaffold engineering technologies. The phase behaviour of these polymer-solvent systems is described and potential mechanisms leading to the observed structure formation are presented. The nano-domains have thereafter been functionalised with CGRGDS peptides throughout the scaffold and shown to effect changes in cell attachment and spreading, in agreement with previous 2-dimensional studies. These multi-scale, functional scaffolds are easy to manufacture and scaleable, making them ideal candidates for tissue engineering applications.

  9. Amorphous Alloy Membranes Prepared by Melt-Spin methods for Long-Term use in Hydrogen Separation Applications

    SciTech Connect

    Chandra, Dhanesh; Kim, Sang-Mun; Adibhatla, Anasuya; Dolan, Michael; Paglieri, Steve; Flanagan, Ted; Chien, Wen-Ming; Talekar, Anjali; Wermer, Joseph

    2013-02-28

    Amorphous Ni-based alloy membranes show great promise as inexpensive, hydrogenselective membrane materials. In this study, we developed membranes based on nonprecious Ni-Nb-Zr alloys by adjusting the alloying content and using additives. Several studies on crystallization of the amorphous ribbons, in-situ x-ray diffraction, SEM and TEM, hydrogen permeation, hydrogen solubility, hydrogen deuterium exchange, and electrochemical studies were conducted. An important part of the study was to completely eliminate Palladium coatings of the NiNbZr alloys by hydrogen heattreatment. The amorphous alloy (Ni0.6Nb0.4)80Zr20 membrane appears to be the best with high hydrogen permeability and good thermal stability.

  10. The phase reversal phenomenon at flow separation and reattachment

    NASA Technical Reports Server (NTRS)

    Stack, J. Pete; Mangalam, S. M.; Kalburgi, V.

    1988-01-01

    Tests were conducted on two different airfoils, one of them in a low-turbulence tunnel, to detect laminar separation and turbulent reattachment locations. A 'nonintrusive' multielement sensor consisting of a large number of closely spaced individual nickel films was vacuum deposited on a thin substrate and bonded to the airfoil model surface. Each sensor element was a part of an independent constant temperature anemometer system. Time history as well as spectral analysis of signals from surface film gauges were used to determine the surface shear flow characteristics. A major breakthrough was achieved with the discovery of phase reversal in low-frequency dynamic shear stress signals across regions of flow separation and reattachment.

  11. Deuterium dynamics in the icosahedral and amorphous phases of the Ti40Zr40Ni20 hydrogen-absorbing alloy studied by 2H NMR

    NASA Astrophysics Data System (ADS)

    Gradišek, A.; Kocjan, A.; McGuiness, P. J.; Apih, T.; Kim, Hae Jin; Dolinšek, J.

    2008-11-01

    The Ti40Zr40Ni20 hydrogen-absorbing alloy was prepared in the icosahedral and amorphous phases by controlling the rotation speed of the melt-spinning method of sample preparation, and the deuterium dynamics was investigated by 2H NMR dynamic lineshape and spin-lattice relaxation. The results were analysed by the lineshape and relaxation models that assume deuterium thermally activated hopping within a manifold of different chemical environments. The observed 8% larger activation energy for the deuterium hopping over the interstitial sites and the 10% larger static spectrum width of the amorphous phase, as compared to the icosahedral phase, can be accounted for by the larger deuterium content of the investigated amorphous sample. From the deuterium dynamics point of view, the icosahedral phase is not special with respect to the amorphous modification of the same material.

  12. Competing phases, phase separation, and coexistence in the extended one-dimensional bosonic Hubbard model

    DOE PAGES

    Batrouni, G. G.; Rousseau, V. G.; Scalettar, R. T.; ...

    2014-11-17

    Here, we study the phase diagram of the one-dimensional bosonic Hubbard model with contact (U) and near neighbor (V ) interactions focusing on the gapped Haldane insulating (HI) phase which is characterized by an exotic nonlocal order parameter. The parameter regime (U, V and μ) where this phase exists and how it competes with other phases such as the supersolid (SS) phase, is incompletely understood. We use the Stochastic Green Function quantum Monte Carlo algorithm as well as the density matrix renormalization group to map out the phase diagram. The HI exists only at = 1, the SS phase existsmore » for a very wide range of parameters (including commensurate fillings) and displays power law decay in the one body Green function were our main conclusions. Additionally, we show that at fixed integer density, the system exhibits phase separation in the (U, V ) plane.« less

  13. Competing phases, phase separation, and coexistence in the extended one-dimensional bosonic Hubbard model

    SciTech Connect

    Batrouni, G. G.; Rousseau, V. G.; Scalettar, R. T.; Grémaud, B.

    2014-11-17

    Here, we study the phase diagram of the one-dimensional bosonic Hubbard model with contact (U) and near neighbor (V ) interactions focusing on the gapped Haldane insulating (HI) phase which is characterized by an exotic nonlocal order parameter. The parameter regime (U, V and μ) where this phase exists and how it competes with other phases such as the supersolid (SS) phase, is incompletely understood. We use the Stochastic Green Function quantum Monte Carlo algorithm as well as the density matrix renormalization group to map out the phase diagram. The HI exists only at = 1, the SS phase exists for a very wide range of parameters (including commensurate fillings) and displays power law decay in the one body Green function were our main conclusions. Additionally, we show that at fixed integer density, the system exhibits phase separation in the (U, V ) plane.

  14. Polymer-induced phase separation in suspensions of bacteria

    NASA Astrophysics Data System (ADS)

    Schwarz-Linek, J.; Dorken, G.; Winkler, A.; Wilson, L. G.; Pham, N. T.; French, C. E.; Schilling, T.; Poon, W. C. K.

    2010-03-01

    We study phase separation in suspensions of two unrelated species of rod-like bacteria, Escherichia coli and Sinorhizobium meliloti, induced by the addition of two different anionic polyelectrolytes, sodium polystyrene sulfonate or succinoglycan, the former being synthetic and the latter of natural origin. Comparison with the known behaviour of synthetic colloid-polymer mixtures and with simulations show that "depletion" (or, equivalently, "macromolecular crowding") is the dominant mechanism: exclusion of the non-adsorbing polymer from the region between two neighbouring bacteria creates an unbalanced osmotic force pushing them together. The implications of our results for understanding phenomena such as biofilm formation are discussed.

  15. Phase/Shape Transitions and the Two Neutron Separation Energies

    SciTech Connect

    Zamfir, N. V.; Anghel, Sabina; Cata-Danil, G.

    2008-11-11

    We investigated the evolution of experimental two-neutron separation energies (S{sub 2n}) along the isotopic chains for the even-even nuclei. In order to enhance the sensitivity of our search, differential variation of the S{sub 2n} has been investigated. The emphasis is on finding nonmonotonic behaviors which can be correlated with phase/shape transition. Correlations of the ground state S{sub 2n} values with the excited states energies R{sub 4/2} ratio are also discussed.

  16. Anomalous Phase Separation Kinetics Observed in a Micelle Solution

    NASA Astrophysics Data System (ADS)

    Wilcoxon, Jess P.; Martin, James E.; Odinek, Judy

    1995-08-01

    We report a real-time, two-dimensional light scattering study of the evolution of structure in a two-component nonionic micelle system undergoing phase separation. We find that the structure of the domains is qualitatively similar to that observed in binary fluid systems, with some anomalies observed. However, compared to the Lifshitz-Slyozov prediction for simple binary fluids, the domain growth is unexpectedly slow. In fact, the growth kinetics can be empirically described as a stretched exponential approach to a pinned domain size. This anomalous behavior may be due to the ability of the spherical micelles to reorganize into more complex structures.

  17. Nanopatterns by phase separation of patterned mixed polymer monolayers

    DOEpatents

    Huber, Dale L; Frischknecht, Amalie

    2014-02-18

    Micron-size and sub-micron-size patterns on a substrate can direct the self-assembly of surface-bonded mixed polymer brushes to create nanoscale patterns in the phase-separated mixed polymer brush. The larger scale features, or patterns, can be defined by a variety of lithographic techniques, as well as other physical and chemical processes including but not limited to etching, grinding, and polishing. The polymer brushes preferably comprise vinyl polymers, such as polystyrene and poly(methyl methacrylate).

  18. Vapors-liquid phase separator. [infrared telescope heat sink

    NASA Technical Reports Server (NTRS)

    Frederking, T. H. K.; Brown, G. S.; Chuang, C.; Kamioka, Y.; Kim, Y. I.; Lee, J. M.; Yuan, S. W. K.

    1980-01-01

    The use of porous plugs, mostly with in the form of passive devices with constant area were considered as vapor-liquid phase separators for helium 2 storage vessels under reduced gravity. The incorporation of components with variable cross sectional area as a method of flow rate modification was also investigated. A particular device which uses a shutter-type system for area variation was designed and constructed. This system successfully permitted flor rate changes of up to plus or minus 60% from its mean value.

  19. Children in divorce: intervention in the phase of separation.

    PubMed

    Derdeyn, A P

    1977-07-01

    Divorce of their parents can create difficulties for the development of young children. The ability of children to integrate the various losses involved in the breaking up of a family is impeded by limitations of their cognitive understanding of events taking place during the separation phase. Because their thinking process is as yet immature, children often feel responsible for the divorce, and they otherwise distort the meaning of the events about them. The pediatrician can often guide and encourage parents to facilitate their children's understanding and acceptance of the changes in their lives.

  20. Liquid-liquid phase separation: characterisation of a novel device capable of separating particle carrying multiphase flows.

    PubMed

    Castell, Oliver K; Allender, Christopher J; Barrow, David A

    2009-02-07

    Capillary forces on the microscale are exploited to create a continuous flow liquid-liquid phase separator. Segmented flow regimes of immiscible fluids are generated and subsequently separated into their component phases through an array of high aspect ratio, laser machined, separation ducts (36 microm wide, 130 microm deep) in a planar, integrated, polytetrafluoroethylene (PTFE) microdevice. A controlled pressure differential across the phase separator architecture facilitates the selective passage of the wetting, organic, phase through the separator ducts, enabling separation of microfluidic multiphase flow streams. The reported device is demonstrated to separate water and chloroform segmented flow regimes at flow rates up to 0.4 ml min(-1). Separation efficiency is quantified over a range of flow rates and applied pressure differentials, characterising device behaviour and limits of operation. Experimental measurements and observations are supported by theoretical hydrodynamic and capillary pressure modelling. The influence of material properties and geometric design parameters on phase separation is quantified and optimisation strategies proposed. The novel ability of the membrane free device to separate an organic phase containing suspended microparticulates, from an aqueous phase, is also demonstrated.

  1. Accelerated sintering in phase-separating nanostructured alloys

    PubMed Central

    Park, Mansoo; Schuh, Christopher A.

    2015-01-01

    Sintering of powders is a common means of producing bulk materials when melt casting is impossible or does not achieve a desired microstructure, and has long been pursued for nanocrystalline materials in particular. Acceleration of sintering is desirable to lower processing temperatures and times, and thus to limit undesirable microstructure evolution. Here we show that markedly enhanced sintering is possible in some nanocrystalline alloys. In a nanostructured W–Cr alloy, sintering sets on at a very low temperature that is commensurate with phase separation to form a Cr-rich phase with a nanoscale arrangement that supports rapid diffusional transport. The method permits bulk full density specimens with nanoscale grains, produced during a sintering cycle involving no applied stress. We further show that such accelerated sintering can be evoked by design in other nanocrystalline alloys, opening the door to a variety of nanostructured bulk materials processed in arbitrary shapes from powder inputs. PMID:25901420

  2. Vortex motion phase separator for zero gravity liquid transfer

    NASA Technical Reports Server (NTRS)

    Howard, Frank S. (Inventor); Fraser, Wilson M., Jr. (Inventor)

    1989-01-01

    A vortex motion phase separator is disclosed for transferring a liquid in a zero gravity environment while at the same time separating the liquid from vapors found within either the sender or the receiving tanks. The separator comprises a rigid sender tank having a circular cross-section and rigid receiver tank having a circular cross-section. A plurality of ducts connects the sender tank and the receiver tank. Disposed within the ducts connecting the receiver tank and the sender tank is a pump and a plurality of valves. The pump is powered by an electric motor and is adapted to draw either the liquid or a mixture of the liquid and the vapor from the sender tank. Initially, the mixture drawn from the sender tank is directed through a portion of the ductwork and back into the sender tank at a tangent to the inside surface of the sender tank, thereby creating a swirling vortex of the mixture within the sender tank. As the pumping action increases, the speed of the swirling action within the sender tank increases creating an increase in the centrifugal force operating on the mixture. The effect of the centrifugal force is to cause the heavier liquid to migrate to the inside surface of the sender tank and to separate from the vapor. When this separation reaches a predetermined degree, control means is activated to direct the liquid conveyed by the pump directly into the receiver tank. At the same time, the vapor within the receiver tank is directed from the receiver tank back into the sender tank. This flow continues until substantially all of the liquid is transferred from the sender tank to the receiver tank.

  3. 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.

  4. Colossal magnetoresistance and phase separation in manganite thin films

    NASA Astrophysics Data System (ADS)

    Srivastava, M. K.; Agarwal, V.; Kaur, A.; Singh, H. K.

    2017-05-01

    In the present work, polycrystalline Sm0.55Sr0.45MnO3 thin films were prepared on LSAT (001) single crystal substrates by ultrasonic nebulized spray pyrolysis technique. The X-ray diffraction θ-2θ scan reveals that these films (i) have very good crystallinity, (ii) are oriented along out-of-plane c-direction, and (iii) are under small tensile strain. The impact of oxygen vacancy results into (i) higher value of paramagnetic insulator (PMI) to ferromagnetic metal (FMM) transition temperature, i.e., TC/TIM, (ii) sharper PMI-FMM transition, (iii) higher value of magnetization and magnetic saturation moment, and (iv) higher value of magnetoresistance (˜99%). We suggest here that oxygen vacancy favors FMM phase while oxygen vacancy annihilation leads to antiferromagnetic-charge ordered insulator (AFM-COI) phase. The observed results have been explained in context of phase separation (PS) caused by different fractions of the competing FMM and AFM-COI phases.

  5. Modeling reaction fronts of separated condensed phase reactants

    NASA Astrophysics Data System (ADS)

    Koundinyan, Sushilkumar; Stewart, D. Scott; Matalon, Moshe

    2017-01-01

    We present a Gibbs free energy approach to modeling reaction fronts in condensed phase reactive materials. The current interest is in chemical reactions of condensed phase reactants that are initially separated. In energetic materials such reactions are observed to occur extremely fast and at relatively sharp fronts. The condensed phase combustion process differs in several aspects from classical gaseous combustion due to the disparity between the characteristic thermal conductivity length and the mass diffusion lengths and a volume, temperature, stress, mass fraction equation of state that principally depends only on the component reference volumes and the current mixture composition. To retain a simple planar configuration, we consider the two reactants, in solid phase, are in motion towards each other characterized by counter-flow geometry. We apply the model to a simplified Titanium-Boron system and present the analysis of reaction zone length for various strain rates. The numerical results are validated with asymptotic approximations at the Burke-Schumann (complete combustion) limit.

  6. Digital holographic microscopy of phase separation in multicomponent lipid membranes

    NASA Astrophysics Data System (ADS)

    Farzam Rad, Vahideh; Moradi, Ali-Reza; Darudi, Ahmad; Tayebi, Lobat

    2016-12-01

    Lateral in-homogeneities in lipid compositions cause microdomains formation and change in the physical properties of biological membranes. With the presence of cholesterol and mixed species of lipids, phospholipid membranes segregate into lateral domains of liquid-ordered and liquid-disordered phases. Coupling of two-dimensional intralayer phase separations and interlayer liquid-crystalline ordering in multicomponent membranes has been previously demonstrated. By the use of digital holographic microscopy (DHMicroscopy), we quantitatively analyzed the volumetric dynamical behavior of such membranes. The specimens are lipid mixtures composed of sphingomyelin, cholesterol, and unsaturated phospholipid, 1,2-dioleoyl-sn-glycero-3-phosphocholine. DHMicroscopy in a transmission mode is an effective tool for quantitative visualization of phase objects. By deriving the associated phase changes, three-dimensional information on the morphology variation of lipid stacks at arbitrary time scales is obtained. Moreover, the thickness distribution of the object at demanded axial planes can be obtained by numerical focusing. Our results show that the volume evolution of lipid domains follows approximately the same universal growth law of previously reported area evolution. However, the thickness of the domains does not alter significantly by time; therefore, the volume evolution is mostly attributed to the changes in area dynamics. These results might be useful in the field of membrane-based functional materials.

  7. Transition from a nanocrystalline phase to an amorphous phase in In-Si-O thin films: The correlation between the microstructure and the optical properties

    SciTech Connect

    Park, Jun-Woo; So, Hyeon Seob; Lee, Hosun; Lee, Hye-Min; Kim, Hyo-Joong; Kim, Han-Ki

    2015-04-21

    We investigated the structural and optical properties of In-Si-O thin films as the phase abruptly changes from nanocrystalline (nc) to amorphous (a) with increasing Si content. In-Si-O thin films were deposited on Si substrate using a co-sputtering deposition method. The RF power of the In{sub 2}O{sub 3} target was fixed at 100 W, while the power applied to the SiO{sub 2} target was varied between 0 W and 60 W. At the Si = 2.8 at. %, i.e., at the onset of amorphous phase, the optical properties, including the dielectric functions, optical gap energies, and phonon modes, changed abruptly which were triggered by changes in the crystallinity and surface morphology. X-ray diffraction (XRD) spectra showed crystalline (c-) In{sub 2}O{sub 3}-like peaks below Si = 2.2%. Additionally, a broad peak associated with an amorphous (a-) In{sub 2}O{sub 3} phase appeared above 2.8%. However, the Raman spectra of In-Si-O showed very weak peaks associated with c-In{sub 2}O{sub 3} below 2.2%, and then showed a strong Raman peak associated with a-In-Si-O above 2.8%. X-ray photoelectron spectroscopy measurements showed that oxygen vacancy-related peak intensities increased abruptly above Si = 2.8%. The contrasting results of XRD and Raman measurements can be explained as follows: first, the large enhancement in Drude tails in the a-In-Si-O phase was caused by Si-induced amorphization and a large increase in the density of oxygen vacancies in the In-Si-O thin films. Second, the apparently drastic increase of the Raman peak intensity near 364 cm{sup −1} (for amorphous phase, i.e., above Si = 2.8%) is attributed to a disorder-activated infrared mode caused by both the amorphization and the increase in the oxygen vacancy density in In-Si-O thin films.

  8. Phase Separation in Lean Grade Duplex Stainless Steel 2101

    DOE PAGES

    Garfinkel, D.; Poplawsky, Jonathan D.; Guo, Wei; ...

    2015-08-19

    The use of duplex stainless steels (DSS) in nuclear power generation systems is limited by thermal instability that leads to embrittlement in the temperature range of 204°C - 538°C. New lean grade alloys, such as 2101, offer the potential to mitigate these effects. Thermal embrittlement was quantified through impact toughness and hardness testing on samples of alloy 2101 after aging at 427°C for various durations (1-10,000 hours). Additionally, atom probe tomography (APT) was utilized in order to observe the kinetics of α-α’ separation and G-phase formation. Mechanical testing and APT data for two other DSS alloys, 2003 and 2205 weremore » used as a reference to 2101. The results show that alloy 2101 exhibits superior performance compared to the standard grade DSS alloy, 2205, but inferior to the lean grade alloy, 2003, in mechanical testing. APT data demonstrates that the degree of α-α’ separation found in alloy 2101 closely resembles that of 2205, and greatly exceeds 2003. Additionally, contrary to what was observed in 2003, 2101 demonstrated G-phase like precipitates after long aging times, though precipitates were not as abundant as was observed in 2205.« less

  9. Phase separation like dynamics during Myxococcus xanthus fruiting body formation

    NASA Astrophysics Data System (ADS)

    Liu, Guannan; Thutupalli, Shashi; Wigbers, Manon; Shaevitz, Joshua

    2015-03-01

    Collective motion exists in many living organisms as an advantageous strategy to help the entire group with predation, forage, and survival. However, the principles of self-organization underlying such collective motions remain unclear. During various developmental stages of the soil-dwelling bacterium, Myxococcus xanthus, different types of collective motions are observed. In particular, when starved, M. xanthus cells eventually aggregate together to form 3-dimensional structures (fruiting bodies), inside which cells sporulate in response to the stress. We study the fruiting body formation process as an out of equilibrium phase separation process. As local cell density increases, the dynamics of the aggregation M. xanthus cells switch from a spatio-temporally random process, resembling nucleation and growth, to an emergent pattern formation process similar to a spinodal decomposition. By employing high-resolution microscopy and a video analysis system, we are able to track the motion of single cells within motile collective groups, while separately tuning local cell density, cell velocity and reversal frequency, probing the multi-dimensional phase space of M. xanthus development.

  10. Correlated lateral phase separations in stacks of lipid membranes

    SciTech Connect

    Hoshino, Takuma; Komura, Shigeyuki; Andelman, David

    2015-12-28

    Motivated by the experimental study of Tayebi et al. [Nat. Mater. 11, 1074 (2012)] on phase separation of stacked multi-component lipid bilayers, we propose a model composed of stacked two-dimensional Ising spins. We study both its static and dynamical features using Monte Carlo simulations with Kawasaki spin exchange dynamics that conserves the order parameter. We show that at thermodynamical equilibrium, due to strong inter-layer correlations, the system forms a continuous columnar structure for any finite interaction across adjacent layers. Furthermore, the phase separation shows a faster dynamics as the inter-layer interaction is increased. This temporal behavior is mainly due to an effective deeper temperature quench because of the larger value of the critical temperature, T{sub c}, for larger inter-layer interaction. When the temperature ratio, T/T{sub c}, is kept fixed, the temporal growth exponent does not increase and even slightly decreases as a function of the increased inter-layer interaction.

