Cell partition in two phase polymer systems

NASA Technical Reports Server (NTRS)

Brooks, D. E.

1979-01-01

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

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

PubMed

Sandmann, Gerhard

2010-01-01

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

Applications of the solvation parameter model in reversed-phase liquid chromatography.

PubMed

Poole, Colin F; Lenca, Nicole

2017-02-24

The solvation parameter model is widely used to provide insight into the retention mechanism in reversed-phase liquid chromatography, for column characterization, and in the development of surrogate chromatographic models for biopartitioning processes. The properties of the separation system are described by five system constants representing all possible intermolecular interactions for neutral molecules. The general model can be extended to include ions and enantiomers by adding new descriptors to encode the specific properties of these compounds. System maps provide a comprehensive overview of the separation system as a function of mobile phase composition and/or temperature for method development. The solvation parameter model has been applied to gradient elution separations but here theory and practice suggest a cautious approach since the interpretation of system and compound properties derived from its use are approximate. A growing application of the solvation parameter model in reversed-phase liquid chromatography is the screening of surrogate chromatographic systems for estimating biopartitioning properties. Throughout the discussion of the above topics success as well as known and likely deficiencies of the solvation parameter model are described with an emphasis on the role of the heterogeneous properties of the interphase region on the interpretation and understanding of the general retention mechanism in reversed-phase liquid chromatography for porous chemically bonded sorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

Liquid Crystals in Chromatography

NASA Astrophysics Data System (ADS)

Witkiewicz, Zygfryd

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

A review of molecular phase separation in binary self-assembled monolayers of thiols on gold surfaces

NASA Astrophysics Data System (ADS)

Ong, Quy; Nianias, Nikolaos; Stellacci, Francesco

2017-09-01

Binary self-assembled monolayers (SAMs) on gold surfaces have been known to undergo molecular phase separation to various degrees and have been subject to both experimental and theoretical studies. On gold nanoparticles in particular, binary SAMs ligand shells display intriguing morphologies. Consequently, unexpected behaviors of the nanoparticles with respect to their biological, chemical, and interfacial properties have been observed. It is critical that the phase separation of binary SAMs be understood at both molecular and macroscopic level to create, and then manipulate, the useful properties of the functionalized surfaces. We look into the current understanding of molecular phase separation of binary SAMs on gold surfaces, represented by Au(111) flat surfaces and Au nanoparticles, from both theoretical and experimental aspects. We point out shortcomings and describe several research strategies that will address them in the future. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Pule Pileni.

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.

Hygroscopic and phase separation properties of ammonium sulfate/organic/water ternary solutions

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Proud, S. R.; Seppalainen, S. S.; Cziczo, D. J.

2015-03-01

Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance, and therefore, particles prepared in this study should mimic atmospheric mixed phase aerosol particles. The results of this study tend to be in agreement with previous microscopy experiments, with several key differences, which possibly reveal a size-dependent effect on phase separation in organic/inorganic aerosol particles.

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

PubMed

Cole, S R; Dorsey, J G

1997-01-01

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

Simulations of irradiated-enhanced segregation and phase separation in Fe-Cu-Mn alloys

NASA Astrophysics Data System (ADS)

Li, Boyan; Hu, Shenyang; Li, Chengliang; Li, Qiulin; Chen, Jun; Shu, Guogang; Henager, Chuck, Jr.; Weng, Yuqing; Xu, Ben; Liu, Wei

2017-09-01

For reactor pressure vessel steels, the addition of Cu, Mn, and Ni has a positive effect on their mechanical, corrosion and radiation resistance properties. However, experiments show that radiation-enhanced segregation and/or phase separation is one of the important material property degradation processes. In this work, we develop a model integrating rate theory and phase-field approaches to investigate the effect of irradiation on solute segregation and phase separation. The rate theory is used to describe the accumulation and clustering of radiation defects, while the phase-field approach describes the effect of radiation defects on phase stability and microstructure evolution. The Fe-Cu-Mn ternary alloy is taken as a model system. The free energies used in the phase-field model are from CALPHAD. Spatial dependent radiation damage from atomistic simulations is introduced into the simulation cell for a given radiation dose rate. The radiation effect on segregation and phase separation is taken into account through the defect concentration dependence of solute mobility. Using the model, the effect of temperature and radiation rates on Cu and Mn segregation and Cu-rich phase nucleation were systematically investigated. The segregation and nucleation mechanisms were analyzed. The simulations demonstrate that the nucleus of Cu precipitates has a core-shell composition profile, i.e. Cu-rich at the center and Mn-rich at the interface, in good agreement with theoretical calculations as well as experimental observations.