  11. Phase Separation in Lean Grade Duplex Stainless Steel 2101

    SciTech Connect

    Garfinkel, D.; Poplawsky, Jonathan D.; Guo, Wei; Young, Jr., George A.; Tucker, Julie

    2015-08-19

    The use of duplex stainless steels (DSS) in nuclear power generation systems is limited by thermal instability that leads to embrittlement in the temperature range of 204°C - 538°C. New lean grade alloys, such as 2101, offer the potential to mitigate these effects. Thermal embrittlement was quantified through impact toughness and hardness testing on samples of alloy 2101 after aging at 427°C for various durations (1-10,000 hours). Additionally, atom probe tomography (APT) was utilized in order to observe the kinetics of α-α’ separation and G-phase formation. Mechanical testing and APT data for two other DSS alloys, 2003 and 2205 were used as a reference to 2101. The results show that alloy 2101 exhibits superior performance compared to the standard grade DSS alloy, 2205, but inferior to the lean grade alloy, 2003, in mechanical testing. APT data demonstrates that the degree of α-α’ separation found in alloy 2101 closely resembles that of 2205, and greatly exceeds 2003. Additionally, contrary to what was observed in 2003, 2101 demonstrated G-phase like precipitates after long aging times, though precipitates were not as abundant as was observed in 2205.

  12. Internal Phase Separation Induces Dewetting in Multicomponent Polymer Films

    NASA Astrophysics Data System (ADS)

    Chung, Hyun-Joong; Composto, Russell J.; Ohno, Kohji; Fukuda, Takeshi

    2006-03-01

    Thin liquid films that dewet from their substrate are ubiquitous as demonstrated by the beading of paint on oily surface. Although most coatings contain more than one component, the dewetting mechanisms in multicomponent films are not understood. Using dPMMA:SAN (50:50) films (550 nm) with or without nanoparticles (NP), we demonstrate, for the first time, that the Laplace pressure induced by internal phase-separated structure is the driving force for roughening and rupture in polymer blend films. Three NP were investigated, namely NPA, NPB, and NPC which either partition into dPMMA or weakly and strongly segregate to the dPMMA/SAN interface, respectively. NPB are more effective than NPA at stabilizing the film, whereas NPC are able to prevent film rupture. Upon annealing, roughened films display a periodic, lacey structure, resembling patterns from spinodal dewetting. The fluctuation periodicity scales with roughness evolution as λs Rq^1/4 for neat blends and blends with NPA, whereas the scaling breaks down for blends containing NPB and NPC. These studies show that phase separation is responsible for film roughening.

  13. The mechanical properties of phase separated protein droplets

    NASA Astrophysics Data System (ADS)

    Jawerth, Louise; Ijavi, Mahdiye; Patel, Avinash; Saha, Shambaditya; Jülicher, Frank; Hyman, Anthony

    In vivo, numerous proteins associate into liquid compartments by de-mixing from the surrounding solution, similar to oil molecules in water. Many of these proteins and their corresponding liquid compartments play a crucial role in important biological processes, for instance germ line specification in C. elegans or in neurodegenerative diseases such as Amyotrophic lateral sclerosis (ALS). However, despite their importance, very little is known about the physical properties of the resulting droplets as well as the physical mechanisms that control their phase separation from solution. To gain a deeper understanding of these aspects, we study a few such proteins in vitro. When these proteins are purified and added to a physiological buffer, they phase separate into droplets ranging in size from a few to tens of microns with liquid-like behavior similar to their physiological counterparts. By attaching small beads to the surface of the droplets, we can deform the droplets by manipulating the beads directly using optical tweezers. By measuring the force required to deform the droplets we determine their surface tension, elasticity and viscosity as well as the frequency response of these properties. We also measure these properties using passive micro-rheology.

  14. Dynamic phase separation: from coarsening to turbulence via structure formation.

    PubMed

    Golovin, A A; Pismen, L M

    2004-09-01

    We investigate some new two-dimensional evolution models belonging to the class of convective Cahn-Hilliard models: (i) a local model with a scalar order parameter, (ii) a nonlocal model with a scalar order parameter, and (iii) a model with a vector order parameter. These models are applicable to phase-separating system where concentration gradients cause hydrodynamic motion due to buoyancy or Marangoni effect. The numerical study of the models shows transition from coarsening, typical of Cahn-Hilliard systems, to spatiotemporally irregular behavior (turbulence), typical of the Kuramoto-Sivashinsky equation, which is obtained in the limit of very strong driving. The transition occurs not in a straightforward way, but through the formation of spatial patterns that emerge for intermediate values of the driving intensity. As in driven one-dimensional models studied before, the mere presence of the driving force, however small, breaks the symmetry between the two separating phases, as well as increases the coarsening rate. With increasing driving, coarsening stops. The dynamics is generally irregular at strong driving, but exhibits specific structural features.

  15. Liquid-Liquid Phase Separation of Oil Bodies from Seeds.

    PubMed

    Nykiforuk, Cory L

    2016-01-01

    Fundamentally, oil bodies are discrete storage organelles found in oilseeds, comprising a hydrophobic triacylglycerol core surrounded by a half-unit phospholipid membrane and an outer shell of specialized proteins known as oleosins. Oil bodies possess a number of attributes that were exploited by SemBioSys Genetics to isolate highly enriched fractions of oil bodies through liquid-liquid phase separation for a number of commercial applications. The current chapter provides a general guide for the isolation of oil bodies from Arabidopsis and/or safflower seed, from which protocols can be refined for different oilseed sources. For SemBioSys Genetic's recombinant technology, therapeutic proteins were covalently attached to oleosins or fused in-frame with ligands which bound oil bodies, facilitating their recovery to high levels of purity during "upstream processing" of transformed seed. Core to this technology was oil body isolation consisting of simple manipulation including homogenization of seeds to free the oil bodies, followed by the removal of insoluble fractions, and phase separation to recover the oil bodies. During oil body enrichment (an increase in oil body content concomitant with removal of impurities), a number of options and tips are provided to aid researchers in the manipulation and monitoring of these robust organelles.

  16. Detection of a minor amorphous phase in crystalline etoricoxib by dynamic mechanical analysis: comparison with Raman spectroscopy and modulated differential scanning calorimetry.

    PubMed

    Clas, Sophie-Dorothee; Lalonde, Karine; Khougaz, Karine; Dalton, Chad R; Bilbeisi, Rana

    2012-02-01

    Detection and quantification of the amorphous phase of etoricoxib bulk drug substances, a selective cycloogenase-2 inhibitor used for the treatment of osteoarthritis, rheumatoid arthritis, and dental pain, was carried out using modulated differential scanning calorimetry (MDSC), dynamic mechanical analysis (DMA), and Raman spectroscopy. Detection of amorphous content in pharmaceutical powders by DMA is a special application of dynamic mechanical spectroscopy. DMA was found to be a sensitive technique, able to detect the presence of an amorphous phase in a crystalline phase at concentrations as low as 0.5%. The limit of detection (LOD) determined for DMA was 2.5%. In comparison, Raman spectroscopy and MDSC had LOD values of 2% and 5% amorphous, respectively.

  17. Amorphous and crystalline aerosol particles interacting with water vapor: conceptual framework and experimental evidence for restructuring, phase transitions and kinetic limitations

    NASA Astrophysics Data System (ADS)

    Mikhailov, E.; Vlasenko, S.; Martin, S. T.; Koop, T.; Pöschl, U.

    2009-12-01

    Interactions with water are crucial for the properties, transformation and climate effects of atmospheric aerosols. Here we present a conceptual framework for the interaction of amorphous aerosol particles with water vapor, outlining characteristic features and differences in comparison to crystalline particles. We used a hygroscopicity tandem differential mobility analyzer (H-TDMA) to characterize the hydration and dehydration of crystalline ammonium sulfate, amorphous oxalic acid and amorphous levoglucosan particles (diameter ~100 nm, relative humidity 5-95% at 298 K). The experimental data and accompanying Köhler model calculations provide new insights into particle microstructure, surface adsorption, bulk absorption, phase transitions and hygroscopic growth. The results of these and related investigations lead to the following conclusions: (1) Many organic substances, including carboxylic acids, carbohydrates and proteins, tend to form amorphous rather than crystalline phases upon drying of aqueous solution droplets. Depending on viscosity and microstructure, the amorphous phases can be classified as glasses, rubbers, gels or viscous liquids. (2) Amorphous organic substances tend to absorb water vapor and undergo gradual deliquescence and hygroscopic growth at lower relative humidity than their crystalline counterparts. (3) In the course of hydration and dehydration, certain organic substances can form rubber- or gel-like structures (supramolecular networks) and undergo transitions between swollen and collapsed network structures. (4) Organic gels or (semi-)solid amorphous shells (glassy, rubbery, ultra-viscous) with low molecular diffusivity can kinetically limit the uptake and release of water and may influence the hygroscopic growth and activation of aerosol particles as cloud condensation nuclei (CCN) and ice nuclei (IN). Moreover, (semi-)solid amorphous phases may influence the uptake of gaseous photo-oxidants and the chemical transformation and aging of

  18. The extent of the Cooper pair insulator phase in amorphous Pb0.9Bi0.1 nanohoneycomb films

    NASA Astrophysics Data System (ADS)

    Hollen, S. M.; Joy, J. C.; Berg, A. H.; Fernandes, G. E.; Shainline, J.; Xu, J. M.; Valles, J. M., Jr.

    2012-02-01

    Amorphous Bi nanohoneycomb (NHC) thin films, which contain a nanometer-scale array of holes and regular thickness undulations, exhibit an insulating phase made up of localized Cooper pairs (CPs) near their thickness-driven insulator to superconductor transition (IST). This Cooper pair insulator (CPI) phase includes a giant magnetoresistance peak, also observed in InOx and TiN. We have now produced NHC films of a new material, Pb0.9Bi0.1, that show a qualitatively similar CPI phase. We will show the evolution of this CPI phase from deep in the insulating state to the IST using transport measurements. Throughout this regime, we will track the appearance, growth, and range of the magnetoresistance oscillations (which indicate CP transport) and giant magnetoresistance peak. Considering these observations, we will discuss the likely extent of CP transport in these insulators.

  19. Cooper pair insulator phase induced in amorphous Pb0.9Bi0.1 thin films

    NASA Astrophysics Data System (ADS)

    Hollen, S. M.; Shainline, J.; Xu, J. M.; Valles, J. M.

    2013-03-01

    A Cooper pair insulator (CPI) phase emerges near the superconductor-insulator transitions of a number of strongly-disordered thin film systems. Much recent study has focused on a mechanism driving the underlying Cooper pair localization. We present data showing that a CPI phase develops in amorphous Pb0.9Bi0.1 films deposited onto nano-porous anodized aluminum oxide surfaces just as it has been shown to develop for a-Bi films. This result confirms the assertion that this CPI phase emerges due to the structure of the substrate. It supports the picture that nanoscale film thickness variations induced by the substrate drive the localization. Moreover, it implies that the CPI phase can be induced in any superconducting material that can be deposited onto this surface.

  20. Formation of physically stable amorphous phase of ibuprofen by solid state milling with kaolin.

    PubMed

    Mallick, Subrata; Pattnaik, Satyanarayan; Swain, Kalpana; De, Pintu K; Saha, Arindam; Ghoshal, Gaurisankar; Mondal, Arijit

    2008-02-01

    Ibuprofen was milled in the solid state with kaolin (hydrated aluminium silicate) in different ratio to examine the extent of transformation from crystalline to amorphous state. The physical stability of the resultant drug was also investigated. X-ray powder diffractometry (XRD) and birefringence by Scanning Electron Microscopy (SEM) studies indicated almost complete amorphization of the drug on ball milling with kaolin at 1:2 ratio. Fourier transform infrared spectroscopy (FTIR) data showed a reduction in the absorbance of the free and the hydrogen-bonded acid carbonyl peak of carboxylic acid group accompanied by a corresponding increase in the absorbance of the carboxylate peak, indicating an acid-base reaction between the carboxylic acid containing ibuprofen and kaolin on milling. The extent of amorphization and reduction in the carbonyl peak and increase in carboxylate peak was a function of kaolin concentration in the milled powder. On storage of milled powder (at 40 degrees C and 75% RH for 10 weeks), XRD and birefringence of SEM study showed the absence of reversion to the crystalline state and FTIR data revealed continued reduction of carbonyl peak, whereas, ibuprofen converted from its crystalline acid form to amorphous salt form on milling with kaolin. Kaolin-bound state of ibuprofen was physically stable during storage. In-vitro dissolution studies revealed that percent release of ibuprofen from the kaolin co-milled powder is in the order: 1:2>1:1>1:0.5>1:0.1>milled alone ibuprofen>crystalline ibuprofen.

  1. SIMS Study of Elemental Diffusion During Solid Phase Crystallization of Amorphous Silicon

    SciTech Connect

    Reedy, R. C.; Young, D.; Branz, H. M.; Wang, Q.

    2005-11-01

    Crystallization of hydrogenated amorphous silicon (a-Si:H) films deposited on low-cost substrates shows potential for solar cell applications. Secondary ion mass spectrometry (SIMS) was used to study impurity incorporation, hydrogen evolution, and dopant diffusion during the crystallization process

  2. Modeling reaction fronts of separated condensed phase reactants

    NASA Astrophysics Data System (ADS)

    Koundinyan, Sushilkumar; Matalon, Moshe; Stewart, D. Scott; Bdzil, John

    2015-06-01

    We present a Gibbs free energy approach to modeling reaction fronts in condensed phase reactive materials. The current interest is in chemical reactions of condensed phase reactants that are initially separated. In energetic materials such reactions are observed to occur extremely fast and at relatively sharp fronts. The solid-to-solid combustion process differs in several aspects from classical gaseous combustion due to the disparity between the characteristic thermal conductivity length and the mass diffusion lengths and a volume, temperature, stress, mass fraction equation of state that principally depends only on the component reference volumes and the current mixture composition. To retain a simple planar configuration, we consider the two reactants, in solid phase, are in motion towards each other characterized by counter-flow geometry. We apply the model to a simplified Titanium-Boron system and present the analysis of reaction zone length for various strain rates. The numerical results are validated with asymptotic approximations at the Burke-Schumann limit. Supported by HDTRA1-10-1-0020 (DTRA), AF Sub MO C00039417-1 (AFOSR/TRE).

  3. Dual Phase Membrane for High Temperature CO2 Separation

    SciTech Connect

    Jerry Lin

    2007-06-30

    This project aimed at synthesis of a new inorganic dual-phase carbonate membrane for high temperature CO{sub 2} separation. Metal-carbonate dual-phase membranes were prepared by the direct infiltration method and the synthesis conditions were optimized. Permeation tests for CO{sub 2} and N{sub 2} from 450-750 C showed very low permeances of those two gases through the dual-phase membrane, which was expected due to the lack of ionization of those two particular gases. Permeance of the CO{sub 2} and O{sub 2} mixture was much higher, indicating that the gases do form an ionic species, CO{sub 3}{sup 2-}, enhancing transport through the membrane. However, at temperatures in excess of 650 C, the permeance of CO{sub 3}{sup 2-} decreased rapidly, while predictions showed that permeance should have continued to increase with temperature. XRD data obtained from used membrane indicated that lithium iron oxides formed on the support surface. This lithium iron oxide layer has a very low conductivity, which drastically reduces the flow of electrons to the CO{sub 2}/O{sub 2} gas mixture; thus limiting the formation of the ionic species required for transport through the membrane. These results indicated that the use of stainless steel supports in a high temperature oxidative environment can lead to decreased performance of the membranes. This revelation created the need for an oxidation resistant support, which could be gained by the use of a ceramic-type membrane. Work was extended to synthesize a new inorganic dual-phase carbonate membrane for high temperature CO{sub 2} separation. Helium permeance of the support before and after infiltration of molten carbonate are on the order of 10{sup -6} and 10{sup -10} moles/m{sup 2} {center_dot} Pa {center_dot} s respectively, indicating that the molten carbonate is able to sufficiently infiltrate the membrane. It was found that La{sub 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} (LSCF) was a suitable candidate for the support

  4. Far infrared spectra of amorphous and crystalline water ice and changes in these phases as the result of proton irradiation

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Moore, Marla H.

    1992-01-01

    Far infrared spectra from 20 microns (500 cm(sup -1)) to 100 microns (100 cm(sup -1)) of water ice were measured. Amorphous ice deposited at 13 K has one absorption band at 45 microns (220 cm(sup -1)). Amorphous ice evolves into a crystalline form with absorptions at 44 microns (229 cm(sup -1)) and 62 microns (162 cm(sup -1)) as the temperature is increased to 155 K. Spectra documenting this phase change are presented as well as spectra of crystalline ice at temperatures between 13 K and 155 K. Far infrared spectra of amorphous and crystalline water ice before and after proton irradiation are also presented. Changes in these two forms are discussed in relation to ices in comets, grains, and planetary satellites in various radiation environments. Observations of non-terrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over forty years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. A methanol (CH3OH) clathrate hydrate, using a recently published procedure, was prepared and its far-IR spectrum investigated. The spectrum is quite differenct from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

  5. Quantitative analysis of aqueous phase composition of model dentin adhesives experiencing phase separation

    PubMed Central

    Ye, Qiang; Park, Jonggu; Parthasarathy, Ranganathan; Pamatmat, Francis; Misra, Anil; Laurence, Jennifer S.; Marangos, Orestes; Spencer, Paulette

    2013-01-01

    There have been reports of the sensitivity of our current dentin adhesives to excess moisture, for example, water-blisters in adhesives placed on over-wet surfaces, and phase separation with concomitant limited infiltration of the critical dimethacrylate component into the demineralized dentin matrix. To determine quantitatively the hydrophobic/hydrophilic components in the aqueous phase when exposed to over-wet environments, model adhesives were mixed with 16, 33, and 50 wt % water to yield well-separated phases. Based upon high-performance liquid chromatography coupled with photodiode array detection, it was found that the amounts of hydrophobic BisGMA and hydrophobic initiators are less than 0.1 wt % in the aqueous phase. The amount of these compounds decreased with an increase in the initial water content. The major components of the aqueous phase were hydroxyethyl methacrylate (HEMA) and water, and the HEMA content ranged from 18.3 to 14.7 wt %. Different BisGMA homologues and the relative content of these homologues in the aqueous phase have been identified; however, the amount of crosslinkable BisGMA was minimal and, thus, could not help in the formation of a crosslinked polymer network in the aqueous phase. Without the protection afforded by a strong crosslinked network, the poorly photoreactive compounds of this aqueous phase could be leached easily. These results suggest that adhesive formulations should be designed to include hydrophilic multimethacrylate monomers and water compatible initiators. PMID:22331596

  6. Tobacco protein separation by aqueous two-phase extraction.

    PubMed

    Balasubramaniam, Deepa; Wilkinson, Carol; Van Cott, Kevin; Zhang, Chenming

    2003-03-07

    Tobacco has long been considered as a host to produce large quantity of high-valued recombinant proteins. However, dealing with large quantities of biomass is a challenge for downstream processing. Aqueous two-phase extraction (ATPE) has been widely used in purifying proteins from various sources. It is a protein-friendly process and can be scaled up easily. In this paper, ATPE was studied for its applicability to recombinant protein purification from tobacco with egg white lysozyme as the model protein. Separate experiments with poly(ethylene glycol) (PEG)-salt-tobacco extract and PEG-salt-lysozyme were carried out to determine the partition behavior of tobacco protein and lysozyme, respectively. Two-level fractional factorial designs were used to study the effects of factors such as, PEG molecular mass, PEG concentration, the concentration of phase forming salt, sodium chloride concentration and pH, on protein partitioning. The results showed that, among the studied systems, PEG-sodium sulfate system was most suitable for lysozyme purification. Detailed experiments were conducted by spiking lysozyme into the tobacco extract. The conditions with highest selectivity of lysozyme over native tobacco protein were determined using a response surface design. The purification factor was further improved by decreasing the phase ratio along the tie line corresponding to the phase compositions with the highest selectivity. Under selected conditions the lysozyme yield was predicted to be 87% with a purification factor of 4 and concentration factor of 14. From this study, ATPE was shown to be suitable for initial protein recovery and partial purification from transgenic tobacco.

  7. Model system studies with a phase separated membrane bioreactor

    NASA Technical Reports Server (NTRS)

    Petersen, G. R.; Seshan, P. K.; Dunlop, Eric H.

    1989-01-01

    The operation and evaluation of a bioreactor designed for high intensity oxygen transfer in a microgravity environment is described. The reactor itself consists of a zero headspace liquid phase separated from the air supply by a long length of silicone rubber tubing through which the oxygen diffuses in and the carbon dioxide diffuses out. Mass transfer studies show that the oxygen is film diffusion controlled both externally and internally to the tubing and not by diffusion across the tube walls. Methods of upgrading the design to eliminate these resistances are proposed. Cell growth was obtained in the fermenter using Saccharomyces cerevisiae showing that this concept is capable of sustaining cell growth in the terrestial simulation.

  8. Role of Dislocation in InGaN Phase Separation

    NASA Astrophysics Data System (ADS)

    Sugahara, Tomoya; Hao, Maosheng; Wang, Tao; Nakagawa, Daisuke; Naoi, Yoshiki; Nishino, Katsusi; Sakai, Shiro

    1998-10-01

    The role of dislocation for luminescence in InGaN grown on sapphire substrateby metal organic chemical vapor deposition (MOCVD) method was investigated by cathodoluminescence (CL) and atomic force microscopy (AFM). The CL emission area and dark spots between InGaN and GaN layers in InGaN/GaN single quantum well (SQW) and multiple quantum well (MQW) structures showed completely one to one correspondence. These results indicate that dislocations in InGaN work as non-radiative recombination centers. Furthermore it was confirmed that the phase separation in InGaN is caused by spiral growth due to mixed dislocations, and such a growth mechanism is discussed.