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.

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

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

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

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

Binding Affinity Effects on Physical Characteristics of a Model Phase-Separated Protein Droplet

NASA Astrophysics Data System (ADS)

Chuang, Sara; Banani, Salman; Rosen, Michael; Brangwynne, Clifford

2015-03-01

Non-membrane bound organelles are associated with a range of biological functions. Several of these structures exhibit liquid-like properties, and may represent droplets of phase-separated RNA and/or proteins. These structures are often enriched in multi-valent molecules, however little is known about the interactions driving the assembly, properties, and function. Here, we address this question using a model multi-valent protein system consisting of repeats of Small Ubiquitin-like Modifier (SUMO) protein and a SUMO-interacting motif (SIM). These proteins undergo phase separation into liquid-like droplets. We combine microrheology and quantitative microscopy to determine affect of binding affinity on the viscosity, density and surface tension of these droplets. We also use fluorescence recovery after photobleaching (FRAP), fluorescence correlation spectroscopy (FCS) and partitioning experiments to probe the structure and dynamics within these droplets. Our results shed light on how inter-molecular interactions manifests in droplet properties, and lay the groundwork for a comprehensive biophysical picture of intracellular RNA/protein organelles.

Rebound spiking in layer II medial entorhinal cortex stellate cells: Possible mechanism of grid cell function

PubMed Central

Shay, Christopher F.; Ferrante, Michele; Chapman, G. William; Hasselmo, Michael E.

2015-01-01

Rebound spiking properties of medial entorhinal cortex (mEC) stellate cells induced by inhibition may underlie their functional properties in awake behaving rats, including the temporal phase separation of distinct grid cells and differences in grid cell firing properties. We investigated rebound spiking properties using whole cell patch recording in entorhinal slices, holding cells near spiking threshold and delivering sinusoidal inputs, superimposed with realistic inhibitory synaptic inputs to test the capacity of cells to selectively respond to specific phases of inhibitory input. Stellate cells showed a specific phase range of hyperpolarizing inputs that elicited spiking, but non-stellate cells did not show phase specificity. In both cell types, the phase range of spiking output occurred between the peak and subsequent descending zero crossing of the sinusoid. The phases of inhibitory inputs that induced spikes shifted earlier as the baseline sinusoid frequency increased, while spiking output shifted to later phases. Increases in magnitude of the inhibitory inputs shifted the spiking output to earlier phases. Pharmacological blockade of h-current abolished the phase selectivity of hyperpolarizing inputs eliciting spikes. A network computational model using cells possessing similar rebound properties as found in vitro produces spatially periodic firing properties resembling grid cell firing when a simulated animal moves along a linear track. These results suggest that the ability of mEC stellate cells to fire rebound spikes in response to a specific range of phases of inhibition could support complex attractor dynamics that provide completion and separation to maintain spiking activity of specific grid cell populations. PMID:26385258

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

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

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Fine mist versus large droplets in phase separated manganites

NASA Astrophysics Data System (ADS)

Khomskii, D.; Khomskii, L.

2003-02-01

The properties of phase-separated systems, e.g., manganites close to a first-order phase transition between charge-ordered insulator and ferromagnetic metal, are usually described by percolation picture. We argue that the correlated occupation of metallic sites leads to the preferential formation of larger metallic clusters, and their size distribution depends on the thermal history. This can explain several puzzling effects in manganites, such as the often observed inverse, or “overshot” hysteresis, and the recently discovered thermal cycling effect. Thus in treating this and similar systems in percolation picture, not only the total concentration of metallic phase, but also the distribution of metallic clusters by shape and size may significantly influence the properties of the system and has to be taken into account.