  9. Chronotaxic systems with separable amplitude and phase dynamics

    NASA Astrophysics Data System (ADS)

    Suprunenko, Yevhen F.; Clemson, Philip T.; Stefanovska, Aneta

    2014-01-01

    Until recently, deterministic nonautonomous oscillatory systems with stable amplitudes and time-varying frequencies were not recognized as such and have often been mistreated as stochastic. These systems, named chronotaxic, were introduced in Phys. Rev. Lett. 111, 024101 (2013), 10.1103/PhysRevLett.111.024101. In contrast to conventional limit cycle models of self-sustained oscillators, these systems posses a time-dependent point attractor or steady state. This allows oscillations with time-varying frequencies to resist perturbations, a phenomenon which is ubiquitous in living systems. In this work a detailed theory of chronotaxic systems is presented, specifically in the case of separable amplitude and phase dynamics. The theory is extended by the introduction of chronotaxic amplitude dynamics. The wide applicability of chronotaxic systems to a range of fields from biological and condensed matter systems to robotics and control theory is discussed.

  10. Phase separated membrane bioreactor - Results from model system studies

    NASA Technical Reports Server (NTRS)

    Petersen, G. R.; Seshan, P. K.; Dunlop, E. H.

    1989-01-01

    The operation and evaluation of a bioreactor designed for high intensity oxygen transfer in a microgravity environment is described. The reactor itself consists of a zero headspace liquid phase separated from the air supply by a long length of silicone rubber tubing through which the oxygen diffuses in and the carbon dioxide diffuses out. Mass transfer studies show that the oxygen is film diffusion controlled both externally and internally to the tubing and not by diffusion across the tube walls. Methods of upgrading the design to eliminate these resistances are proposed. Cell growth was obtained in the fermenter using Saccharomyces cerevisiae showing that this concept is capable of sustaining cell growth in the terrestrial simulation.

  11. Phase separated membrane bioreactor - Results from model system studies

    NASA Technical Reports Server (NTRS)

    Petersen, G. R.; Seshan, P. K.; Dunlop, E. H.

    1989-01-01

    The operation and evaluation of a bioreactor designed for high intensity oxygen transfer in a microgravity environment is described. The reactor itself consists of a zero headspace liquid phase separated from the air supply by a long length of silicone rubber tubing through which the oxygen diffuses in and the carbon dioxide diffuses out. Mass transfer studies show that the oxygen is film diffusion controlled both externally and internally to the tubing and not by diffusion across the tube walls. Methods of upgrading the design to eliminate these resistances are proposed. Cell growth was obtained in the fermenter using Saccharomyces cerevisiae showing that this concept is capable of sustaining cell growth in the terrestrial simulation.

  12. Phase separated membrane bioreactor: Results from model system studies

    NASA Astrophysics Data System (ADS)

    Petersen, G. R.; Seshan, P. K.; Dunlop, E. H.

    The operation and evaluation of a bioreactor designed for high intensity oxygen transfer in a microgravity environment is described. The reactor itself consists of a zero headspace liquid phase separated from the air supply by a long length of silicone rubber tubing through which the oxygen diffuses in and the carbon dioxide diffuses out. Mass transfer studies show that the oxygen is film diffusion controlled both externally and internally to the tubing and not by diffusion across the tube walls. Methods of upgrading the design to eliminate these resistances are proposed. Cell growth was obtained in the fermenter using Saccharomyces cerevisiae showing that this concept is capable of sustaining cell growth in the terrestial simulation.

  13. Phase separated membrane bioreactor: results from model system studies.

    PubMed

    Petersen, G R; Seshan, P K; Dunlop, E H

    1989-01-01

    The operation and evaluation of a bioreactor designed for high intensity oxygen transfer in a microgravity environment is described. The reactor itself consists of a zero headspace liquid phase separated from the air supply by a long length of silicone rubber tubing through which the oxygen diffuses in and the carbon dioxide diffuses out. Mass transfer studies show that the oxygen is film diffusion controlled both externally and internally to the tubing and not by diffusion across the tube walls. Methods of upgrading the design to eliminate these resistances are proposed. Cell growth was obtained in the fermenter using Saccharomyces cerevisiae showing that this concept is capable of sustaining cell growth in the terrestrial [correction of terrestial] simulation.

  14. The evolutionary significance of phase-separated microsystems

    NASA Technical Reports Server (NTRS)

    Fox, S. W.

    1976-01-01

    The source, preparation, and properties of phase-separated systems such as lipid layers, coacervate droplets, sulphobes, and proteinoid microspheres are reviewed. These microsystems are of interest as partial models for the cell and as partial or total models for the protocell. Conceptual benefits from the study of such models include clues to experiments on origins, insights into principles of action, and, in some instances, presumable models of the origin of the protocell. The benefits to evolution of organized chemical units are many, and can in part be analyzed. Ease of formation suggests that such units would have arisen early in primordial organic evolution. Integration of these various concepts and the results of consequent experiments have contributed to the developing theory of the origins of primordial and contemporary life.

  15. Electronic phase separation transition as the origin of the superconductivity and pseudogap phase of cuprates

    NASA Astrophysics Data System (ADS)

    de Mello, E. V. L.; Kasal, R. B.; Passos, C. A. C.

    2009-06-01

    To deal with the physics of cuprate superconductivity we propose an electronic phase separation transition that segregates the holes into high and low density domains. The calculated grain boundary potential favors the development of intragrain superconducting amplitudes. The zero resistivity transition arises only when the intergrain Josephson coupling EJ is of the order of the thermal energy and phase locking takes place among the superconducting grains. We show that this approach explains the pseudogap and superconducting phases and it also reproduces some recent scanning tunneling microscopy data.

  16. Electronic phase separation transition as the origin of the superconductivity and pseudogap phase of cuprates.

    PubMed

    de Mello, E V L; Kasal, R B; Passos, C A C

    2009-06-10

    To deal with the physics of cuprate superconductivity we propose an electronic phase separation transition that segregates the holes into high and low density domains. The calculated grain boundary potential favors the development of intragrain superconducting amplitudes. The zero resistivity transition arises only when the intergrain Josephson coupling E(J) is of the order of the thermal energy and phase locking takes place among the superconducting grains. We show that this approach explains the pseudogap and superconducting phases and it also reproduces some recent scanning tunneling microscopy data.

  17. Atomic scale observation of phase separation and formation of silicon clusters in Hf higk-{kappa} silicates

    SciTech Connect

    Talbot, E.; Roussel, M.; Genevois, C.; Pareige, P.; Khomenkova, L.; Portier, X.; Gourbilleau, F.

    2012-05-15

    Hafnium silicate films were fabricated by RF reactive magnetron sputtering technique. Fine microstructural analyses of the films were performed by means of high-resolution transmission electron microscopy and atom probe tomography. A thermal treatment of as-grown homogeneous films leads to a phase separation process. The formation of SiO{sub 2} and HfO{sub 2} phases as well as pure Si one was revealed. This latter was found to be amorphous Si nanoclusters, distributed uniformly in the film volume. Their mean diameter and density were estimated to be about 2.8 nm and (2.9 {+-} 0.4) x 10{sup 17} Si-ncs/cm{sup 3}, respectively. The mechanism of the decomposition process was proposed. The obtained results pave the way for future microelectronic and photonic applications of Hf-based high-{kappa} dielectrics with embedded Si nanoclusters.

  18. Mesoporous VN prepared by solid-solid phase separation

    SciTech Connect

    Yang Minghui; Ralston, Walter T.; Tessier, Franck; Allen, Amy J.; DiSalvo, Francis J.

    2013-01-15

    We recently reported a simple route to prepare mesoporous, conducting nitrides from Zn containing ternary transition metal oxides. Those materials result from the condensation of atomic scale voids created by the loss of Zn by evaporation, the replacement of 3 oxygen anions by 2 nitrogen anions, and in most cases the loss of oxygen to form water on the reduction of the transition metal. In this report, we present a different route to prepare mesoporous VN from K containing vanadium oxides. In this case, ammonolysis results in a multiphase solid product that contains VN, and other water soluble compounds such as KOH or KNH{sub 2}. On removing the K containing products by washing with degassed water, only mesoporous VN remains. VN materials with different pore sizes (10 nm-20 nm) were synthesized at 600 Degree-Sign C by varying the reaction time, while larger pores are obtained at higher temperatures (50 nm at 800 Degree-Sign C). - Graphical Abstract: The synthesis process of mesoporous VN from solid-solid separation. Highlights: Black-Right-Pointing-Pointer Mesoporous VN has been prepared by solid-solid phase separation. Black-Right-Pointing-Pointer Mesoporous VN was characterized by Rietveld refinement of PXRD, SEM and nitrogen physisorption. Black-Right-Pointing-Pointer VN materials with different pore sizes (10 nm-50 nm) were synthesized.

  19. Phase stability, porosity distribution and microstructural evolution of amorphous Al{sub 50}Ti{sub 50} powders consolidated by electrical resistance sintering

    SciTech Connect

    Urban, P. Montes, J. M.; Cintas, J.

    2015-03-30

    The effect of intensity and duration of the electrical resistance sintering process on the phase stability, porosity distribution and microstructural evolution of Al{sub 50}Ti{sub 50} amorphous powders is studied. The phase transformations during the consolidation process were determined by X-ray diffraction. The porosity distribution was observed by optical and scanning electron microscopy. The amorphous phase is partially transformed to the crystalline phase during the sintering process, and formation of AlTi and AlTi{sub 3} intermetallic compounds occurs for temperatures higher than 300 °C. Finally, it is observed that the compacts core have lower porosity and a higher tendency to the amorphous-crystalline phase transformation than the periphery.

  20. A Temperature-Dependent Phase-Field Model for Phase Separation and Damage

    NASA Astrophysics Data System (ADS)

    Heinemann, Christian; Kraus, Christiane; Rocca, Elisabetta; Rossi, Riccarda

    2017-07-01

    In this paper we study a model for phase separation and damage in thermoviscoelastic materials. The main novelty of the paper consists in the fact that, in contrast with previous works in the literature concerning phase separation and damage processes in elastic media, in our model we encompass thermal processes, nonlinearly coupled with the damage, concentration and displacement evolutions. More particularly, we prove the existence of "entropic weak solutions", resorting to a solvability concept first introduced in Feireisl (Comput Math Appl 53:461-490, 2007) in the framework of Fourier-Navier-Stokes systems and then recently employed in Feireisl et al. (Math Methods Appl Sci 32:1345-1369, 2009) and Rocca and Rossi (Math Models Methods Appl Sci 24:1265-1341, 2014) for the study of PDE systems for phase transition and damage. Our global-in-time existence result is obtained by passing to the limit in a carefully devised time-discretization scheme.

  1. Anomalous vortex motion in the quantum-liquid phase of amorphous MoxSi1-x films.

    PubMed

    Okuma, S; Kobayashi, M; Kamada, M

    2005-02-04

    We measure, in real time (t), the fluctuating component of the flux-flow voltage V(t), deltaV(t) identical withV(t)-V0, about the average V0 in the vortex-liquid phase of amorphous MoxSi1-x films. For the thick film, deltaV(t) originating from the vortex motion is clearly visible in the quantum-liquid phase, where the distribution of deltaV(t) is asymmetric, indicative of large velocity and/or number fluctuations of driven vortices. For the thin film the similar anomalous vortex motion is observed in nearly the same (reduced-)temperature regime. These results suggest that vortex dynamics in the low-temperature liquid phase of thick and thin films is dominated by common physical mechanisms, presumably related to quantum effects.

  2. Microscopic origin of resistance drift in the amorphous state of the phase-change compound GeTe

    NASA Astrophysics Data System (ADS)

    Gabardi, S.; Caravati, S.; Sosso, G. C.; Behler, J.; Bernasconi, M.

    2015-08-01

    Aging is a common feature of the glassy state. In the case of phase-change chalcogenide alloys the aging of the amorphous state is responsible for an increase of the electrical resistance with time. This phenomenon called drift is detrimental in the application of these materials in phase-change nonvolatile memories, which are emerging as promising candidates for storage class memories. By means of combined molecular dynamics and electronic structure calculations based on density functional theory, we have unraveled the atomistic origin of the resistance drift in the prototypical phase-change compound GeTe. The drift results from a widening of the band gap and a reduction of Urbach tails due to structural relaxations leading to the removal of chains of Ge-Ge homopolar bonds. The same structural features are actually responsible for the high mobility above the glass transition which boosts the crystallization speed exploited in the device.

  3. Amorphous-Si waveguide on a garnet magneto-optical isolator with a TE mode nonreciprocal phase shift.

    PubMed

    Ishida, Eiichi; Miura, Kengo; Shoji, Yuya; Yokoi, Hideki; Mizumoto, Tetsuya; Nishiyama, Nobuhiko; Arai, Shigehisa

    2017-01-09

    We fabricated a magneto-optical (MO) isolator with a TE mode nonreciprocal phase shift. The isolator is based on a Mach-Zehnder interferometer composed of 3-dB directional couplers, a reciprocal phase shifter, and a nonreciprocal phase shifter. To realize TE mode operation in the optical isolator, we designed a novel waveguide structure composed of a hydrogenated amorphous silicon waveguide with an asymmetric MO garnet lateral clad on a garnet substrate. The isolator operation is successfully demonstrated in a fabricated device showing the different transmittances between forward and backward directions. The maximum isolation of the fabricated isolator is 17.9 dB at a wavelength of 1561 nm for the TE mode.

  4. Evolution of a phase separated gravity independent bioreactor

    NASA Astrophysics Data System (ADS)

    Villeneuve, Peter E.; Dunlop, Eric H.

    The evolution of a phase-separated gravity-independent bioreactor is described. The initial prototype, a zero head-space manifold silicone membrane based reactor, maintained large diffusional resistances. Obtaining oxygen transfer rates needed to support carbon-recycling aerobic microbes is impossible if large resistances are maintained. Next generation designs (Mark I and II) mimic heat exchanger design to promote turbulence at the tubing-liquid interface, thereby reducing liquid and gas side diffusional resistances. While oxygen transfer rates increased by a factor of ten, liquid channeling prevented further increases. To overcome these problems, a Mark III reactor was developed which maintains inverted phases, i.e., media flows inside the silicone tubing, oxygen gas is applied external to the tubing. This enhances design through changes in gas side driving force concentration and liquid side turbulence levels. Combining an applied external pressure of four atmospheres with increased Reynolds numbers resulted in oxygen transfer intensities of 232 mmol O2/l/h (1000 times greater than first prototype and comparable to a conventional fermenter). A 1.0 liter Mark III reactor can potentially deliver oxygen supplies necessary to support cell cultures needed to recycle a 10 astronaut carbon load continuously.

  5. Diffusion-limited phase separation in eukaryotic chemotaxis

    PubMed Central

    Gamba, Andrea; de Candia, Antonio; Di Talia, Stefano; Coniglio, Antonio; Bussolino, Federico; Serini, Guido

    2005-01-01

    The ability of cells to sense spatial gradients of chemoattractant factors governs the development of complex eukaryotic organisms. Cells exposed to shallow chemoattractant gradients respond with strong accumulation of the enzyme phosphatidylinositol 3-kinase (PI3K) and its D3-phosphoinositide product (PIP3) on the plasma membrane side exposed to the highest chemoattractant concentration, whereas PIP3-degrading enzyme PTEN and its product PIP2 localize in a complementary pattern. Such an early symmetry-breaking event is a mandatory step for directed cell movement elicited by chemoattractants, but its physical origin is still mysterious. Here, we propose that directional sensing is the consequence of a phase-ordering process mediated by phosphoinositide diffusion and driven by the distribution of chemotactic signal. By studying a realistic reaction–diffusion lattice model that describes PI3K and PTEN enzymatic activity, recruitment to the plasma membrane, and diffusion of their phosphoinositide products, we show that the effective enzyme–enzyme interaction induced by catalysis and diffusion introduces an instability of the system toward phase separation for realistic values of physical parameters. In this framework, large reversible amplification of shallow chemotactic gradients, selective localization of chemical factors, macroscopic response timescales, and spontaneous polarization arise naturally. The model is robust with respect to order-of-magnitude variations of the parameters. PMID:16291809

  6. Evolution of a phase separated gravity independent bioreactor

    NASA Technical Reports Server (NTRS)

    Villeneuve, Peter E.; Dunlop, Eric H.

    1992-01-01

    The evolution of a phase-separated gravity-independent bioreactor is described. The initial prototype, a zero head-space manifold silicone membrane based reactor, maintained large diffusional resistances. Obtaining oxygen transfer rates needed to support carbon-recycling aerobic microbes is impossible if large resistances are maintained. Next generation designs (Mark I and II) mimic heat exchanger design to promote turbulence at the tubing-liquid interface, thereby reducing liquid and gas side diffusional resistances. While oxygen transfer rates increased by a factor of ten, liquid channeling prevented further increases. To overcome these problems, a Mark III reactor was developed which maintains inverted phases, i.e., media flows inside the silicone tubing, oxygen gas is applied external to the tubing. This enhances design through changes in gas side driving force concentration and liquid side turbulence levels. Combining an applied external pressure of 4 atm with increased Reynolds numbers resulted in oxygen transfer intensities of 232 mmol O2/l per hr (1000 times greater than the first prototype and comparable to a conventional fermenter). A 1.0 liter Mark III reactor can potentially deliver oxygen supplies necessary to support cell cultures needed to recycle a 10-astronaut carbon load continuously.

  7. Evolution of a phase separated gravity independent bioreactor

    NASA Technical Reports Server (NTRS)

    Villeneuve, Peter E.; Dunlop, Eric H.

    1992-01-01

    The evolution of a phase-separated gravity-independent bioreactor is described. The initial prototype, a zero head-space manifold silicone membrane based reactor, maintained large diffusional resistances. Obtaining oxygen transfer rates needed to support carbon-recycling aerobic microbes is impossible if large resistances are maintained. Next generation designs (Mark I and II) mimic heat exchanger design to promote turbulence at the tubing-liquid interface, thereby reducing liquid and gas side diffusional resistances. While oxygen transfer rates increased by a factor of ten, liquid channeling prevented further increases. To overcome these problems, a Mark III reactor was developed which maintains inverted phases, i.e., media flows inside the silicone tubing, oxygen gas is applied external to the tubing. This enhances design through changes in gas side driving force concentration and liquid side turbulence levels. Combining an applied external pressure of 4 atm with increased Reynolds numbers resulted in oxygen transfer intensities of 232 mmol O2/l per hr (1000 times greater than the first prototype and comparable to a conventional fermenter). A 1.0 liter Mark III reactor can potentially deliver oxygen supplies necessary to support cell cultures needed to recycle a 10-astronaut carbon load continuously.

  8. Raman spectroscopic study of the phase transition of amorphous to crystalline beta-carbonic acid.

    PubMed

    Kohl, Ingrid; Winkel, Katrin; Bauer, Marion; Liedl, Klaus R; Loerting, Thomas; Mayer, Erwin

    2009-01-01

    What's the matter? The laboratory Raman spectra for carbonic acid (H(2)CO(3)), both for the beta-polymorph and its amorphous state, are required to detect carbonic acid on the surface of the pole caps of Mars in 2009, when the Mars Microbeam Raman Spectrometer lands on the planet. The picture shows a martian crater with ice of unknown composition, possibly containing carbonic acid (image adapted from DLR, with permission from ESA, DLR, and FU Berlin--G. Neukum).

  9. DUAL PHASE MEMBRANE FOR HIGH TEMPERATURE CO2 SEPARATION

    SciTech Connect

    Jerry Y.S. Lin; Seungjoon Chung; Matthew Anderson

    2005-12-01

    This project is intended to expand upon the previous year's research en route to the development of a sustainable dual phase membrane for CO{sub 2} separation. It was found that the pores within the supports had to be less than 9 {micro}m in order to maintain the stability of the dual phase membrane. Pores larger than 9 {micro}m would be unable to hold the molten carbonate phase in place, rendering the membrane ineffective. Calculations show that 80% of the pore volume of the 0.5 media grade metal support was filled with the molten carbonate. Information obtained from EDS and SEM confirmed that the molten carbonate completely infiltrated the pores on both the contact and non-contact size of the metal support. Permeation tests for CO{sub 2} and N{sub 2} at 450-750 C show very low permeance of those two gases through the dual phase membrane, which was expected due to the lack of ionization of those two gases. Permeance of the CO{sub 2} and O{sub 2} mixture was much higher, indicating that the gases do form an ionic species, CO{sub 3}{sup 2-}, enhancing transport through the membrane. However, at temperatures in excess of 650 C, the permeance of CO{sub 3}{sup 2-} decreased quite rapidly, while predictions showed that permeance should have continued to increase. XRD data obtained form the surface of the membrane indicated the formation of lithium iron oxides on the support. This layer has a very low conductivity, which drastically reduces the flow of electrons to the CO{sub 2}/O{sub 2} gas mixture, limiting the formation of the ionic species. These results indicate that the use of stainless steel supports in a high temperature oxidative environment can lead to decreased performance of the membranes. This revelation has created the need for an oxidation resistant support, which can be gained by the use of a ceramic-type membrane. Future research efforts will be directed towards preparation of a new ceramic-carbonate dual phase membrane. The membrane will based on an

  10. Ferromagnetic order in silicon-manganese alloys with phase separation

    SciTech Connect

    Men'shov, V. N. Tugushev, V. V.

    2011-07-15

    A phenomenological model of high-temperature ferromagnetism in silicon-manganese alloys has been proposed taking into account phase separation in these alloys, where manganese-rich particles of the secondary phase (precipitate MnSi{sub 2-z} with z Almost-Equal-To 0.25-0.30) are formed inside a manganese-depleted matrix of almost pure silicon. Precipitate MnSi{sub 2-z} is considered as the silicide MnSi{sub 1.7} containing a certain number of magnetic defects whose origin is due to the presence of weakly hybridized 3d orbitals of manganese. The silicide MnSi{sub 1.7} is a weak band ferromagnet in which strong fluctuations of the spin density (paramagnons) are present at a temperature much higher than its Curie temperature. It has been shown that the ferromagnetic exchange interactions between the magnetic moments of defects in precipitate exists due to thermal excitations of the spin density and the ferromagnetic order can appear at a temperature much higher than the Curie temperature of the silicide. The spatial structures and characteristics of this order have been described in the framework of the proposed approach for both homogeneous bulk precipitate and precipitate particles of various shapes and sizes. The short-range magnetic order near the bulk phase transition has been analyzed taking into account inhomogeneities in the distribution of magnetic defects in precipitate. The experimental data on the magnetic properties of silicon-manganese alloys have been interpreted in terms of the theoretical results obtained in this work.

  11. Phase separation in a polarized Fermi gas with spin-orbit coupling

    SciTech Connect

    Yi, W.; Guo, G.-C.

    2011-09-15

    We study the phase separation of a spin-polarized Fermi gas with spin-orbit coupling near a wide Feshbach resonance. As a result of the competition between spin-orbit coupling and population imbalance, the phase diagram for a uniform gas develops a rich structure of phase separation involving topologically nontrivial gapless superfluid states. We then demonstrate the phase separation induced by an external trapping potential and discuss the optimal parameter region for the experimental observation of the gapless superfluid phases.

  12. Mircomagnetic Simulation of Amorphous TbFeCo Thin Films with Self Exchange Bias

    NASA Astrophysics Data System (ADS)

    Ma, Chung; Li, Xiaopu; Lu, Jiwei; Poon, Joseph

    Amorphous ferrimagnetic TbFeCo thin films are found to exhibit self exchange bias effect near compensation temperature by magnetic hysteresis loop measurement. Atom probe tomography, scanning transmission electron microscopy, and energy dispersive spectroscopy mapping have revealed two nanoscale amorphous phases with different Tb concentrations distributed within the amorphous films. The observed exchange anisotropy originates from the exchange interaction between the two nanoscale amorphous phases. Here, we present a computational model of TbFeCo with two nanoscale amorphous phases using micromagnetic simulation. To obtain a structure similar to the two nanoscale amorphous phases, two kinds of cells with different Tb concentration are distributed within the simulated space. Each cell contains separated Tb and FeCo components, forming two antiferromagnetically coupled sublattices. Using this model, we show exchange bias effect near compensation temperature, in agreement with experimental results. The effect can be tuned by controlling the microstructure and composition. The work was supported by the Defense Threat Reduction Agency grant.

  13. Interfacial reaction induced phase separation in La{sub x}Hf{sub y}O films

    SciTech Connect

    Ma, J. W.; Lee, W. J.; Cho, M.-H.; Lee, K. M.; Sohn, H. C.; Kim, C. S.; Cho, H. J.

    2011-06-15

    Amorphous La{sub x}Hf{sub y}O films containing La at concentrations (x) of 50 and 20% were prepared by atomic layer deposition on ultrathin SiO{sub 2} films (1 nm). We examined the electronic structures and microstructures of the La{sub x}Hf{sub y}O films by x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). Phase separation into La{sub 2}O{sub 3} and HfO{sub 2} was observed in the La{sub x}Hf{sub y}O films subjected to annealing temperatures over 900 deg. C, although the mixture of La{sub 2}O{sub 3} and HfO{sub 2} is thermodynamically stable. The structural changes that occurred as the result of phase separation were dependent on the concentrations of La and Hf in the films. During the annealing treatment, silicate was produced due to interfacial reactions and the interfacial reactions were found to be dependent on the La{sub 2}O{sub 3} content in the La{sub x}Hf{sub y}O films, which has a significant influence on the phase separation process and resulting film structure.

  14. Amorphic complexity

    NASA Astrophysics Data System (ADS)

    Fuhrmann, G.; Gröger, M.; Jäger, T.

    2016-02-01

    We introduce amorphic complexity as a new topological invariant that measures the complexity of dynamical systems in the regime of zero entropy. Its main purpose is to detect the very onset of disorder in the asymptotic behaviour. For instance, it gives positive value to Denjoy examples on the circle and Sturmian subshifts, while being zero for all isometries and Morse-Smale systems. After discussing basic properties and examples, we show that amorphic complexity and the underlying asymptotic separation numbers can be used to distinguish almost automorphic minimal systems from equicontinuous ones. For symbolic systems, amorphic complexity equals the box dimension of the associated Besicovitch space. In this context, we concentrate on regular Toeplitz flows and give a detailed description of the relation to the scaling behaviour of the densities of the p-skeletons. Finally, we take a look at strange non-chaotic attractors appearing in so-called pinched skew product systems. Continuous-time systems, more general group actions and the application to cut and project quasicrystals will be treated in subsequent work.

  15. 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.

  16. Dual phase separation in a two-dimensional driven diffusive system

    NASA Astrophysics Data System (ADS)

    Hao, Qing-Yi; Jiang, Rui; Hu, Mao-Bin; Jia, Bin

    2017-05-01

    This paper studies a bidirectional multilane driven diffusive system with two type of particles. Phase separation phenomenon emerges in the system. In particular, a novel dual phase separation could be observed under certain circumstance. Mean field analysis has been carried out, which indicates that occurrence of phase separation might be related to minimization of system current. Specifically, the occurrence of dual phase separation is due to (i) existence of a local minimum in the fundamental diagram of flow rate J versus density ρ and (ii) ∂ J / ∂ ρ|ρ=1 < 0. Our findings offer sights to understand deeply dynamic features of multilane transportation system, especially phase separation of nonequilibrium state systems.

  17. Biogenic fish-gut calcium carbonate is a stable amorphous phase in the gilt-head seabream, Sparus aurata.

    PubMed

    Foran, Elizabeth; Weiner, Steve; Fine, Maoz

    2013-01-01

    The main source of calcium carbonate (CaCO₃) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO₃ are also produced in fish intestines. The precipitation of CaCO₃ assists fish in intestinal water absorption and aids in whole body Ca²⁺ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg²⁺, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration.

  18. Dual Phase Membrane for High Temperature CO2 Separation

    SciTech Connect

    Jerry Y.S. Lin; Matthew Anderson

    2006-09-29

    Dual-phase membranes consisting of stainless steel supports infiltrated with molten carbonate have been shown to be selective to CO{sub 2} at high temperatures (400-650 C). However, over time at high temperatures, the formation of iron oxides on the surface of the stainless steel supports render the membranes ineffective. This report details synthesis and characteristics of dual-phase carbonate membrane with an oxidation resistant perovskite type ceramic (lanthanum-strontium-cobaltite-iron; LSCF) support. Porous LSCF supports were prepared from its powder synthesized by the citrate method. Both steady state permeation and mercury porosimetry confirmed that the LSCF membrane sintered at 900 C has pores large enough to absorb molten carbonate, yet small enough to retain the molten carbonate under high pressure conditions. Results of XRD analysis have shown that LSCF and the molten carbonate mixture do not react with each other at temperatures below 700 C. Four-point method conductivity tests indicate that the support material has sufficiently high electronic conductivity for this application. Li-Na-K carbonate was coated to the porous LSCF support by a liquid infiltration method. Helium permeance of the support before and after infiltration of molten carbonate are on the order of 10{sup -6} and 10{sup -10} moles/m{sup 2} {center_dot} Pa {center_dot} s respectively, indicating that the molten carbonate is able to sufficiently infiltrate the membrane. Preliminary high temperature permeation experiments indicate that the membrane does separate CO{sub 2} in the presence of O{sub 2}, with a maximum flux of 0.623 ml/cm{sup 2} {center_dot} min obtained at 850 C.

  19. Comparison of liquid and supercritical fluid chromatography mobile phases for enantioselective separations on polysaccharide stationary phases.

    PubMed

    Khater, Syame; Lozac'h, Marie-Anne; Adam, Isabelle; Francotte, Eric; West, Caroline

    2016-10-07

    Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercritical fluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity.

  20. Kinetics of the laser-induced solid phase crystallization of amorphous silicon-Time-resolved Raman spectroscopy and computer simulations

    NASA Astrophysics Data System (ADS)

    Očenášek, J.; Novák, P.; Prušáková, L.

    2017-01-01

    This study demonstrates that a laser-induced crystallization instrumented with Raman spectroscopy is, in general, an effective tool to study the thermally activated crystallization kinetics. It is shown, for the solid phase crystallization of an amorphous silicon thin film, that the integral intensity of Raman spectra corresponding to the crystalline phase grows linearly in the time-logarithmic scale. A mathematical model, which assumes random nucleation and crystal growth, was designed to simulate the crystallization process in the non-uniform temperature field induced by laser. The model is based on solving the Eikonal equation and the Arhenius temperature dependence of the crystal nucleation and the growth rate. These computer simulations successfully approximate the crystallization process kinetics and suggest that laser-induced crystallization is primarily thermally activated.

  1. Nanoscale phase separation in ultra-tough hydrogels

    NASA Astrophysics Data System (ADS)

    Nixon, Ryan; Ten Hove, Jan Bart; Orozco, Adrian; Sawyer, W. Gregory; Angelini, Thomas

    2014-03-01

    Soft, wettable, water permeable materials that resist protein adsorption are essential to countless biomaterials, adaptive optics and microfluidics technologies. Hydrogels would be ideal for these applications, but are notoriously brittle and weak. For example, hydrogel coatings of synovial joint prosthetics exhibit irrecoverable damage after a single cycle of wear. The development of elastomer-like hydrogels that are tough, soft, and mechanically resilient would improve their versatility and create opportunities for a wide range of new applications. Here we present studies of an ultra-tough hydrogel, synthesized by the co-polymerization of two monomer species that polymerize at different rates and have strongly differing degrees of solvation. The resulting blended hydrogel network forms with both covalent and labile adhesive bonds, greatly improving recoverable energy dissipation and reducing fatigue relative to networks made from either constituent alone. We have studied the structural origins of the strengthening behavior using small angle x-ray scattering (SAXS) and found that the constituent polymers phase separate into nanoscale domains, which may prevent crack nucleation and propagation.

  2. Electroresistance and electronic phase separation in mixed-valent manganites.

    PubMed

    Wu, T; Ogale, S B; Garrison, J E; Nagaraj, B; Biswas, A; Chen, Z; Greene, R L; Ramesh, R; Venkatesan, T; Millis, A J

    2001-06-25

    The sensitivity of transport in colossal magnetoresistance (CMR) manganites to external electric and magnetic fields is examined using field effect configurations with La(0.7)Ca(0.3)MnO(3) (LCMO), Na(0.7)Sr(0.3)MnO(3), La(0.7)Ba(0.3)MnO(3), and La(0.5)Ca(0.5)MnO(3) (0.5-doped LCMO) channels, and ferroelectric PbZr(0.2)Ti(0.8)O(3) (PZT) or dielectric (SrTiO(3)) gates. A large electroresistance (ER) of approximately 76% at 4 x 10(5) V/cm is found in LCMO with PZT-ferroelectric gate, but the magnitude of the effect is much smaller (a few percent) in the other three channels. The ER and CMR effects are remarkably complimentary. The size and systematics of the effect strongly favor a percolative phase separation picture.

  3. Confinement-Driven Phase Separation of Quantum Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Prisk, T. R.; Pantalei, C.; Kaiser, H.; Sokol, P. E.

    2012-08-01

    We report small-angle neutron scattering studies of liquid helium mixtures confined in Mobil Crystalline Material-41 (MCM-41), a porous silica glass with narrow cylindrical nanopores (d=3.4nm). MCM-41 is an ideal model adsorbent for fundamental studies of gas sorption in porous media because its monodisperse pores are arranged in a 2D triangular lattice. The small-angle scattering consists of a series of diffraction peaks whose intensities are determined by how the imbibed liquid fills the pores. Pure He4 adsorbed in the pores show classic, layer-by-layer film growth as a function of pore filling, leaving the long range symmetry of the system intact. In contrast, the adsorption of He3-He4 mixtures produces a structure incommensurate with the pore lattice. Neither capillary condensation nor preferential adsorption of one helium isotope to the pore walls can provide the symmetry-breaking mechanism. The scattering is consistent with the formation of randomly distributed liquid-liquid microdomains ˜2.3nm in size, providing evidence that confinement in a nanometer scale capillary can drive local phase separation in quantum liquid mixtures.

  4. Light scattering investigation of phase separation in a micelle system

    SciTech Connect

    Wilcoxon, J.P.; Martin, J.E.; Odinek, J.

    1993-12-31

    We report a real-time, two-dimensional light scattering study of the evolution of structure in a two component nonionic micelle system during phase separation via spinodal decomposition. Our principal finding is that domain growth proceeds much slower than the cube root of time prediction for simple binary fluids. In fact, the growth kinetics can be empirically described as a stretched exponential approach to a pinned domain size. Although the kinetics are not yet understood, this anomalous behavior may be due to the ability of the spherical micelles to reorganize into more complex structures. The domain structure also shows some anomalies. Although at short times the expected structure factor for a critical quench is observed, at long times the structure factor crosses over to the off-critical form. However, in all cases the average scattered intensity is proportional to the cube of the domain size. These findings are discussed in comparison to standard theories of and experimental work on binary fluids.

  5. Dual Phase Membrane for High temperature CO2 Separation

    SciTech Connect

    Jerry Y.S. Lin; Matthew Anderson

    2005-12-01

    Research in the previous years in this project found that stainless steel supports are oxidized during high temperature, dual phase membrane separation of carbon dioxide (with oxygen). Consequently, a new material has been sought to alleviate the problems with oxidation. Lanthanum cobaltite oxide is a suitable candidate for the support material in the dual phase membrane due to its oxidation resistance and electronic conductivity. Porous lanthanum cobaltite membranes were prepared via the citrate method, using nitrate metal precursors as the source of La, Sr, Co and Fe. The material was prepared and ground into a powder, which was subsequently pressed into disks for sintering at 900 C. Conductivity measurements were evaluated using the four-probe DC method. Support pore size was determined by helium permeation. Conductivity of the lanthanum cobaltite material was found to be at a maximum of 0.1856 S/cm at 550 C. The helium permeance of the lanthanum cobaltite membranes for this research was on the order of 10{sup -6} moles/m{sup 2} {center_dot} Pa {center_dot} s, proving that the membranes are porous after sintering at 900 C. The average pore size based on steady state helium permeance measurements was found to be between 0.37 and 0.57 {micro}m. The lanthanum cobaltite membranes have shown to have desired porosity, pore size and electric conductivity as the support for the dual-phase membranes. Molten carbonate was infiltrated to the pores of lanthanum cobaltite membranes support. After infiltration with molten carbonate, the helium permeance of the membranes decreased by three orders of magnitude to 10{sup -9} moles/m{sup 2} {center_dot} Pa {center_dot} s. This number, however, is one order of magnitude larger than the room temperate permeance of the stainless steel supports after infiltration with molten carbonate. Optimization of the dip coating process with molten carbonate will be evaluated to determine if lower permeance values can be obtained with the

  6. Carbon Dioxide Separation from Flue Gas by Phase Enhanced Absorption

    SciTech Connect

    Liang Hu

    2006-06-30

    A new process, phase enhanced absorption, was invented. The method is carried out in an absorber, where a liquid carrier (aqueous solution), an organic mixture (or organic compound), and a gas mixture containing a gas to be absorbed are introduced from an inlet. Since the organic mixture is immiscible or at least partially immiscible with the liquid carrier, the organic mixture forms a layer or small parcels between the liquid carrier and the gas mixture. The organic mixture in the absorber improves mass transfer efficiency of the system and increases the absorption rate of the gas. The organic mixture serves as a transportation media. The gas is finally accumulated in the liquid carrier as in a conventional gas-liquid absorption system. The presence of the organic layer does not hinder the regeneration of the liquid carrier or recovery of the gas because the organic layer is removed by a settler after the absorption process is completed. In another aspect, the system exhibited increased gas-liquid separation efficiency, thereby reducing the costs of operation and maintenance. Our study focused on the search of the organic layer or transportation layer to enhance the absorption rate of carbon dioxide. The following systems were studied, (1) CO{sub 2}-water system and CO{sub 2}-water-organic layer system; (2) CO{sub 2}-Potassium Carbonate aqueous solution system and CO{sub 2}-Potassium Carbonate aqueous solution-organic layer system. CO{sub 2}-water and CO{sub 2}-Potassium Carbonate systems are the traditional gas-liquid absorption processes. The CO{sub 2}-water-organic layer and CO{sub 2}-Potassium Carbonate-organic layer systems are the novel absorption processes, phase enhanced absorption. As we mentioned early, organic layer (transportation layer phase) is used for the increase of absorption rate. Our study showed that the absorption rate can be increased by adding the organic layer. However, the enhanced factor is highly depended on the liquid mass transfer

  7. Relation between the phase separation and the crystallization in protein solutions

    NASA Astrophysics Data System (ADS)

    Tanaka, Shinpei; Yamamoto, Masahiko; Ito, Kohzo; Hayakawa, Reinosuke; Ataka, Mitsuo

    1997-07-01

    Liquid-liquid phase separation and crystallization (or solid-liquid phase separation) both occur in protein solutions. By adopting egg-white lysozyme for a model system, we compared two types of diagrams, a phase diagram of the liquid-liquid phase separation and a morphological diagram of protein crystals. By superimposing these diagrams, we distinguished two types of white precipitates, urchinlike spherulites arising from the crystallization and protein-rich droplets from the liquid-liquid phase separation. Furthermore, we observed a transformation from the protein-rich droplets to the spherulites, and simultaneously an unusual pattern evolution of the protein-rich phase unlike the conventional phase separation of typical binary mixtures. This is understood in terms of the competition between the crystallization and the liquid-liquid phase separation.

  8. Separation of 9,10-anthraquinone derivatives: evaluation of functionalised stationary phases in reversed phase mode.

    PubMed

    Nowik, Witold; Bonose-Crosnier de Bellaistre, Myriam; Tchapla, Alain; Héron, Sylvie

    2011-06-10

    A series of reversed phases bonded with several functional groups was investigated for separation of anthraquinone derivatives, following the previous work, dedicated to the selectivity of octadecyl silica bonded phases. Considering wide diversity of substitutions in hydrophobic anthraquinone skeleton, interactions like dipole-dipole, π-π or H-bond acceptor/donor, as well as inclusion complexes formation can be employed to improve separation. In this study, several phases with grafts like cyano, nitro, aromatic, PEG, diol, calixarene and cyclodextrin were used with water-acetonitrile gradient for separation of thirty anthraquinoids' standards. The evaluation of performances was measured using the symmetry parameter and the number of critical pairs of peaks formed. The results point out the aromatic and calixarene bonded silica as the most interesting in terms of symmetry and critical pairs number. Finally we tested the performance of Caltrex Resorcinaren, Pursuit XRs DP and Luna Phenyl-Hexyl on real samples of anthraquinone natural dye extracted from a red thread taken from a 15th C. tapestry. We observed and compared the retention behaviour of some new anthraquinoids additional to our standards set and showing behaviour particular to substituted anthraquinone carboxylic acids. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Microstructural Evolution and Mechanical Properties of Nanointermetallic Phase Dispersed Al65Cu20Ti15 Amorphous Matrix Composite Synthesized by Mechanical Alloying and Hot Isostatic Pressing

    NASA Astrophysics Data System (ADS)

    Roy, D.; Mitra, R.; Ojo, O. A.; Lojkowski, W.; Manna, I.

    2011-08-01

    The structure and mechanical properties of nanocrystalline intermetallic phase dispersed amorphous matrix composite prepared by hot isostatic pressing (HIP) of mechanically alloyed Al65Cu20Ti15 amorphous powder in the temperature range 573 K to 873 K (300 °C to 600 °C) with 1.2 GPa pressure were studied. Phase identification by X-ray diffraction (XRD) and microstructural investigation by transmission electron microscopy confirmed that sintering in this temperature range led to partial crystallization of the amorphous powder. The microstructures of the consolidated composites were found to have nanocrystalline intermetallic precipitates of Al5CuTi2, Al3Ti, AlCu, Al2Cu, and Al4Cu9 dispersed in amorphous matrix. An optimum combination of density (3.73 Mg/m3), hardness (8.96 GPa), compressive strength (1650 MPa), shear strength (850 MPa), and Young's modulus (182 GPa) were obtained in the composite hot isostatically pressed ("hipped") at 773 K (500 °C). Furthermore, these results were compared with those from earlier studies based on conventional sintering (CCS), high pressure sintering (HPS), and pulse plasma sintering (PPS). HIP appears to be the most preferred process for achieving an optimum combination of density and mechanical properties in amorphous-nanocrystalline intermetallic composites at temperatures ≤773 K (500 °C), while HPS is most suited for bulk amorphous alloys. Both density and volume fraction of intermetallic dispersoids were found to influence the mechanical properties of the composites.

  10. Effect of OH content on phase separation behavior of soda-silica glasses

    NASA Technical Reports Server (NTRS)

    Neilson, G. F.; Weinberg, M. C.; Smith, G. L.

    1986-01-01

    The kinetics of phase separation in a gel and ordinary soda-silica glass are followed by use of small angle X-ray scattering. Also, the influence of OH on the phase separation behavior is studied. It is found that OH accelerates the growth of the secondary phase, and that gel and ordinary glasses of similar composition and OH concentration exhibit similar phase separation characteristics.