Simulations of irradiated-enhanced segregation and phase separation in Fe–Cu–Mn alloys

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

Li, Boyan; Hu, Shenyang; Li, Chengliang

2017-06-13

For reactor pressure vessel steels, the addition of Cu, Mn, and Ni has a positive effect on mechanical, corrosion and radiation resistance properties. However, experiments show that radiation-enhanced segregation and/or phase separation is one of important material property degradation processes. In this work, we developed a model integrating rate theory and phase-field approaches to investigate the effect of irradiation on solute segregation and phase separation. The rate theory is used to describe the accumulation and clustering of radiation defects while the phase-field approach describes the effect of radiation defects on phase stability and microstructure evolution. The Fe-Cu-Mn ternary alloy ismore » taken as a model system. The free energies used in the phase-field model are from CALPHAD. Spatial dependent radiation damage from atomistic simulations is introduced into the simulation cell for a given radiation dose rate. The radiation effect on segregation and phase separation is taken into account through the defect concentration dependence of solute mobility. With the model the effect of temperatures and radiation rates on Cu and Mn segregation and Cu-rich phase nucleation are systematically investigated. The segregation and nucleation mechanisms are analyzed. The simulations demonstrated that the nucleus of Cu precipitates has a core-shell composition profile, i.e., Cu rich at center and Mn rich at the interface, in good agreement with the theoretical calculation as well as experimental observations.« less

Simplified thermodynamic functions for vapor-liquid phase separation and fountain effect pumps

NASA Technical Reports Server (NTRS)

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

1984-01-01

He-4 fluid handling devices near 2 K require novel components for non-Newtonian fluid transport in He II. Related sizing of devices has to be based on appropriate thermophysical property functions. The present paper presents simplified equilibrium state functions for porous media components which serve as vapor-liquid phase separators and fountain effect pumps.

Structural and hydrodynamic properties of an intrinsically disordered region of a germ cell-specific protein on phase separation

PubMed Central

Brady, Jacob P.; Farber, Patrick J.; Sekhar, Ashok; Lin, Yi-Hsuan; Huang, Rui; Bah, Alaji; Chan, Hue Sun; Forman-Kay, Julie D.; Kay, Lewis E.

2017-01-01

Membrane encapsulation is frequently used by the cell to sequester biomolecules and compartmentalize their function. Cells also concentrate molecules into phase-separated protein or protein/nucleic acid “membraneless organelles” that regulate a host of biochemical processes. Here, we use solution NMR spectroscopy to study phase-separated droplets formed from the intrinsically disordered N-terminal 236 residues of the germ-granule protein Ddx4. We show that the protein within the concentrated phase of phase-separated Ddx4, Ddx4cond, diffuses as a particle of 600-nm hydrodynamic radius dissolved in water. However, NMR spectra reveal sharp resonances with chemical shifts showing Ddx4cond to be intrinsically disordered. Spin relaxation measurements indicate that the backbone amides of Ddx4cond have significant mobility, explaining why high-resolution spectra are observed, but motion is reduced compared with an equivalently concentrated nonphase-separating control. Observation of a network of interchain interactions, as established by NOE spectroscopy, shows the importance of Phe and Arg interactions in driving the phase separation of Ddx4, while the salt dependence of both low- and high-concentration regions of phase diagrams establishes an important role for electrostatic interactions. The diffusion of a series of small probes and the compact but disordered 4E binding protein 2 (4E-BP2) protein in Ddx4cond are explained by an excluded volume effect, similar to that found for globular protein solvents. No changes in structural propensities of 4E-BP2 dissolved in Ddx4cond are observed, while changes to DNA and RNA molecules have been reported, highlighting the diverse roles that proteinaceous solvents play in dictating the properties of dissolved solutes. PMID:28894006

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

PubMed

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

2012-06-21

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

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.

Using neutrons, X-rays and nuclear magnetism to determine the role of transition metal oxide inclusions on both glass structure and stability in automotive glass enamels.

PubMed

Bowron, Daniel T; Booth, Jonathan; Barrow, Nathan S; Sutton, Patricia; Johnson, Simon R

2018-05-23

Low levels of transition metal oxides in alkali borosilicate glass systems can drastically influence crystallisation and phase separation properties. We investigated the non-monotonic effect of manganese doping on suppressing crystallisation, and the influence on optical properties by iron oxide doping, in terms of local atomic structure. Structural models based on empirical potential structure refinement were generated from neutron and X-ray scattering data, and compared against multinuclear solid-state NMR. This revealed that a 2.5% manganese doping had a disruptive effect on the entire glass network, supressing crystallisation of an undesired bismuth silicate phase, and that iron species preferentially locate near borate tetrahedra. Preventing phase separation and controlling crystallisation behaviour of glass are critical to the ultimate properties of automotive glass enamels.