  11. Effect of solid-phase amorphization on the spectral characteristics of europium-doped gadolinium molybdate

    NASA Astrophysics Data System (ADS)

    Shmurak, S. Z.; Kiselev, A. P.; Kurmasheva, D. M.; Red'Kin, B. S.; Sinitsyn, V. V.

    2010-05-01

    A method is proposed for detecting spectral characteristics of optically inactive molybdates of rare-earth elements by their doping with rare-earth ions whose luminescence lies in the transparency region of all structural modifications of the sample. Gadolinium molybdate is chosen as the object of investigations, while europium ions are used as an optically active and structurally sensitive admixture. It is shown that after the action of a high pressure under which gadolinium molybdate passes to the amorphous state, the spectral characteristics of Gd1.99Eu0.01(MoO4)3 (GMO:Eu) change radically; namely, considerable line broadening is observed in the luminescence spectra and the luminescence excitation spectra, while the long-wave threshold of optical absorption is shifted considerably (by approximately 1.1 eV) towards lower energies. It is found that by changing the structural state of GMO:Eu by solid-state amorphization followed by annealing, the spectral characteristics of the sample can be purposefully changed. This is extremely important for solving the urgent problem of designing high-efficiency light-emitting diodes producing “white” light.

  12. Confined Pattern-Directed Assembly of Polymer-Grafted Nanoparticles in a Phase Separating Blend with a Homopolymer Matrix.

    PubMed

    Zhang, Ren; Lee, Bongjoon; Bockstaller, Michael R; Douglas, Jack F; Stafford, Christopher M; Kumar, Sanat K; Raghavan, Dharmaraj; Karim, Alamgir

    The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. We show that the phase separation of polymer-tethered nanoparticles immersed in a chemically different polymer matrix provides an effective and scalable method for fabricating defined submicron-sized amorphous NP domains in melt polymer thin films. We investigate this phenomenon with a view towards understanding and controlling the phase separation process through directed nanoparticle assembly. In particular, we consider isothermally annealed thin films of polystyrene-grafted gold nanoparticles (AuPS) dispersed in a poly(methyl methacrylate) (PMMA) matrix. Classic binary polymer blend phase separation related morphology transitions, from discrete AuPS domains to bicontinuous to inverse domain structure with increasing nanoparticle composition is observed, yet the kinetics of the AuPS/PMMA polymer blends system exhibit unique features compared to the parent PS/PMMA homopolymer blend. We further illustrate how to pattern-align the phase-separated AuPS nanoparticle domain shape, size and location through the imposition of a simple and novel external symmetry-breaking perturbation via soft-lithography. Specifically, submicron-sized topographically patterned elastomer confinement is introduced to direct the nanoparticles into kinetically controlled long-range ordered domains, having a dense yet well-dispersed distribution of non-crystallizing nanoparticles. The simplicity, versatility and roll-to-roll adaptability of this novel method for controlled nanoparticle assembly should make it useful in creating desirable patterned nanoparticle domains for a variety of functional materials and applications.

  13. Amorphous Solid Water (ASW): Macroscale Environmentally-Neutral Application for Remediation of Hazardous Pollutants using Condensed-Phase Cryogenic Fluids

    NASA Astrophysics Data System (ADS)

    de Strulle, Ronald; Rheinhart, Maximilian

    2012-03-01

    We report macroscale environmentally-neutral use of cryogenic fluids to induce phase transitions from crystalline water-ices to amorphous solid water (ASW). New IP and uses in remediation of oil-spills and hazardous immiscibles from aquatic environments. We display high-resolution images of the transitions from hexagonal to cubic crystalline water-ice, then to hydrophobic ASW. Accretion and encapsulation of viscous pollutants within crystalline water-ice, and sequestration of condensed volatiles (PAH, methane) and low viscosity fluids within the interstitial cavities of ASW are shown and differentiated for: crude oils, diesel (heating) and blended oils, petroleum byproducts, vegetable and mineral oils, lipids, and light immiscible fluids. The effects of PdV work and thermal energy transfers during phase changes are shown, along with the sequestration efficiencies for hexagonal and cubic ice lattices vs. non-crystalline ASW, for a range of pollutant substances. The viability of ASW as a medium for study of quantum criticality phases is also proposed. The process is environmentally-neutral in that only substantially condensed-phase air liquefaction products, e.g. nitrogen in >90% liquid phase are employed as an active agent. The applications are also presented in terms of the scale-up of experiments performed at the nanoscale.

  14. Carbon Dioxide Separation from Flue Gas by Phase Enhanced Absorption

    SciTech Connect

    Tim Fout

    2007-06-30

    A new process, phase enhanced absorption, was invented. The method is carried out in an absorber, where a liquid carrier (aqueous solution), an organic mixture (or organic compound), and a gas mixture containing a gas to be absorbed are introduced from an inlet. Since the organic mixture is immiscible or at least partially immiscible with the liquid carrier, the organic mixture forms a layer or small parcels between the liquid carrier and the gas mixture. The organic mixture in the absorber improves mass transfer efficiency of the system and increases the absorption rate of the gas. The organic mixture serves as a transportation media. The gas is finally accumulated in the liquid carrier as in a conventional gas-liquid absorption system. The presence of the organic layer does not hinder the regeneration of the liquid carrier or recovery of the gas because the organic layer is removed by a settler after the absorption process is completed. In another aspect, the system exhibited increased gas-liquid separation efficiency, thereby reducing the costs of operation and maintenance. Our study focused on the search of the organic layer or transportation layer to enhance the absorption rate of carbon dioxide. The following systems were studied, (1) CO{sub 2}-water system and CO{sub 2}-water-organic layer system; (2) CO{sub 2}-Potassium Carbonate aqueous solution system and CO{sub 2}-Potassium Carbonate aqueous solution-organic layer system. CO{sub 2}-water and CO{sub 2}-Potassium Carbonate systems are the traditional gas-liquid absorption processes. The CO{sub 2}-water-organic layer and CO{sub 2}-Potassium Carbonate-organic layer systems are the novel absorption processes, phase enhanced absorption. As we mentioned early, organic layer is used for the increase of absorption rate, and plays the role of transportation of CO{sub 2}. Our study showed that the absorption rate can be increased by adding the organic layer. However, the enhanced factor is highly depended on the

  15. Amorphous Aggregation of Cytochrome c with Inherently Low Amyloidogenicity Is Characterized by the Metastability of Supersaturation and the Phase Diagram.

    PubMed

    Lin, Yuxi; Kardos, József; Imai, Mizue; Ikenoue, Tatsuya; Kinoshita, Misaki; Sugiki, Toshihiko; Ishimori, Koichiro; Goto, Yuji; Lee, Young-Ho

    2016-03-01

    Despite extensive studies on the folding and function of cytochrome c, the mechanisms underlying its aggregation remain largely unknown. We herein examined the aggregation behavior of the physiologically relevant two types of cytochrome c, metal-bound cytochrome c, and its fragment with high amyloidogenicity as predicted in alcohol/water mixtures. Although the aggregation propensity of holo cytochrome c was low due to high solubility, markedly unfolded apo cytochrome c, lacking the heme prosthetic group, strongly promoted the propensity for amorphous aggregation with increases in hydrophobicity. Silver-bound apo cytochrome c increased the capacity of fibrillar aggregation (i.e., protofibrils or immature fibrils) due to subtle structural changes of apo cytochrome c by strong binding of silver. However, mature amyloid fibrils were not detected for any of the cytochrome c variants or its fragment, even with extensive ultrasonication, which is a powerful amyloid inducer. These results revealed the intrinsically low amyloidogenicity of cytochrome c, which is beneficial for its homeostasis and function by facilitating the folding and minimizing irreversible amyloid formation. We propose that intrinsically low amyloidogenicity of cytochrome c is attributed to the low metastability of supersaturation. The phase diagram constructed based on solubility and aggregate type is useful for a comprehensive understanding of protein aggregation. Furthermore, amorphous aggregation, which is also viewed as a generic property of proteins, and amyloid fibrillation can be distinguished from each other by the metastability of supersaturation.

  16. Osteoselection supported by phase separated polymer blend films.

    PubMed

    Gulsuner, Hilal Unal; Gengec, Nevin Atalay; Kilinc, Murat; Erbil, H Yildirim; Tekinay, Ayse B

    2015-01-01

    The instability of implants after placement inside the body is one of the main obstacles to clinically succeed in periodontal and orthopedic applications. Adherence of fibroblasts instead of osteoblasts to implant surfaces usually results in formation of scar tissue and loss of the implant. Thus, selective bioadhesivity of osteoblasts is a desired characteristic for implant materials. In this study, we developed osteoselective and biofriendly polymeric thin films fabricated with a simple phase separation method using either homopolymers or various blends of homopolymers and copolymers. As adhesive and proliferative features of cells are highly dependent on the physicochemical properties of the surfaces, substrates with distinct chemical heterogeneity, wettability, and surface topography were developed and assessed for their osteoselective characteristics. Surface characterizations of the fabricated polymer thin films were performed with optical microscopy and SEM, their wettabilities were determined by contact angle measurements, and their surface roughness was measured by profilometry. Long-term adhesion behaviors of cells to polymer thin films were determined by F-actin staining of Saos-2 osteoblasts, and human gingival fibroblasts, HGFs, and their morphologies were observed by SEM imaging. The biocompatibility of the surfaces was also examined through cell viability assay. Our results showed that heterogeneous polypropylene polyethylene/polystyrene surfaces can govern Saos-2 and HGF attachment and organization. Selective adhesion of Saos-2 osteoblasts and inhibited adhesion of HGF cells were achieved on micro-structured and hydrophobic surfaces. This work paves the way for better control of cellular behaviors for adjustment of cell material interactions. © 2014 Wiley Periodicals, Inc.

  17. Investigation of the micro-mechanical properties of femtosecond laser-induced phases in amorphous silica

    NASA Astrophysics Data System (ADS)

    Athanasiou, Christos-Edward; Bellouard, Yves

    2016-03-01

    Femtosecond pulses used in the regime where self-organized patterns are found have two noticeable effects in amorphous silica's (a-SiO2) optical and chemical properties: The decrease of the material's refractive index as well as an enhanced etching selectivity. However, the effect on the material mechanical properties is unexplored. In this paper, we present elastic modulus measurements of fused silica exposed to femtosecond laser pulses in the regime where nanogratings are found. The measurement principle is based on the use of femtosecond laser fabricated displacement amplification mechanism combined with a discrete stiffness model. In this laser exposure regime, a significant decrease of the elastic modulus is observed. Our findings are consistent with the existence of a porous structure found within nanogratings lamellas.

  18. Amorphous silicon research. Phase III technical progress report, August 1, 1996--July 31, 1997

    SciTech Connect

    Guha, S.

    1997-11-01

    The principal objective of this R&D program is to expand, enhance and accelerate knowledge and capabilities for the development of high-performance, two-terminal multijunction hydrogenated amorphous silicon (a-Si) alloy cells and modules. The near-term goal of the program is to achieve 12% stable active-area efficiency using the multijunction approach. The long-term goal is to achieve 15% stable efficiency multijunction modules. The major effort of this program is to develop high efficiency component cells and incorporate them in the triple-junction structure to obtain the highest stable efficiency. New and improved deposition regimes were investigated to obtain better cell performance. Fundamental studies to obtain better understanding of material and cell performance were undertaken.

  19. Amorphous silicon research Phase I. Annual subcontract report, August 1, 1994--July 31, 1995

    SciTech Connect

    Guha, S.

    1995-10-01

    The Principal objective of this R&D program is to expand, enhance and accelerate knowledge and capabilities for the development of high-performance, two-terminal multifunction hydrogenated amorphous silicon (a-Si:H) alloy modules. The near-term goal of the program is to achieve 12% stable efficiency by 1998 using the multifunction approach. The major effort of this program is to develop high efficiency component cells and incorporate them in the triple-junction structure to obtain the highest stable efficiency. The bulk of the effort was directed toward the middle and bottom cell structure. New and improved deposition regimes were investigated to obtain better cell performance. Fundamental studies to obtain better understanding of material and cell performance were undertaken.

  20. Characterizing the Phyllosilicates and Amorphous Phases Found by MSL Using Laboratory XRD and EGA Measurements of Natural and Synthetic Materials (Invited)

    NASA Astrophysics Data System (ADS)

    Rampe, E. B.; Morris, R. V.; Chipera, S.; Bish, D. L.; Bristow, T.; Archer, P. D.; Blake, D.; Achilles, C.; Ming, D. W.; Vaniman, D.; Crisp, J. A.; Des Marais, D. J.; Downs, R.; Farmer, J. D.; Morookian, J.; Morrison, S.; Sarrazin, P.; Spanovich, N.; Treiman, A. H.; Yen, A. S.; Team, M.

    2013-12-01

    The Curiosity Rover landed on the Peace Vallis alluvial fan in Gale crater on August 5, 2012. A primary mission science objective is to search for past habitable environments, and, in particular, to assess the role of past water. Identifying the minerals and mineraloids that result from aqueous alteration at Gale crater is essential for understanding past aqueous processes at the MSL landing site and hence for interpreting the site's potential habitability. X-ray diffraction (XRD) data from the CheMin instrument and evolved gas analyses (EGA) from the SAM instrument have helped the MSL science team identify phases that resulted from aqueous processes: phyllosilicates and amorphous phases were measure in two drill samples (John Klein and Cumberland) obtained from the Sheepbed Member, Yellowknife Bay Fm., which is believed to represent a fluvial-lacustrine environment. A third set of analyses was obtained from scoop samples from the Rocknest sand shadow. Chemical data from the APXS instrument have helped constrain the chemical compositions of these secondary phases and suggest that the phyllosilicate component is Mg-enriched and the amorphous component is Fe-enriched, relatively Si-poor, and S- and H-bearing. To refine the phyllosilicate and amorphous components in the samples measured by MSL, we measured XRD and EGA data for a variety of relevant natural terrestrial phyllosilicates and synthetic mineraloids in laboratory testbeds of the CheMin and SAM instruments. Specifically, Mg-saturated smectites and vermiculites were measured with XRD at low relative humidity to understand the behavior of the 001 reflections under Mars-like conditions. Our laboratory XRD measurements suggest that interlayer cation composition affects the hydration state of swelling clays at low RH and, thus, the 001 peak positions. XRD patterns of synthetic amorphous materials, including allophane, ferrihydrite, and hisingerite were used in full-pattern fitting (FULLPAT) models to help

  1. A Temperature-Dependent Phase-Field Model for Phase Separation and Damage

    NASA Astrophysics Data System (ADS)

    Heinemann, Christian; Kraus, Christiane; Rocca, Elisabetta; Rossi, Riccarda

    2017-03-01

    In this paper we study a model for phase separation and damage in thermoviscoelastic materials. The main novelty of the paper consists in the fact that, in contrast with previous works in the literature concerning phase separation and damage processes in elastic media, in our model we encompass thermal processes, nonlinearly coupled with the damage, concentration and displacement evolutions. More particularly, we prove the existence of "entropic weak solutions", resorting to a solvability concept first introduced in uc(Feireisl) (Comput Math Appl 53:461-490, 2007) in the framework of Fourier-Navier-Stokes systems and then recently employed in uc(Feireisl) et al. (Math Methods Appl Sci 32:1345-1369, 2009) and uc(Rocca) and uc(Rossi) (Math Models Methods Appl Sci 24:1265-1341, 2014) for the study of PDE systems for phase transition and damage. Our global-in-time existence result is obtained by passing to the limit in a carefully devised time-discretization scheme.

  2. 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.

  3. Using Environment-Sensitive Fluorescent Probes to Characterize Liquid-Liquid Phase Separation in Supersaturated Solutions of Poorly Water Soluble Compounds.

    PubMed

    Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

    2015-11-01

    Highly supersaturated aqueous solutions of poorly soluble compounds can undergo liquid-liquid phase separation (LLPS) when the concentration exceeds the "amorphous solubility". This phenomenon has been widely observed during high throughput screening of new molecular entities as well as during the dissolution of amorphous solid dispersions. In this study, we have evaluated the use of environment-sensitive fluorescence probes to investigate the formation and properties of the non-crystalline drug-rich aggregates formed in aqueous solutions as a result of LLPS. Six different environment-sensitive fluorophores were employed to study LLPS in highly supersaturated solutions of several model compounds, all dihydropyridine derivatives. Each fluoroprobe exhibited a large hypsochromic shift with decreasing environment polarity. Upon drug aggregate formation, the probes partitioned into the drug-rich phase and exhibited changes in emission wavelength and intensity consistent with sensing a lower polarity environment. The LLPS onset concentrations determined using the fluorescence measurements were in good agreement with light scattering measurements as well as theoretically estimated amorphous solubility values. Environment-sensitive fluorescence probes are useful to help understand the phase behavior of highly supersaturated aqueous solutions, which in turn is important in the context of developing enabling formulations for poorly soluble compounds.

  4. Preparation of a hierarchically porous AlPO4 monolith via an epoxide-mediated sol-gel process accompanied by phase separation

    NASA Astrophysics Data System (ADS)

    Li, Wenyan; Zhu, Yang; Guo, Xingzhong; Nakanishi, Kazuki; Kanamori, Kazuyoshi; Yang, Hui

    2013-08-01

    Monolithic aluminum phosphate (AlPO4) with a macro-mesoporous structure has been successfully prepared via the sol-gel process accompanied by phase separation in the presence of poly(ethylene oxide) (PEO). Gelation of the system has been mediated by propylene oxide (PO), while PEO induces a phase separation. The dried gel is amorphous, whereas the crystalline tridymite phase precipitates upon heating above 1000 °C. Heat treatment does not spoil the macroporous morphology of the AlPO4 monoliths. Nitrogen adsorption-desorption measurements revealed that the skeletons of the dried gels possess a mesostructure with a median pore size of about 30 nm and a surface area as high as 120 m2 g-1. Hydrothermal treatment before heat treatment can increase the surface area to 282 m2 g-1.

  5. A computational model for swirl vane phase separators

    NASA Astrophysics Data System (ADS)

    Lider, Serhat

    The main objective of this study is to develop a mechanistic separator-dryer model for the TRAC-BF1 code to solve the problems associated with the modeling of the steam separation phenomena. This model, in a sense, is an extension to the existing separator-dryer model in the TRAC-BF1 code. The phasic velocities and the pressures for the vapor core and the liquid film regions of the swirl vane separator are solved by the use of phasic mass and momentum equations along with pressure drop. A new dryer efficiency model is also introduced. In this model, the dryer efficiency is calculated by the corrugated plate efficiency model. The important part of the study focuses on the implementation of the separator-dryer model to the code. The implementation uses the correct convective parameters in the solution of the conservation equation for the mixing cell of separator-dryer component. The model is tested and assessed against the experimental data, an actual reactor transient, and the results of the existing model. The results indicates that the new steam separation model is more accurate and more robust when compared to the separator-dryer model.

  6. Interplay between gelation and phase separation in aqueous solutions of methylcellulose and hydroxypropylmethylcellulose.

    PubMed

    Fairclough, J Patrick A; Yu, Hao; Kelly, Oscar; Ryan, Anthony J; Sammler, Robert L; Radler, Michael

    2012-07-17

    Thermally induced gelation in aqueous solutions of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) has been studied by rheological, optical microscopy, and turbidimetry measurements. The structural and mechanical properties of these hydrogels are dominated by the interplay between phase separation and gelation. In MC solutions, phase separation takes place almost simultaneously with gelation. An increase in the storage modulus is coupled to the appearance of a bicontinuous structure upon heating. However, a thermal gap exists between phase separation and gelation in the case of HPMC solutions. The storage modulus shows a dramatic decrease during phase separation and then rises in the subsequent gelation. A macroporous structure forms in the gels via "viscoelastic phase separation" linked to "double phase separation".

  7. A vibrational spectroscopic study on amorphous phase associated with crystallization and deformation behavior of poly(lactic acid)

    NASA Astrophysics Data System (ADS)

    Kang, Shuhui; Hsu, Shaw Ling

    2002-03-01

    We have used Raman spectroscopy in conjunction with differential scanning calorimetry to characterize the structure of biodegradable poly(lactic acid). It is known that crystallization behavior of this bio-commodity polymer is strongly dependent on the amount and sequence of configurational defects, i. e. D isomer. Relatively little effort has been devoted to the study of the amorphous phase. Based on a number of normal coordinate analyses, specific spectroscopic features have been identified which is capable of identifying defect content. By introducing D defects, which have the opposite chirality to native L-unit s, the number of curved conformational sequences increase, or conversely the number of straight conformational sequences decrease. We found that deformation will increase the latter and decrease the former. In addition, the changes in chain persistance length, nucleation rate with different D defects content, sequence distribution, and draw ratio are discussed.

  8. Controlled synthesis of crystalline calcium carbonate aggregates with unusual morphologies involving the phase transformation from amorphous calcium carbonate

    SciTech Connect

    Tang Hua; Yu Jiaguo Zhao Xiufeng

    2009-04-02

    Peanut-shaped CaCO{sub 3} aggregates, featured of two dandelion-like heads built up from rod-like subunits, have been synthesized via a facile precipitation reaction between Na{sub 2}CO{sub 3} and CaCl{sub 2} at ambient temperature in the presence of magnesium ions and ethanol solvent. The as-prepared products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a high magnesium concentration and ethanol solvent are necessary for the formation of the unusual peanut-like aggregates. In addition, a multistep phase transformation process from amorphous calcium carbonate (ACC) to a mixture of ACC and calcite and ultimately to calcite and aragonite was observed in the formation process of the unusual structures. A possible mechanism for the formation of the unusual peanut-shape aggregates has been proposed and discussed.

  9. Ultrasonic study of solid-phase amorphization and polyamorphism in an H2O-D2O (1: 1) solid solution

    NASA Astrophysics Data System (ADS)

    Gromnitskaya, E. L.; Lyapin, A. G.; Stalgorova, O. V.; Danilov, I. V.; Brazhkin, V. V.

    2013-02-01

    The elastic moduli and volume of H2O-D2O (1: 1) isotopically mixed ice (solid solution) have been studied at the solid-phase amorphization of normal 1 h ice under compression at a temperature of 77 K and at the transition from high-density amorphous ice to low-density amorphous ice with subsequent successive crystallization to cubic (1 c) and hexagonal (1 h) ice at isobaric (0.05 GPa) heating. Comparison of the results with the respective data for H2O and D2O ices indicates that the observed concentration (in the isotopic composition) dependences of the elastic moduli and their derivatives for different phases of ice at isotopic hydrogen substitution in the H2O, H2O-D2O (1: 1), and D2O chain can be both monotonic and significantly nonmonotonic.

  10. Femtosecond laser-induced phase transformations in amorphous Cu{sub 77}Ni{sub 6}Sn{sub 10}P{sub 7} alloy

    SciTech Connect

    Zhang, Y.; Zou, G.; Wu, A.; Bai, H.; Liu, L.; Chen, N.; Zhou, Y.

    2015-01-14

    In this study, the femtosecond laser-induced crystallization of CuNiSnP amorphous ribbons was investigated by utilizing an amplified Ti:sapphire laser system. X-ray diffraction and scanning electronic microscope were applied to examine the phase and morphology changes of the amorphous ribbons. Micromachining without crystallization, surface patterning, and selective crystallization were successfully achieved by changing laser parameters. Obvious crystallization occurred under the condition that the laser fluence was smaller than the ablation threshold, indicating that the structural evolution of the material depends strongly on the laser parameters. Back cooling method was used to inhibit heat accumulation; a reversible transformation between the disordered amorphous and crystalline phases can be achieved by using this method.

  11. Amorphous rare earth magnet powders

    SciTech Connect

    Sellers, C.H.; Branagan, D.J.; Hyde, T.A.; Lewis, L.H.; Panchanathan, V.

    1996-08-01

    Gas atomization (GA) processing does not generally have a high enough cooling rate to produce the initial amorphous microstructure needed to obtain optimal magnetic properties in RE{sub 2}Fe{sub 14}B alloys. Phase separation and an underquenched microstructure result from detrimental {alpha}-Fe precipitation, and the resulting magnetic domain structure is very coarse. Additionally, there is a dramatic dependence of the magnetic properties on the cooling rate (and therefore the particle size) and the powders can be sensitive to environmental degradation. Alloy compositions designed just for GA (as opposed to melt spinning) are necessary to produce an amorphous structure that can be crystallized to result in a fine structure with magnetic properties which are independent of particle size. The addition of titanium and carbon to the melt has been found to change the solidification process sufficiently to result in an ``overquenched`` state in which most of the powder size fractions have an amorphous component. Crystallization with a brief heat treatment produces a structure which has improved magnetic properties, in part due to the ability to use compositions with higher Fe contents without {alpha}-Fe precipitation. Results from magnetometry, magnetic force microscopy, and x-ray analyses will be used to contrast the microstructure, domain structure, and magnetic properties of this new generation of amorphous powders with their multiphase predecessors.

  12. SANS study of phase separation in solid {sup 3}He-{sup 4}He

    SciTech Connect

    Koster, J.P.; Nagler, S.E.; Adams, E.D.; Wignall, G.D.

    1994-12-31

    Small angle neutron scattering has been used to study phase separation in a quantum alloy, solid {sup 3}He{sub x}-{sup 4}He{sub 1{minus}x}. The onset of phase separation is marked by a dramatic increase in the measured scattering. A simple interpretation of the results suggests that the late-stage phase separation kinetics are dominated by an increase in the concentration of {sup 3}He atoms in preexisting precipitate regions.

  13. Liquid crystal alignment with a molecular template of imprinted polymer layer during phase separation

    NASA Astrophysics Data System (ADS)

    Kim, Hak-Rin; Jung, Jong-Wook; Lee, You-Jin; Kim, Jae-Hoon

    2006-03-01

    We developed a liquid crystal (LC) alignment method using a molecular template of an imprinted polymer layer during polymerization-induced phase separation. Our results showed that the nematic ordering of LC is transferred to the polymer chain ordering during an anisotropic phase separation, which produces an anisotropic azimuthal surface anchoring. Using in-plane field treatment during phase separation, a twisted nematic cell is demonstrated.

  14. Phase separation of integral membrane proteins in Triton X-114 solution.

    PubMed

    Bordier, C

    1981-02-25

    A solution of the nonionic detergent Triton X-114 is homogeneous at 0 degrees C but separates in an aqueous phase and a detergent phase above 20 degrees C. The extent of this detergent phase separation increases with the temperature and is sensitive to the presence of other surfactants. The partition of proteins during phase separation in solutions of Triton X-114 is investigated. Hydrophilic proteins are found exclusively in the aqueous phase, and integral membrane proteins with an amphiphilic nature are recovered in the detergent phase. Triton X-114 is used to solubilize membranes and whole cells, and the soluble material is submitted to phase separation. Integral membrane proteins can thus be separated from hydrophilic proteins and identified as such in crude membrane or cellular detergent extracts.

  15. A Novel High-Density Phase and Amorphization of Nitrogen-Rich 1H-Tetrazole (CH2N4) under High Pressure

    PubMed Central

    Li, Wenbo; Huang, Xiaoli; Bao, Kuo; Zhao, Zhonglong; Huang, Yanping; Wang, Lu; Wu, Gang; Zhou, Bo; Duan, Defang; Li, Fangfei; Zhou, Qiang; Liu, Bingbing; Cui, Tian

    2017-01-01

    The high-pressure behaviors of nitrogen-rich 1H-tetrazole (CH2N4) have been investigated by in situ synchrotron X-ray diffraction (XRD) and Raman scattering up to 75 GPa. A first crystalline-to-crystalline phase transition is observed and identified above ~3 GPa with a large volume collapse (∼18% at 4.4 GPa) from phase I to phase II. The new phase II forms a dimer-like structure, belonging to P1 space group. Then, a crystalline-to-amorphous phase transition takes place over a large pressure range of 13.8 to 50 GPa, which is accompanied by an interphase region approaching paracrystalline state. When decompression from 75 GPa to ambient conditions, the final product keeps an irreversible amorphous state. Our ultraviolet (UV) absorption spectrum suggests the final product exhibits an increase in molecular conjugation. PMID:28218236

  16. A Novel High-Density Phase and Amorphization of Nitrogen-Rich 1H-Tetrazole (CH2N4) under High Pressure

    NASA Astrophysics Data System (ADS)

    Li, Wenbo; Huang, Xiaoli; Bao, Kuo; Zhao, Zhonglong; Huang, Yanping; Wang, Lu; Wu, Gang; Zhou, Bo; Duan, Defang; Li, Fangfei; Zhou, Qiang; Liu, Bingbing; Cui, Tian

    2017-02-01

    The high-pressure behaviors of nitrogen-rich 1H-tetrazole (CH2N4) have been investigated by in situ synchrotron X-ray diffraction (XRD) and Raman scattering up to 75 GPa. A first crystalline-to-crystalline phase transition is observed and identified above ~3 GPa with a large volume collapse (∼18% at 4.4 GPa) from phase I to phase II. The new phase II forms a dimer-like structure, belonging to P1 space group. Then, a crystalline-to-amorphous phase transition takes place over a large pressure range of 13.8 to 50 GPa, which is accompanied by an interphase region approaching paracrystalline state. When decompression from 75 GPa to ambient conditions, the final product keeps an irreversible amorphous state. Our ultraviolet (UV) absorption spectrum suggests the final product exhibits an increase in molecular conjugation.

  17. Modeling of the Structural State of Amorphous Phases of the Nano-Sized Al2O3 Produced by Different Synthesis Methods

    NASA Astrophysics Data System (ADS)

    Abzaev, U. A.; Syzrantsev, V. V.; Bardakhanov, S. P.

    2017-07-01

    The paper examines the structural state of the Al2O3 alloy nanopowders synthesized by different methods: electron beam evaporation, hydrolysis, and plasma-chemical method. X-ray structural analysis demonstrated that Al2O3 nanopowders synthesized by different methods are in X-ray amorphous and semi-amorphous states. These synthesis methods stimulate the creation of amorphous structures with different specific surfaces. The structural state of the Al2O3 alloy was studied by methods of X-ray structural analysis and simulation modeling. In order to identify the internal structure, modeling of the amorphous state of the elementary cell of the Al2O3 phase was performed within molecular dynamics. As a result of full-profile refinement of parameters of the model phases of Al2O3 nanopowders, complete structural information was identified for the synthesized Al2O3 alloys. It was shown from first principles that the cells of X-ray amorphous Al2O3 turned out to be highly stable. Researchers identified the parameters of elementary cells, spatial distribution of atoms, and node occupancy. It was shown that specific surface increases in the Al2O3 alloy nanopowders with the increase in bond energy of atoms in the cell.

  18. Phase behavior, intermolecular interaction, and solid state characterization of amorphous solid dispersion of Febuxostat.

    PubMed

    Kini, Ashwini; Patel, Sarsvatkumar B

    2017-02-01

    The aim of this work was to prepare and characterize the amorphous molecular dispersion of Febuxostat (FXT) using PVP K30, HPMC-AS, Soluplus®, and PVP VA64. The solid dispersions were prepared by solvent evaporation technique. Their physical properties were studied by differential scanning calorimetry, powder X-ray diffraction, Fourier transformation infrared spectroscopy, and compared to that of same physical mixtures. The success of physicochemical stability of the dispersions is often revealed as glass transition temperature (Tg) versus composition (w) dependencies. The shape of the Tg versus composition was mathematically modeled using the Gordon-Taylor equation, Couchman-Karasz equation, Brekner-Schneider-Cantow equation, and a three-parameter BCKV equation. In this work, different types of Tg patterns obtained for FXT-polymer binary mixtures are analyzed in terms of the above equations and relations between their prime fitting parameters are presented. The theoretical values and modeled parameters were compared using various results obtained by thermal analysis. The influence of important physicochemical phenomena and properties of the mixtures on the shape of the Tg versus composition patterns are also illustrated. The interaction between drug and polymers and the model parameters were analyzed, aiming to assess the state of mixing and intermolecular interactions.

  19. Amorphous to crystalline phase transition: Onset of pattern formation during ion erosion of Si(001)

    NASA Astrophysics Data System (ADS)

    Engler, Martin; Michely, Thomas

    2016-02-01

    The morphological evolution of Si(001) is investigated for normal incidence 2 keV Kr+ion irradiation under ultra-high vacuum conditions as a function of temperature and ion fluence through scanning tunneling microscopy and low energy electron diffraction. Under the conditions chosen, the selvage of Si(001) amorphizes below the critical temperature Tc of 670 K, while above it remains crystalline. Below Tc the sample remains flat, irrespective of the ion fluence. Above Tc, the crystalline sample displays for fixed ion fluence and as a function of sample temperature a pronounced roughness maximum at 700 K. Around this temperature, with increasing ion fluence a strong increase of roughness as well as coarsening are observed. Pyramidal pits and mounds develop, with facets formed by Si steps and narrow reconstructed terraces. Most exciting, with increasing ion fluence the pattern reorients from pits and mounds with edges along the <110 > directions to ridges and valleys rotated ≈45 ∘ to the <110 > directions.

  20. Observation of amorphous to crystalline phase transformation in Te substituted Sn-Sb-Se thin films

    SciTech Connect

    Chander, Ravi

    2015-05-15

    Thin films of Sn-Sb-Se-Te (8 ≤ x ≤ 14) chalcogenide system were prepared by thermal evaporation technique using melt quenched bulk samples. The as-prepared thin films were found amorphous as evidenced from X-ray diffraction studies. Resistivity measurement showed an exponential decrease with temperature upto critical temperature (transition temperature) beyond which a sharp decrease was observed and with further increase in temperature showed an exponential decrease in resistivity with different activation energy. The transition temperature showed a decreasing trend with tellurium content in the sample. The resistivity measurement during cooling run showed no abrupt change in resistivity. The resistivity measurements of annealed films did not show any abrupt change revealing the structural transformation occurring in the material. The transition width showed an increase with tellurium content in the sample. The resistivity ratio showed two order of magnitude improvements for sample with higher tellurium content. The observed transition temperature in this system was found quite less than already commercialized Ge-Sb-Te system for optical and electronic memories.

  1. Unusual Electro-Optic Kerr Response in a Self-Stabilized Amorphous Blue Phase with Nanoscale Smectic Clusters.

    PubMed

    Le, Khoa V; Hafuri, Miho; Ocak, Hale; Bilgin-Eran, Belkız; Tschierske, Carsten; Sasaki, Takeo; Araoka, Fumito

    2016-05-18

    We investigated the electro-optic response in the "foggy" amorphous blue phase (BPIII) as well as in the isotropic phase. To the best of our knowledge, such a study has not yet been performed due to the very limited thermal range of BPIII. In this study, we used a single-component chiral bent-core liquid crystal with a self-stabilized BPIII, which is stable over a wide temperature range. The results show that the response time is on the order of hundreds of microseconds in the isotropic phase and increases to 1-2 ms in the BPIII (at TI-BP -T <1), then drastically increases up to a few tens of milliseconds upon further cooling in BPIII. Such an unusual behavior was explained on the basis of the high rotational viscosity and/or the existence of nanoscale smectic (Sm) clusters. The Kerr constant was also measured and found to be ∼500 pm V(-2) , which is the largest among bent-core BP systems reported so far and comparable with that of polymer-stabilized BPs.

  2. Trehalose amorphization and recrystallization.

    PubMed

    Sussich, Fabiana; Cesàro, Attilio

    2008-10-13

    The stability of the amorphous trehalose prepared by using several procedures is presented and discussed. Amorphization is shown to occur by melting (T(m)=215 degrees C) or milling (room temperature) the crystalline anhydrous form TRE-beta. Fast dehydration of the di-hydrate crystalline polymorph, TRE-h, also produces an amorphous phase. Other dehydration procedures of TRE-h, such as microwave treatment, supercritical extraction or gentle heating at low scan rates, give variable fractions of the polymorph TRE-alpha, that undergo amorphization upon melting (at lower temperature, T(m)=130 degrees C). Additional procedures for amorphization, such as freeze-drying, spray-drying or evaporation of trehalose solutions, are discussed. All these procedures are classified depending on the capability of the undercooled liquid phase to undergo cold crystallization upon heating the glassy state at temperatures above the glass transition temperature (T(g)=120 degrees C). The recrystallizable amorphous phase is invariably obtained by the melt of the polymorph TRE-alpha, while other procedures always give an amorphous phase that is unable to crystallize above T(g). The existence of two different categories is analyzed in terms of the transformation paths and the hypothesis that the systems may exhibit different molecular mobilities.

  3. Secondary Structure-Induced Micro- and Macro-Phase Separation in Polypeptide Diblock, Triblock and Star-Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sanchez-Ferrer, Antoni; Mezzenga, Raffaele

    2010-03-01

    Self-organized polypeptide block copolymers are of great interest due to their potential uses as materials for nano-devices and bio-engineering. In order to explore the effect of block copolymer topologies on their structures, a series of di-, tri- and tetra-block copolymers has been synthesized. A coil-like soft block based on poly(propylene oxide) chemistry was chosen due to its low glass transition temperature, amorphous nature and immiscibility with biological systems. On the other hand, rod-like block polypeptide based on poly(L-glutamic acid γ-benzyl ester) was selected and grown from the coil soft macroinitiator by ring opening polymerization. Because of the mono-, bi-, or tri-functionality of the coiled blocks, linear di-block, tri-block and star-like tetra-block copolymers could be successfully synthesized. The resulting materials show micro-phase separated liquid-crystalline morphologies, in which the architecture or connectivity of the blocks, the molecular weight of the coil segment, the volume fraction and the secondary structure of the polypeptide blocks all contribute to their micro-phase separated features. These materials can be seen as model reference systems towards the design of biocompatible scaffolds and artificial muscles.

  4. On separability of A-phases during the cyclic alternating pattern.

    PubMed

    Mendez, M O; Alba, A; Chouvarda, I; Milioli, G; Grassi, A; Terzano, M G; Parrino, L

    2014-01-01

    A statistical analysis of the separability of EEG A-phases, with respect to basal activity, is presented in this study. A-phases are short central events that build up the Cyclic Alternating Pattern (CAP) during sleep. The CAP is a brain phenomenon which is thought to be related to the construction, destruction and instability of sleep stages dynamics. From the EEG signals, segments obtained around the onset and offset of the A-phases were used to evaluate the separability between A-phases and basal sleep stage oscillations. In addition, a classifier was trained to separate the different A-phase types (A1, A2 and A3). Temporal, energy and complexity measures were used as descriptors for the classifier. The results show a percentage of separation between onset and preceding basal oscillations higher than 85 % for all A-phases types. For Offset separation from following baseline, the accuracy is higher than 80 % but specificity is around 75%. Concerning to A-phase type separation, A1-phase and A3-phase are well separated with accuracy higher than 80, while A1 and A2-phases show a separation lower than 50%. These results encourage the design of automatic classifiers for Onset detection and for separating among A-phases type A1 and A3. On the other hand, the A-phase Offsets present a smooth transition towards the basal sleep stage oscillations, and A2-phases are very similar to A1-phases, suggesting that a high uncertainty may exist during CAP annotation.

  5. Formation of binary phase gratings in photopolymer-liquid crystal composites by a surface-controlled anisotropic phase separation

    SciTech Connect

    Park, Jae-Hong; Khoo, Iam Choon; Yu, Chang-Jae; Jung, Min-Sik; Lee, Sin-Doo

    2005-01-10

    We report on formation of binary phase gratings in photopolymer-liquid crystal (PLC) composites using a surface-controlled phase separation method. The binary nature of the PLC phase gratings is produced by employing a single step photo-ablation through an amplitude photomask which precisely controls the interfacial interactions between the LC and the photopolymer on the alignment layer. A subsequent illumination of the ultraviolet light onto the whole PLC promotes an anisotropic phase separation resulting in the formation of distinct binary patterns for the PLC structure. The electrically tunable diffraction properties of the binary phase gratings are presented.

  6. Analysis of a Rapidly Solidified High-Phosphorus Austenitic Steel Containing an Amorphous Phase.

    DTIC Science & Technology

    1981-12-01

    of hardening phases is limited by the requirement for a moderate alloy carbon content (e,0.3 wt.".,C) to ensure a high work hardening effect from the...transformation behavior, but fracture duc- tility and fabricability were limited hy the severe phosphorus segregation as- sociated with conventional... ingot metallurgy [3]. In the first phase of an in- vestigation of the effect of rapid solidification processing on this alloy, some unusual

  7. Lateral phase separation in polymer-blend thin films: surface bifurcation.

    PubMed

    Coveney, Sam; Clarke, Nigel

    2014-06-01

    We use simulations of a binary polymer blend confined between selectively attracting walls to identify and explain the mechanism of lateral phase separation via a transient wetting layer. We first show that equilibrium phases in the film are described by one-dimensional phase equilibria in the vertical (depth) dimension, and demonstrate that effective boundary conditions imposed by the film walls pin the film profile at the walls. We then show that, prior to lateral phase separation, distortion of the interface in a transient wetting layer is coupled to lateral phase separation at the walls. Using Hamiltonian phase portraits, we explain a "surface bifurcation mechanism" whereby the volume fraction at the walls evolves and controls the dynamics of the phase separation. We suggest how solvent evaporation may assist our mechanism.

  8. Detection of various phases in liquids from the hypersound velocity and damping near closed phase-separation regions of solutions

    NASA Astrophysics Data System (ADS)

    Kovalenko, K. V.; Krivokhizha, S. V.; Chaban, I. A.; Chaikov, L. L.

    2008-02-01

    Theoretical analysis revealed that experimental results obtained in our studies on hypersound propagation in a guaiacol-glycerol solution in the vicinity of the closed phase-separation region, double critical point, and special point, as well as the origin of these regions, can be explained by the presence of two different phases (I and II) of the solution with phase-transition temperature T 0. Temperature T 0 coincides with the temperature at the center of closed phase-separation regions, as well as with the double critical point and with the special point. In (Frenkel) phase I, molecules are in potential wells whose depth exceeds the thermal energy of a molecule, while thermal energy in (gaslike) phase II is higher than the potential well depth. At the lower critical point, the thermodynamic potential of phase I is equal to the thermodynamic potential of the phase-separated solution. At the upper critical point, the thermodynamic potential of phase II is equal to the thermodynamic potential of the phase-separated solution. The observed broad dome of the hypersound absorption coefficient near T 0 can be explained by the contribution associated with fluctuations of the order parameter corresponding to the transition from phase I to phase II. The difference in the temperature coefficients of hypersound velocity on different sides of T 0 and some other effects are also explained.

  9. Two-phase, passive separator-and-filter assembly

    NASA Technical Reports Server (NTRS)

    Erickson, A. C.; Porter, F. J., Jr.

    1974-01-01

    Assembly separates liquid from gas by passive hydrophilic/hydrophobic material approach. Apparatus is comprised of porous glass hydrophilic tubes. Quantity, lateral size, and pore size of glass tubes are determined by particular design requirements with regard to water rate, water quality contamination level, application endurance life, and operating differential pressure level.

  10. Separations/pretreatment considerations for Hanford privatization phase 2

    SciTech Connect

    Hunt, R.D.; McGinnis, C.P.; Welch, T.D.