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

PubMed

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

2017-05-19

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

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

PubMed

Xie, Sheng-Ming; Yuan, Li-Ming

2017-01-01

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

The rheology and phase separation kinetics of mixed-matrix membrane dopes

NASA Astrophysics Data System (ADS)

Olanrewaju, Kayode Olaseni

Mixed-matrix hollow fiber membranes are being developed to offer more efficient gas separations applications than what the current technologies allow. Mixed-matrix membranes (MMMs) are membranes in which molecular sieves incorporated in a polymer matrix enhance separation of gas mixtures based on the molecular size difference and/or adsorption properties of the component gases in the molecular sieve. The major challenges encountered in the efficient development of MMMs are associated with some of the paradigm shifts involved in their processing, as compared to pure polymer membranes. For instance, mixed-matrix hollow fiber membranes are prepared by a dry-wet jet spinning method. Efficient large scale processing of hollow fibers by this method requires knowledge of two key process variables: the rheology and kinetics of phase separation of the MMM dopes. Predicting the rheological properties of MMM dopes is not trivial; the presence of particles significantly affects neat polymer membrane dopes. Therefore, the need exists to characterize and develop predictive capabilities for the rheology of MMM dopes. Furthermore, the kinetics of phase separation of polymer solutions is not well understood. In the case of MMM dopes, the kinetics of phase separation are further complicated by the presence of porous particles in a polymer solution. Thus, studies on the phase separation kinetics of polymer solutions and suspensions of zeolite particles in polymer solutions are essential. Therefore, this research thesis aims to study the rheology and phase separation kinetics of mixed-matrix membrane dopes. In our research efforts to develop predictive models for the shear rheology of suspensions of zeolite particles in polymer solutions, it was found that MFI zeolite suspensions have relative viscosities that dramatically exceed the Krieger-Dougherty predictions for hard sphere suspensions. Our investigations showed that the major origin of this discrepancy is the selective absorption of solvent molecules from the suspending polymer solution into the zeolite pores. Consequently, both the viscosity of the polymer solution and the particle contribution to the suspension viscosity are greatly increased. A predictive model for the viscosity of porous zeolite suspensions incorporating a solvent absorption parameter, alpha, into the Krieger-Dougherty model was developed. We experimentally determined the solvent absorption parameter and our results are in good agreement with the theoretical pore volume of MFI particles. In addition, fundamental studies were conducted with spherical nonporous silica suspensions to elucidate the role of colloidal and hydrodynamic forces on the rheology of mixed-matrix membrane dopes. Also in this thesis, details of a novel microfluidic device for measuring the phase separation kinetics of membrane dopes are presented. We have used this device to quantify the phase separation kinetics (PSK) of polymer solutions and MMM dopes upon contact with an array of relevant nonsolvent. For the polymer solution, we found that PSK is governed by the micro-rheological and thermodynamic properties of the polymer solution and nonsolvent. For the MMM dopes, we found that the PSK may increase with increase in particles surface area due to surface diffusion enhancement. In addition, it was found that the dispersed particles alter the thermodynamic properties of the dope based on the hydrophilicity and porosity of the particle.

LIGHT NONAQUEOUS PHASE LIQUIDS

EPA Science Inventory

Nonaqueous phase liquids (NAPLS) are hydrocarbons that exist as a separate, immiscible phase when in contact with water and/or air. ifferences in the physical and chemical properties of water and NAPL result in the formation of a physical interface between the liquids which preve...

Impact of x-Linkable Polymer Blends on Phase Morphology and Adhesion

NASA Astrophysics Data System (ADS)

Liu, Chun; Wan, Grace; Keene, Ellen; Harris, Joseph; Zhang, Sipei; Anderson, Stephanie; Li Pi Shan, Colin

Adhesion to dissimilar substrate is highly important to multiple industrial applications such as automotive adhesives, food packaging, transportation etc. Adhesive design has to include components that are affinity to both substrates, e.g. high surface energy polar and low surface non-polar substrates. Typically, these adhesive components are thermodynamically incompatible with each other, leading to macrophase separation and thus adhesive failure. By using functional adhesive components plus some additives, the adhesive can be in-situ cross-linked to prevent the macrophase separation with controlled phase morphology. Herein, we present the study on a cross-linkable adhesive formulation consisting of acrylic emulsion and polyolefin aqueous dispersion with additives for enhancing cross-linking and controlled phase morphologies. Contact angle measurement and ATR-IR spectroscopy are used to characterize the properties of adhesive surface. DMA is used to study the mechanical property of adhesive before and after cross-linking. The detailed phase morphologies are revealed by AFM, SEM and TEM. The resulting adhesive morphologies are correlated with the adhesive performance to establish structure-property relationship.