    1998-05-01

    The Tank Focus Area is funded to develop, demonstrate, and deploy technologies that will assist in the treatment and closure of its nuclear waste tanks. Pretreatment technologies developed to support the privatization effort by the Department of Energy are reviewed. Advancements in evaporation, solid-liquid separation, sludge treatment, solids controls, sodium management, and radionuclide removal are considered.

  11. 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.

  12. Phase separation in fluids exposed to spatially periodic external fields.

    PubMed

    Vink, R L C; Archer, A J

    2012-03-01

    When a fluid is confined within a spatially periodic external field, the liquid-vapor transition is replaced by a different transition called laser-induced condensation (LIC) [Götze et al., Mol. Phys. 101, 1651 (2003)]. In d=3 dimensions, the periodic field induces an additional phase, characterized by large density modulations along the field direction. At the triple point, all three phases (modulated, vapor, and liquid) coexist. At temperatures slightly above the triple point and for low (high) values of the chemical potential, two-phase coexistence between the modulated phase and the vapor (liquid) is observed; by increasing the temperature further, both coexistence regions terminate in critical points. In this paper, we reconsider LIC using the Ising model to resolve a number of open issues. To be specific, we (1) determine the universality class of the LIC critical points and elucidate the nature of the correlations along the field direction, (2) present a mean-field analysis to show how the LIC phase diagram changes as a function of the field wavelength and amplitude, (3) develop a simulation method by which the extremely low tension of the interface between modulated and vapor or liquid phase can be measured, (4) present a finite-size scaling analysis to accurately extract the LIC triple point from finite-size simulation data, and (5) consider the fate of LIC in d=2 dimensions.

  13. Identification of phase separation in solid dispersions of itraconazole and Eudragit E100 using microthermal analysis.

    PubMed

    Six, Karel; Murphy, John; Weuts, Ilse; Craig, Duncan Q M; Verreck, Geert; Peeters, Jef; Brewster, Marcus; Van den Mooter, Guy

    2003-01-01

    To evaluate the phase separation in itraconazole/Eudragit E100 solid dispersions prepared by hot-stage extrusion. Extrudates were prepared using a corotating twin-screw extruder at 180 degrees C. Micro-TA was used to evaluate the phase separation, where the AFM mode is used to visualize the different phases and local thermal analysis (LTA) to characterize the different phases Itraconazole formed a homogeneous mixture with Eudragit E100 with drug concentrations up to approximately 20%. Above this concentration, phase separation was observed. MTDSC revealed two Tgs and the mesophase of free glassy itraconazole. Performing micro-TA on the surface of these dispersions indicated an increase in sample roughness in the z-axis piezo signal, which could be an indication of free glassy itraconazole. However, thermal conductivity did not reveal differences between separate phases. Performing LTA, where only a small area (20 x 20 microm) is heated, showed two separate and mixed phases of itraconazole and Eudragit E100. Tip penetration in itraconazole and Eudragit E100 occurred at 332K and 383K respectively. The difference in tip penetration was explained in terms of the difference in fragility. Micro-TA makes it possible to characterize separate phases of itraconazole and Eudragit E100, thereby confirming the MTDSC results on phase separation.

  14. Demixing kinetics of phase separated polymer solutions in microgravity. [cell separation

    NASA Technical Reports Server (NTRS)

    Brooks, D. E.; Bamberger, S. B.; Harris, J. M.; Vanalstine, J.; Snyder, R. S.

    1987-01-01

    In preparation for performing cell partitioning in space the demixing behavior of aqueous two phase systems containing dextran and poly(ethylene glycol) in microgravity was modeled with an isopycnic system and studied on aircraft flights and on STS 51-D. In all types of experiments demixing occurs, eventually producing one phase localized around the wall of the container with the other internalized within it. The demixing kinetics were analyzed in each case.

  15. Synthesis methods and character of iron-based mixed-anion superconductor with suppression of the amorphous FeAs impurity phase

    NASA Astrophysics Data System (ADS)

    Fujioka, Masaya; Ozaki, Toshinori; Okazaki, Hiroyuki; Saleem, Denholme; Deguchi, Keita; Demura, Satoshi; Hara, Hiroshi; Watanabe, Tohru; Takeya, Hiroyuki; Yamaguchi, Takahide; Kumakura, Hiroaki; Takano, Yoshihiko

    2013-03-01

    To obtain the high superconducting properties of polycrystalline SmFeAsO1-xFx, we investigated the following three synthesis methods: a high pressure synthesis, a low temperature synthesis with gradual cooling and a metal added synthesis. Generally, polycrystalline SmFeAsO1-xFx is composed of superconducting grains and a little amorphous FeAs compounds. These areas randomly co-exist and amorphous areas are located between the superconducting grains. Therefore, we suggest that the superconducting current is prevented by the amorphous areas. In fact, although the single crystal of this material shows a large critical current density of 106 A/cm2, polycrystalline SmFeAsO1-xFx shows a significant depression of critical current density due to this grain boundary blocking effect. To obtain a high global critical current density, it is important to investigate how to remove the amorphous FeAs. It is found that the impurity phase of amorphous FeAs is decreased by using the above three synthesis methods.

  16. Derivatized vancomycin stationary phases for LC chiral separations.

    PubMed

    Berthod, A; Nair, U B; Bagwill, C; Armstrong, D W

    1996-10-01

    In this work, synthetic and natural chiral selectors were combined to form two different chiral stationary phases (CSPs). These were made by bonding R- or S-(1-naphthylethyl) carbamate (R-NEC or S-NEC)-derivatized vancomycin molecules to a silica gel support. The two CSPs were evaluated using a set of 60 enantiomeric pairs. The results were compared to the ones obtained with the commercial underivatized vancomycin CSP. Three Chromatographic modes were used: (i) the normal-phase mode using a nonpolar mobile phase with different ratios of hexane and ethanol; (ii) the reversed-phase mode with hydro-organic mobile phases; and (iii) the polar aprotic organic mode with nonaqueous acetonitrile plus small amounts of methanol and an acid and/or base to control retention and selectivity. It is shown that the polarity of the underivatized vancomycin phase is higher than that of the two R- and S-NEC-derivatized CSPs. In the pH range 4-7, there is no ionization change of the chiral selector for the three CSPs. 43% of the studied compounds were resolved by the NEC-derivatized phases when they could not be resolved by the vancomycin CSP. However, the enantiorecognition for 12% of the compounds on the native vancomycin CSP was lost upon NEC derivatization. 45% of the studied compounds were resolved by the NEC-derivatized and native CSPs. The NEC derivatization procedure may block some useful active sites on the vancomycin molecule. Also, the R- and S-NEC moieties are chiral themselves and can contribute additional interaction sites not available on the native vancomycin molecule.

  17. 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

  18. Phase separation in lipid bilayers triggered by low pH

    SciTech Connect

    Suresh, Swetha; Edwardson, J. Michael

    2010-09-03

    Research highlights: {yields} Lipid bilayers have been imaged by atomic force microscopy (AFM). {yields} At pH 5 phase separation occurs in lipid bilayers containing mixed acyl chains. {yields} Phase separation does not occur when lipids have only unsaturated chains. {yields} Phase separation might drive protein clustering during endocytosis. -- Abstract: Endocytosis involves the capture of membrane from the cell surface in the form of vesicles, which become rapidly acidified to about pH 5. Here we show using atomic force microscopy (AFM) imaging that this degree of acidification triggers phase separation in lipid bilayers containing mixed acyl chains (e.g. palmitoyl/oleoyl) or complex mixtures (e.g. total brain extract) but not in bilayers containing only lipids with unsaturated chains (e.g. dioleoyl). Since mixed-chain lipids are major constituents of the outer leaflet of the plasma membrane, the type of phase separation reported here might support protein clustering and signaling during endocytosis.

  19. Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

    PubMed Central

    Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

    2017-01-01

    Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm−2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec−1. Moreover, we achieve 10 mA cm−2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2. PMID:28485395

  20. Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

    NASA Astrophysics Data System (ADS)

    Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

    2017-05-01

    Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm-2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec-1. Moreover, we achieve 10 mA cm-2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2.

  1. Ultrafast crystalline-to-amorphous phase transition in Ge{sub 2}Sb{sub 2}Te{sub 5} chalcogenide alloy thin film using single-shot imaging spectroscopy

    SciTech Connect

    Takeda, Jun Oba, Wataru; Minami, Yasuo; Katayama, Ikufumi; Saiki, Toshiharu

    2014-06-30

    We have observed an irreversible ultrafast crystalline-to-amorphous phase transition in Ge{sub 2}Sb{sub 2}Te{sub 5} chalcogenide alloy thin film using broadband single-shot imaging spectroscopy. The absorbance change that accompanied the ultrafast amorphization was measured via single-shot detection even for laser fluences above the critical value, where a permanent amorphized mark was formed. The observed rise time to reach the amorphization was found to be ∼130–200 fs, which was in good agreement with the half period of the A{sub 1} phonon frequency in the octahedral GeTe{sub 6} structure. This result strongly suggests that the ultrafast amorphization can be attributed to the rearrangement of Ge atoms from an octahedral structure to a tetrahedral structure. Finally, based on the dependence of the absorbance change on the laser fluence, the stability of the photoinduced amorphous phase is discussed.

  2. Pinning of phase separation of aqueous solution of hydroxypropylmethylcellulose by gelation

    NASA Astrophysics Data System (ADS)

    Kita, Rio; Kaku, Takeshi; Kubota, Kenji; Dobashi, Toshiaki

    1999-08-01

    Opalescence of the aqueous solution of hydroxypropylmethylcellulose (HPMC) induced by heating has been studied in terms of the phase diagram and the phase separation dynamics. The cloud point curve and the sol-to-gel transition curve intersected with each other at about 55 °C. Just above the cloud-point curve at which the spinodal curve has its minimum, a ring-like scattering pattern appeared corresponding to the spinodal decomposition. Temporal growth of the scattering function in the course of phase separation was studied by a time-resolved light scattering technique. The gelation pinned the phase separation (spinodal decomposition) of the aqueous HPMC solution.

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

    PubMed

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

    2011-12-21

    We investigated the phase separation phenomena in dilute surfactant pentaethylene glycol monodedecyl ether (C(12)E(5)) 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.

  4. Initial stage of the phase separation, observed with fluorescent excitation transfer technique

    NASA Astrophysics Data System (ADS)

    Goun, Alexei; Fayer, Michael

    2010-03-01

    The use of the fluorescent resonant excitation transfer (FRET) to study the phase transition kinetics is demonstrated. The laser temperature jump is applied to the water/2,6-lutidine mixture and causes the demixing of the mixture components. Coumarin 480 and hydroxypyrene laser dyes form excitation transfer pair once they are in the uniform phase of the mixture. Due to the differential solubility of these dyes in the componens of the mixture, the excitation transfer ceases once the phase separation occurs. The increase of the donor fluorescence indicates the extent of the phase separation. The spatial resolution of the method is determined by the Forster distance of the excitation transfer pair, and in this case is equal to 3 nm. The phase separation is completed within 1 microsecond. The rising edge of the fluorescence is consistent with polynomial growth of the phase separated domains, and not with Cahn-Hilliard fixed length instability.

  5. Controllable Phase Separation by Boc-Modified Lipophilic Acid as a Multifunctional Extractant

    NASA Astrophysics Data System (ADS)

    Tao, Kai; Adler-Abramovich, Lihi; Gazit, Ehud

    2015-12-01

    While phase separation of immiscible liquid-liquid systems has become increasingly significant in diverse areas, the irreversible nature limits their further application in controllable extraction-concentration or capture-release fields. There is a need for the development of simple, efficient and reversible methods for numerous research and industrial extraction and separation applications. We envisioned Boc-modified lipophilic acids as a simple model for such use based on the studies of the multi-phase transitions of Boc-modified supramolecular polymeric systems. Here, we demonstrate that in the presence of Boc-7-aminoheptanoic acid (Boc-7), phase separation occurs in mixtures of miscible organic solvent and water. The separation behavior was confirmed by differential colorimetric development in aqueous and organic phases using methyl orange staining assays. Component substitution experiments verified that the phase separation results from the subtle balance between the aggregation and the solvation forces of Boc-7, and is reversible by adjusting the solution pH. Owing to the intrinsic hydrophobic properties of the organic phase and the hydrogen bonding-forming ability of the carboxyl group of Boc-7, the phase separation system captures and releases Sudan Red, fluorescein, and streptavidin in a controllable manner. Consequently, a reversible and simple phase separation system can be designed as a multifunctional extractant.

  6. Controllable Phase Separation by Boc-Modified Lipophilic Acid as a Multifunctional Extractant

    PubMed Central

    Tao, Kai; Adler-Abramovich, Lihi; Gazit, Ehud

    2015-01-01

    While phase separation of immiscible liquid-liquid systems has become increasingly significant in diverse areas, the irreversible nature limits their further application in controllable extraction-concentration or capture-release fields. There is a need for the development of simple, efficient and reversible methods for numerous research and industrial extraction and separation applications. We envisioned Boc-modified lipophilic acids as a simple model for such use based on the studies of the multi-phase transitions of Boc-modified supramolecular polymeric systems. Here, we demonstrate that in the presence of Boc-7-aminoheptanoic acid (Boc-7), phase separation occurs in mixtures of miscible organic solvent and water. The separation behavior was confirmed by differential colorimetric development in aqueous and organic phases using methyl orange staining assays. Component substitution experiments verified that the phase separation results from the subtle balance between the aggregation and the solvation forces of Boc-7, and is reversible by adjusting the solution pH. Owing to the intrinsic hydrophobic properties of the organic phase and the hydrogen bonding-forming ability of the carboxyl group of Boc-7, the phase separation system captures and releases Sudan Red, fluorescein, and streptavidin in a controllable manner. Consequently, a reversible and simple phase separation system can be designed as a multifunctional extractant. PMID:26627307

  7. Phase separation in garnet solid solutions and its effect on optical properties.

    PubMed

    Kaveh, Shakiba; Tremblay, Clément P; Norhashim, Nurhakimah; Curry, Richard J; Cheetham, Anthony K

    2013-11-26

    Phase behavior is studied in erbium-doped Y3 Al5 O12 (YAG) garnets synthesized by solid-state reactions. High resolution synchrotron XRD and SEM-EDX studies reveal phase separation at an erbium content between 8 and 50 at%, depending upon the processing conditions. Similar results are found in closely-related garnet systems. The phase separation has a striking effect on the optical properties of YAG:Er(3+) .

  8. Phase conversion and interface growth in phase-separated 3He - 4He liquid mixtures

    NASA Astrophysics Data System (ADS)

    Abe, Haruka; Satoh, Takeo; Burmistrov, Serguei N.

    2005-10-01

    We have developed a method for measuring the transmission coefficient of a sound propagating through the interface in phase-separated He3-He4 liquid mixtures. The method and the results are described with discussions by examining the phase-conversion process of He3 quasiparticles driven to flow across the interface. From the data, we have determined the kinetic growth coefficient of the interface, ξ(T,P,ω) , as a function of temperature, pressure, and frequency. The temperature range of the present investigation is about 2-100mK at the pressure mainly around 1bar with sound frequency 9.64, 14.4, and 32.4MHz . The main specific features observed for the kinetic growth coefficient are, as follows: (i) there is a maximum at some temperature Tm(ω) depending on the frequency, (ii) above Tm(ω) , ξ decreases with the increase of temperature as ∝ω5/2T-3 , and (iii) below Tm(ω) , ξ becomes frequency independent and diminishes as a cube of temperature, T3 .

  9. 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.

  10. Effects of attractive colloids on the phase separation behaviors of binary polymer blends

    NASA Astrophysics Data System (ADS)

    Zhang, Xinghua; Chen, Yunlin; Qu, Lijian; Yan, Dadong

    2013-08-01

    The attractive colloids are added as fillers to control the phase behaviors of binary polymer blends. Because the colloids attract both components in the blends, aggregates are formed by the colloids coated with both kinds of polymer brushes. The aggregation results in two contradictory effects on the phase separation. First, the formation of aggregate decreases the translational entropy, which promotes the phase separation. On the other hand, the phase separation causes the extra free energy penalty due to the stretch of the chains attaching on the colloids, which prevents the phase separation. Furthermore, as the concentration or adsorbability of the colloids increases the local fluctuations within the aggregates become important. This results in a transition from the macro-phase separation to the micro-phase separation and the existence of the Lifshitz point. All of these effects lead to diverse phase behaviors in the polymer nanocomposites system. In present work, these behaviors are studied theoretically by the random phase approximation in a model system.

  11. Nanosecond in situ transmission electron microscope studies of the reversible Ge{sub 2}Sb{sub 2}Te{sub 5} crystalline <==> amorphous phase transformation

    SciTech Connect

    Santala, M. K.; Reed, B. W.; LaGrange, T.; Campbell, G. H.; Browning, N. D.; Topuria, T.; Raoux, S.; Meister, S.; Cui, Y.

    2012-01-15

    Chalcogenide-based phase-change materials have wide use in optical recording media and are growing in importance for use in non-volatile electronic memory. For both applications, rapid switching between the amorphous and crystalline phases is necessary, and understanding the changes during rapidly driven phase transitions is of scientific and technological significance. Laser-induced crystallization and amorphization occur rapidly and changes in atomic structure, microstructure, and temperature are difficult to observe experimentally and determine computationally. We have used nanosecond-scale time-resolved diffraction with intense electron pulses to study Ge{sub 2}Sb{sub 2}Te{sub 5} during laser crystallization. Using a unique and unconventional specimen geometry, cycling between the amorphous and crystalline phases was achieved, enabling in situ transmission electron microscope (TEM) study of both microstructural and crystallographic changes caused by repeated switching. Finite element analysis was used to simulate interactions of the laser with the nano-structured specimens and to model the rapidly changing specimen temperature. Such time-resolved experimental methods combined with simulation of experimentally inaccessible physical characteristics will be fundamental to advancing the understanding of rapidly driven phase transformations.

  12. Distribution of Local Open-Circuit Voltage on Amorphous and Nanocrystalline Mixed-Phase Si:H and SiGe:H Solar Cells: Preprint

    SciTech Connect

    Jiang, C.-S.; Moutinho, H. R.; Al-Jassim, M. M.; Kazmerski, L. L.; Yan, B.; Owens, J. M.; Yang, J.; Guha, S.

    2006-05-01

    Local open-circuit voltage (Voc) distributions on amorphous and nanocrystalline mixed-phase silicon solar cells were measured using a scanning Kelvin probe microscope (SKPM) on the p layer of an n-i-p structure without the top ITO contact. During the measurement, the sample was illuminated with a laser beam that was used for the atomic force microscopy (AFM). Therefore, the surface potential measured by SKPM is the sum of the local Voc and the difference in workfunction between the p layer and the AFM tip. Comparing the SKPM and AFM images, we find that nanocrystallites aggregate in the amorphous matrix with an aggregation size of {approx}0.5 ..mu..m in diameter, where many nanometer-size grains are clustered. The Voc distribution shows valleys in the nanocrystalline aggregation area. The transition from low to high Voc regions is a gradual change within a distance of about 1 ..mu..m. The minimum Voc value in the nanocrystalline clusters in the mixed-phase region is larger than the Voc of a nc-Si:H single-phase solar cell. These results could be due to lateral photo-charge redistribution between the two phases. We have also carried out local Voc measurements on mixed-phase SiGe:H alloy solar cells. The magnitudes of Voc in the amorphous and nanocrystalline regions are consistent with the J-V measurements.

  13. The use of coarse, separable, condensed-phase organic carbon particles to characterize desorption resistance of polycyclic aromatic hydrocarbons in contaminated sediments

    SciTech Connect

    Chai, Y.Z.; Kochetkov, A.; Reible, D.D.

    2007-07-15

    Physical separations were employed to characterize the source of desorption-resistant behavior for polycyclic aromatic hydrocarbons (PAHs) in laboratory- and field-contaminated sediments. Size and density separation of laboratory-contaminated sediments did not effectively separate the amorphous-phase (volatile) and condensed-phase (nonvolatile) organic carbon as measured by thermal oxidation at 375 {sup o}C. These separations also did not result in sediment fractions with significantly different desorption characteristics as measured by apparent partition coefficients. Coarse particles from a field-contaminated sediment from Utica Harbor (UH; Utica, NY, USA), however, could be directly separated into sandy fractions and organic fractions that were composed of woody organic matter, charcoal or charred vegetative matter, and coal-like and coal-cinder particles. Chemical analysis showed that coal-like (glassy, nonporous) and coal-cinder (porous, sintered) particles exhibited very high PAH concentrations and high apparent partition coefficients. These particles also exhibited significantly higher condensed-phase (nonvolatile) organic carbon contents as defined by thermal oxidation at 375{sup o}C. The apparent partition coefficients of PAHs in the coal-cinder particles were a good indication of the apparent partition coefficients in the desorption-resistant fraction of UH sediment, indicating that the coarse particles provided a reasonable characterization of the desorption-resistance phenomena in these sediments even though the coarse fractions represented less than 25% of the organic carbon in the whole sediment.

  14. Plasma phase separation in bismuth and antimony chalcogenide crystals

    NASA Astrophysics Data System (ADS)

    Netesova, Nadezhda P.

    2017-05-01

    Oscillation parameters of narrow band layered crystals of bismuth selenide and telluride and antimony telluride for one and two oscillations are calculated. The electron oscillation crystal model equations of real epsilonr and imaginary epsilonι, ω epsilonι components of dielectric function, electronic losses L, ωL are given, special points of the optical functions epsilonr, epsilonι, ω epsilonι, L, ωL for boundary frequencies ω are probed. Ratios of energy balance of `sublattices on the basis of oscillation electronic model are revealed. It is concluded that these crystals at high hydrostatic pressures and low temperatures are turned into superconductors. In high-temperature superconductors spontaneous division into two phases: superconducting and isolating was revealed. Stratification on two phases in superconducting crystals has been confirmed experimentally: neutron graphic, neutron spectral and spectral researches, an electronic and nuclear paramagnetic resonance.

  15. Phase Separation in Polyurethanes - A Deuterium NMR Study.

    DTIC Science & Technology

    1985-02-18

    from the diphenylmethane diisocyanate (MDI) or the soft segment polyol residues. The deuteriunm NMR spectra’ 9 for these four samples are shown in...other decays more slowly and is assigned to the polyester soft segments. With proton spin diffusion as an experimental probe, Assink and Wilkes3 4 35...evaluated phase mixing in a series of MDI- polyester polyurethanes. Their data require the presence of both short and long range degrees of mixing

  16. Dissipative particle dynamics study of phase separation in binary fluid mixtures in periodic and confined domains.

    PubMed

    Gidituri, Harinadha; Anand, D Vijay; Vedantam, Srikanth; Panchagnula, Mahesh V

    2017-08-21

    We investigate the phase separation behavior of binary mixtures in two-dimensional periodic and confined domains using dissipative particle dynamics. Two canonical problems of fluid mechanics are considered for the confined domains: square cavity with no-slip walls and lid-driven cavity with one driven wall. The dynamics is studied for both weakly and strongly separating mixtures and different area fractions. The phase separation process is analyzed using the structure factor and the total interface length. The dynamics of phase separation in the square cavity and lid-driven cavity are observed to be significantly slower when compared to the dynamics in the periodic domain. The presence of the no-slip walls and the inertial effects significantly influences the separation dynamics. Finally, we show that the growth exponent for the strongly separating case is invariant to changes in the inter-species repulsion parameter.

  17. Dissipative particle dynamics study of phase separation in binary fluid mixtures in periodic and confined domains

    NASA Astrophysics Data System (ADS)

    Gidituri, Harinadha; Anand, D. Vijay; Vedantam, Srikanth; Panchagnula, Mahesh V.

    2017-08-01

    We investigate the phase separation behavior of binary mixtures in two-dimensional periodic and confined domains using dissipative particle dynamics. Two canonical problems of fluid mechanics are considered for the confined domains: square cavity with no-slip walls and lid-driven cavity with one driven wall. The dynamics is studied for both weakly and strongly separating mixtures and different area fractions. The phase separation process is analyzed using the structure factor and the total interface length. The dynamics of phase separation in the square cavity and lid-driven cavity are observed to be significantly slower when compared to the dynamics in the periodic domain. The presence of the no-slip walls and the inertial effects significantly influences the separation dynamics. Finally, we show that the growth exponent for the strongly separating case is invariant to changes in the inter-species repulsion parameter.

  18. In situ imaging and height reconstruction of phase separation processes in polymer blends during spin coating.

    PubMed

    Ebbens, Stephen; Hodgkinson, Richard; Parnell, Andrew J; Dunbar, Alan; Martin, Simon J; Topham, Paul D; Clarke, Nigel; Howse, Jonathan R

    2011-06-28

    Spin coating polymer blend thin films provides a method to produce multiphase functional layers of high uniformity covering large surface areas. Applications for such layers include photovoltaics and light-emitting diodes where performance relies upon the nanoscale phase separation morphology of the spun film. Furthermore, at micrometer scales, phase separation provides a route to produce self-organized structures for templating applications. Understanding the factors that determine the final phase-separated morphology in these systems is consequently an important goal. However, it has to date proved problematic to fully test theoretical models for phase separation during spin coating, due to the high spin speeds, which has limited the spatial resolution of experimental data obtained during the coating process. Without this fundamental understanding, production of optimized micro- and nanoscale structures is hampered. Here, we have employed synchronized stroboscopic illumination together with the high light gathering sensitivity of an electron-multiplying charge-coupled device camera to optically observe structure evolution in such blends during spin coating. Furthermore the use of monochromatic illumination has allowed interference reconstruction of three-dimensional topographies of the spin-coated film as it dries and phase separates with nanometer precision. We have used this new method to directly observe the phase separation process during spinning for a polymer blend (PS-PI) for the first time, providing new insights into the spin-coating process and opening up a route to understand and control phase separation structures.

  19. Thermophysical properties of fluorinated acrylate homopolymers: Mixing and phase separation

    NASA Astrophysics Data System (ADS)

    Roussel, F.; Saidi, S.; Guittard, F.; Geribaldi, S.

    2002-06-01

    The thermophysical properties of fluorinated acrylate homopolymers are investigated by differential scanning calorimetry (DSC) and optical microscopy and discussed in terms of relative lengths of the fluorinated chain and the hydrocarbon spacer between the acrylate moiety and the fluorinated chain. These compounds exhibit an intrinsic microphase-separation (Isotropic+Isotropic morphology) occurring between the fluorinated chains and the acrylate polymer backbone. It is shown that the enthalpy of mixing is a function of the length of the lateral fluorocarbon chains. The thermophysical behaviour of these materials may be regarded as demixed systems exhibiting an Upper Critical Solution Temperature. The photopolymerization process of one of the monomer is studied by isothermal photocalorimetry. High acrylate double-bond conversion and fast curing rates were obtained thus demonstrating the promising use of these materials for coating and film processing applications using UV-curing techniques.

  20. Role of Inelastic Electron–Phonon Scattering in Electron Transport through Ultra-Scaled Amorphous Phase Change Material Nanostructures

    SciTech Connect

    Liu, Jie; Xu, Xu; Anantram, M.P.

    2014-09-01

    The electron transport through ultra-scaled amorphous phase change material (PCM) GeTe is investigated by using ab initio molecular dynamics, density functional theory, and non-equilibrium Green’s function, and the inelastic electron–phonon scattering is accounted for by using the Born approximation. It is shown that, in ultra-scaled PCM device with 6 nm channel length, < 4 % of the energy carried by the incident electrons from the source is transferred to the atomic lattice before reaching the drain, indicating that the electron transport is largely elastic. Our simulation results show that the inelastic electron–phonon scattering, which plays an important role to excite trapped electrons in bulk PCM devices, exerts very limited influence on the current density value and the shape of current–voltage curve of ultra-scaled PCM devices. The analysis reveals that the Poole–Frenkel law and the Ohm’s law, which are the governing physical mechanisms of the bulk PCM devices, cease to be valid in the ultra-scaled PCM devices.

  1. Vapor-phase atomic-controllable growth of amorphous Li2S for high-performance lithium-sulfur batteries.

    PubMed

    Meng, Xiangbo; Comstock, David J; Fister, Timothy T; Elam, Jeffrey W

    2014-10-28

    Lithium-sulfur (Li-S) batteries hold great promise to meet the formidable energy storage requirements of future electrical vehicles but are prohibited from practical implementation by their severe capacity fading and the risks imposed by Li metal anodes. Nanoscale Li(2)S offers the possibility to overcome these challenges, but no synthetic technique exists for fine-tailoring Li(2)S at the nanoscale. Herein we report a vapor-phase atomic layer deposition (ALD) method for the atomic-scale-controllable synthesis of Li(2)S. Besides a comprehensive investigation of the ALD Li(2)S growth mechanism, we further describe the high performance of the resulting amorphous Li(2)S nanofilms as cathodes in Li-S batteries, achieving a stable capacity of ∼ 800 mA · h/g, nearly 100% Coulombic efficiency, and excellent rate capability. Nanoscale Li(2)S holds great potential for both bulk-type and thin-film high-energy Li-S batteries.

  2. Soft nanostructuring of YBCO Josephson junctions by phase separation.

    PubMed

    Gustafsson, D; Pettersson, H; Iandolo, B; Olsson, E; Bauch, T; Lombardi, F

    2010-12-08

    We have developed a new method to fabricate biepitaxial YBa2 Cu3 O7-δ (YBCO) Josephson junctions at the nanoscale, allowing junctions widths down to 100 nm and simultaneously avoiding the typical damage in grain boundary interfaces due to conventional patterning procedures. By using the competition between the superconducting YBCO and the insulating Y2 BaCuO5 phases during film growth, we formed nanometer sized grain boundary junctions in the insulating Y2 BaCuO5 matrix as confirmed by high-resolution transmission electron microscopy. Electrical transport measurements give clear indications that we are close to probing the intrinsic properties of the grain boundaries.

  3. A fuzzy controlled three-phase centrifuge for waste separation

    SciTech Connect

    Parkinson, W.J.; Smith, R.E.; Miller, N.

    1998-02-01

    The three-phase centrifuge technology discussed in this paper was developed by Neal Miller, president of Centech, Inc. The three-phase centrifuge is an excellent device for cleaning up oil field and refinery wastes which are typically composed of hydrocarbons, water, and solids. The technology is unique. It turns the waste into salable oil, reusable water, and landfill-able solids. No secondary waste is produced. The problem is that only the inventor can set up and run the equipment well enough to provide an optimal cleanup. Demand for this device has far exceeded a one man operation. There is now a need for several centrifuges to be operated at different locations at the same time. This has produced a demand for an intelligent control system, one that could replace a highly skilled operator, or at least supplement the skills of a less experienced operator. The control problem is ideally suited to fuzzy logic, since the centrifuge is a highly complicated machine operated entirely by the skill and experience of the operator. A fuzzy control system was designed for and used with the centrifuge.

  4. Laser-driven formation of a high-pressure phase in amorphous silica

    SciTech Connect

    Salleo, Alberto; Taylor, Seth T.; Martin, Michael C.; Panero, Wendy R.; Jeanloz, Raymond; Genin, Francois Y.; Sands, Timothy

    2002-05-31

    A combination of electron diffraction and infrared reflectance measurements shows that synthetic silica transforms partially into stishovite under high-intensity (GW/cm2) laser irradiation, probably by the formation of a dense ionized plasma above the silica surface. During the transformation the silicon coordination changes from four-fold to six-fold and the silicon-oxygen bond changes from mostly covalent to mostly ionic, such that optical properties of the transformed material differ significantly from those of the original glass. This phase transformation offers one suitable mechanism by which laser-induced damage grows catastrophically once initiated, thereby dramatically shortening the service lifetime of optics used for high-power photonics applications such as inertial confinement fusion.

  5. Anomalous Size-Induced Crystalline to Amorphous Uphill Phase Transformation of Hydroxyapatite Nanoparticles

    SciTech Connect

    Mossaad, Christina; Starr, Matthew; Payzant, E Andrew; Howe, Jane Y; Riman, Richard E

    2011-01-01

    The objective of the present paper was to produce nanoscale hydroxyapatite at room temperature under 10 nm through a simple method that requires no specialized equipment, surfactants, or additives. The Ca(C2H3O2)2-K3PO4-H2O synthesis system explored in previous literature was employed and the nanoscale powder product completely characterized through x-ray diffraction, transmission electron microscopy, BET nitrogen surface area adsorption, helium pycnometry, TGA and Karl Fisher titration. In accordance with other materials, it was found that hydroxyapatite under 5 nm produced by this chemistry undergoes an uphill phase transformation when left in dry storage over 5 months. Although it is possible to produce hydroxyapatite (and other materials) in this size range, it is imperative that care is taken through storage alterations to prevent any undesirable changes in structure or surface chemistry

  6. On the relationship between crystalline structure and amorphous phase dynamics during isothermal crystallization of bacterial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymers.

    PubMed

    Sics, I; Ezquerra, T A; Nogales, A; Baltá-Calleja, F J; Kalniņs, M; Tupureina, V

    2001-01-01

    The isothermal crystallization process of a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer, P(HB-co-HV) with a HB/HV ratio 78/22 was investigated by simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and dielectric spectroscopy (DS). By use of this experimental setup (SWD), we have obtained simultaneous information about changes occurring in both the crystalline and the amorphous phases during crystallization. By using the Havriliak-Negami formalism to analyze the dielectric relaxation data, a strong dependence of the relaxation curve shape with the development of the crystalline phase was found. However, in this particular copolymer, the developing crystalline domains do not affect significantly the average segmental mobility in the amorphous phase. This effect is discussed in the light of the enrichment of amorphous phase by HV comonomer units during primary crystallization, hindering the secondary crystallization processes. Results support the hypothesis that the decrease of the physical-aging-like behavior, observed in P(HB-co-HV) copolymers as the amount of HV increases, can be attributed to the progressive inhibition of secondary crystallization mechanisms.

  7. Nanoscale mid-infrared imaging of phase separation in a drug-polymer blend.

    PubMed

    Van Eerdenbrugh, Bernard; Lo, Michael; Kjoller, Kevin; Marcott, Curtis; Taylor, Lynne S

    2012-06-01

    The applicability of nanoscale mid-infrared (mid-IR) spectroscopy for the study of the micro- and nanostructure of pharmaceutical drug-polymer systems was explored. Felodipine-poly(acrylic acid) (PAA) blends were used as model systems. Standard atomic force microscopy evaluation as a function of drug-polymer composition suggested limited miscibility, in line with previous findings. Localized spectra on a 50:50 (w/w) felodipine-PAA dispersion revealed that the discrete submicrometer domains formed corresponded to an amorphous felodipine-rich phase while the continuous phase tended to be rich in PAA. Further, spectroscopic imaging at selected wavenumbers, enabling discrimination between both constituents, confirmed this finding and made it possible to chemically image differences in composition between each phase with submicrometer resolution. Copyright © 2011 Wiley Periodicals, Inc.

  8. Reaction of amorphous Ni-W and Ni-N-W films with substrate silicon

    NASA Technical Reports Server (NTRS)

    Zhu, M. F.; Suni, I.; Nicolet, M.-A.; Sands, T.

    1984-01-01

    Wiley et al. (1982) have studied sputtered amorphous films of Nb-Ni, Mo-Ni, Si-W, and Si-Mo. Kung et al. (1984) have found that amorphous Ni-Mo films as diffusion barriers between multilayer metallizations on silicon demonstrate good electrical and thermal stability. In the present investigation, the Ni-W system was selected because it is similar to the Ni-Mo system. However, W has a higher silicide formation temperature than Mo. Attention is given to aspects of sample preparation, sample characterization, the interaction between amorphous Ni-W films and Si, the crystallization of amorphous Ni(36)W(64) films on SiO2, amorphous Ni-N-W films, silicide formation and phase separation, and the crystallization of amorphous Ni(36)W(64) and Ni(30)N(21)W(49) layers.

  9. 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).

  10. Mixed-mode reversed phase/positively charged repulsion chromatography for intact protein separation.

    PubMed

    Ding, Ling; Guo, Zhimou; Hu, Zhuo; Liang, Xinmiao

    2017-05-10

    A mixed-mode reversed phase/positively charged repulsion stationary phase C8PN composed of octyl and amino group has been developed for separation of intact protein. Before the separation of proteins, a set of probe compounds were employed to evaluate the chromatographic properties of C8PN, demonstrating typical reversed phase/positively charged repulsion interaction on this stationary phase as estimated. Then the new C8PN stationary phase was used to separate a standard protein mixture on the reversed phase mode. Compared with a commercial C4 stationary phase, it showed different selectivity for some proteins. In order to better understand the properties of C8PN, the effect of acetonitrile content was investigated based on retention equation. Higher values of the equation parameters on C8PN demonstrated that the protein retentions were more sensitive to the change of acetonitrile content. Besides, the influences of buffer salt additives on the protein retentions were also studied. The retention factors of the proteins got larger with the increase of buffer salt concentration, which confirmed the positively charged repulsion interaction on the column. Finally, the C8PN was further applied to separate oxidized- and reduced- forms of Recombinant Human Growth Hormone. Our study indicated the advantages and application potential of mixed-mode reversed phase/positively charged repulsion stationary phase for intact protein separation. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. 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.

  12. 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.

  13. Phase separation in star-linear polymer mixtures.

    PubMed

    Camargo, Manuel; Likos, Christos N

    2009-05-28

    We study mixtures of star polymers and linear chains in good solvent conditions. We consider the effect of the addition of small chains on the equilibrium structure as well as on the phase behavior of low- and intermediate-functionality star solutions. By using a recently introduced effective cross interaction between stars and chains [C. Mayer and C. N. Likos, Macromolecules 40, 1196 (2007)], we solve the two-component Ornstein-Zernike equation, finding evidence for cluster formation, which is accompanied by a spinodal instability at moderate chain concentrations. The binodal lines are numerically calculated and the dependence of the observed phenomena on functionality, size, and concentrations is rationalized by considering the attractive contribution, which is displayed by the effective, chain-modified star-star interaction potential.

  14. Phase behavior and molecular dynamics simulation studies of new aqueous two-phase separation systems induced by HEPES buffer.

    PubMed

    Taha, Mohamed; Khoiroh, Ianatul; Lee, Ming-Jer

    2013-01-17

    Here, for the first time, we show that with addition of a biological buffer, 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES), into aqueous solutions of tetrahydrofuran (THF), 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone, the organic solvent can be excluded from water to form a new liquid phase. The phase diagrams have been determined at ambient temperature. In order to understand why and how a zwitterion solute (HEPES) induced phase separation of the investigated systems, molecular dynamics (MD) simulation studies are performed for HEPES + water + THF system. The MD simulations were conducted for the aqueous mixtures with 12 different compositions. The reliability of the simulation results of HEPES in pure water and beyond the phase separation mixtures was justified by comparing the densities obtained from MD with the experimental values. The simulation results of HEPES in pure THF and in a composition inside the phase separation region were justified qualitatively. Interestingly, all HEPES molecules entirely aggregated in pure THF. This reveals that HEPES is insoluble in pure THF, which is consistent with the experimental results. Even more interestingly, the MD simulation for the mixture with composition inside the phase separation region showed the formation of two phases. The THF molecules are squeezed out from the water network into a new liquid phase. The hydrogen bonds (HBs), HB lifetime, HB Gibbs energy (ΔG), radial distribution functions (RDFs), coordination numbers (CNs), electrostatic interactions, and the van der Waals interactions between the different species have been analyzed. Further, MD simulations for the other phase separation systems by choosing a composition inside the two liquids region for each system were also simulated. Our findings will therefore pave the way for designing new benign separation auxiliary agents.

  15. 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

  16. Impact of solid-phase crystallization of amorphous silicon on the chemical structure of the buried Si/ZnO thin film solar cell interface

    SciTech Connect

    Bar, M.; Wimmer, M.; Wilks, R. G.; Roczen, M.; Gerlach, D.; Ruske, F.; Lips, K.; Rech, B.; Weinhardt, L.; Blum, M.; Pookpanratana, S.; Krause, S.; Zhang, Y.; Heske, C.; Yang, W.; Denlinger, J. D.

    2010-04-30

    The chemical interface structure between phosphorus-doped hydrogenated amorphous silicon and aluminum-doped zinc oxide thin films is investigated with soft x-ray emission spectroscopy (XES) before and after solid-phase crystallization (SPC) at 600C. In addition to the expected SPC-induced phase transition from amorphous to polycrystalline silicon, our XES data indicates a pronounced chemical interaction at the buried Si/ZnO interface. In particular, we find an SPC-enhanced formation of Si-O bonds and the accumulation of Zn in close proximity to the interface. For an assumed closed and homogeneous SiO2 interlayer, an effective thickness of (5+2)nm after SPC could be estimated.

  17. Comparative Study of Solid-Phase Crystallization of Amorphous Silicon Deposited by Hot-Wire CVD, Plasma-Enhanced CVD, and Electron-Beam Evaporation

    SciTech Connect

    Stradins, P.; Kunz, O.; Young, D. L.; Yan, Y.; Jones, K. M.; Xu, Y.; Reedy, R. C.; Branz, H. M.; Aberle, A. G.; Wang, Q.

    2007-01-01

    Solid-phase crystallization (SPC) rates are compared in amorphous silicon films prepared by three different methods: hot-wire chemical vapor deposition (HWCVD), plasma-enhanced chemical vapor deposition (PECVD), and electron-beam physical vapor deposition (e-beam). Random SPC proceeds approximately 5 and 13 times slower in PECVD and e-beam films, respectively, as compared to HWCVD films. Doping accelerates random SPC in e-beam films but has little effect on the SPC rate of HWCVD films. In contrast, the crystalline growth front in solid-phase epitaxy experiments propagates at similar speed in HWCVD, PECVD, and e-beam amorphous Si films. This strongly suggests that the observed large differences in random SPC rates originate from different nucleation rates in these materials while the grain growth rates are relatively similar. The larger grain sizes observed for films that exhibit slower random SPC support this suggestion.

  18. Applied catastrophic phase inversion: a continuous non-centrifugal phase separation step in biphasic whole-cell biocatalysis.

    PubMed

    Glonke, Sebastian; Sadowski, Gabriele; Brandenbusch, Christoph

    2016-11-01

    Biphasic whole-cell biotransformations are known to be efficient alternatives to common chemical synthesis routes, especially for the production of, e.g. apolar enantiopure organic compounds. They provide high stereoselectivity combined with high product concentrations owing to the presence of an organic phase serving as substrate reservoir and product sink. Industrial implementation suffers from the formation of stable Pickering emulsions caused by the presence of cells. State-of-the-art downstream processing includes inefficient strategies such as excessive centrifugation, use of de-emulsifiers or thermal stress. In contrast, using the catastrophic phase inversion (CPI) phenomenon (sudden switch of emulsion type caused by addition of dispersed phase), Pickering-type emulsions can be destabilized efficiently. Within this work a model system using bis(2-ethylhexyl) phthalate (BEHP) as organic phase in combination with E. coli, JM101 was successfully separated using a continuous mixer settler setup. Compared to the state-of-the-art centrifugal separations, this process allows complete phase separation with no detectable water content or cells in the organic phase with no utilities/additives required. Furthermore, the concentration of the product is not affected by the separation. It is therefore a simple applicable method that can be used for separation of stable Pickering-type emulsions based on the knowledge of the point of inversion.

  19. 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.

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

    PubMed

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

    2015-07-01

    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.