Control of gel swelling and phase separation of weakly charged thermoreversible gels by salt addition

PubMed Central

Solis, Francisco J.; Vernon, Brent

2009-01-01

Doping of thermoreversible polymer gels with charged monomers provides a way to control phase separation and gelation conditions by coupling the properties of the gel with a tunable ionic environment. We analyze the dependence of the gelation and phase separation conditions on the amount of salt present using a mean field model of weakly charged associative polymers. The ions and co-ions present are explicitly considered at the mean field level, and we determine their concentrations in the different equilibrium phases when the system undergoes phase separation. For weak polymer charge, the entropic contributions of the ions to the free energy of the system play a central role in the determination of the location of phase equilibrium. In the simplest case, when the associative interaction responsible for gel formation is independent of the electrostatic interaction, the addition of salt changes the polymer equilibrium concentrations and indirectly changes the measurable swelling of the gel. We construct phase diagrams of these systems showing the location of the coexistence region, the gel-sol boundary and the location of the tie-lines. We determine the swelling of the gel within the co-existence region. Our main result is that the description of the effect of the salt on the properties of the weakly charged gel can be described through an extra contribution to the effective immiscibility parameter χ proportional to the square of the doping degree f2 and to the inverse square of the added salt concentration s−2. PMID:19759854

Compatibilized Immiscible Polymer Blends for Gas Separations

PubMed Central

Panapitiya, Nimanka; Wijenayake, Sumudu; Nguyen, Do; Karunaweera, Chamaal; Huang, Yu; Balkus, Kenneth; Musselman, Inga; Ferraris, John

2016-01-01

Membrane-based gas separation has attracted a great deal of attention recently due to the requirement for high purity gasses in industrial applications like fuel cells, and because of environment concerns, such as global warming. The current methods of cryogenic distillation and pressure swing adsorption are energy intensive and costly. Therefore, polymer membranes have emerged as a less energy intensive and cost effective candidate to separate gas mixtures. However, the use of polymeric membranes has a drawback known as the permeability-selectivity tradeoff. Many approaches have been used to overcome this limitation including the use of polymer blends. Polymer blending technology synergistically combines the favorable properties of different polymers like high gas permeability and high selectivity, which are difficult to attain with a single polymer. During polymer mixing, polymers tend to uncontrollably phase separate due to unfavorable thermodynamics, which limits the number of completely miscible polymer combinations for gas separations. Therefore, compatibilizers are used to control the phase separation and to obtain stable membrane morphologies, while improving the mechanical properties. In this review, we focus on immiscible polymer blends and the use of compatibilizers for gas separation applications. PMID:28773766

Impact of nanostructuring on the magnetic and magnetocaloric properties of microscale phase-separated La 5/8–yPr yCa 3/8MnO₃ manganites

DOE PAGES

Bingham, N. S.; Lampen, P.; Phan, M. H.; ...

2012-08-16

Bulk manganites of the form La 5/8–yPr yCa 3/8MnO₃ (LPCMO) exhibit a complex phase diagram due to coexisting charge-ordered antiferromagnetic (CO/AFM), charge-disordered paramagnetic (PM), and ferromagnetic (FM) phases. Because phase separation in LPCMO occurs on the microscale, reducing particle size to below this characteristic length is expected to have a strong impact on the magnetic properties of the system. Through a comparative study of the magnetic and magnetocaloric properties of single-crystalline (bulk) and nanocrystalline LPCMO (y=3/8) we show that the AFM, CO, and FM transitions seen in the single crystal can also be observed in the large particle sizes (400more » and 150 nm), while only a single PM to FM transition is found for the small particles (55 nm). Magnetic and magnetocaloric measurements reveal that decreasing particle size affects the balance of competing phases in LPCMO and narrows the range of fields over which PM, FM, and CO phases coexist. The FM volume fraction increases with size reduction, until CO is suppressed below some critical size, ~100 nm. With size reduction, the saturation magnetization and field sensitivity first increase as long-range CO is inhibited, then decrease as surface effects become increasingly important. The trend that the FM phase is stabilized on the nanoscale is contrasted with the stabilization of the charge-disordered PM phase occurring on the microscale, demonstrating that in terms of the characteristic phase separation length, a few microns and several hundred nanometers represent very different regimes in LPCMO.« less

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Polydimethylsiloxane-based Self healing Composite and Coating Materials

DTIC Science & Technology

2006-01-01

TGA thermogravimetric analysis TDCB tapered double cantilever beam RH relative humidity DMDN-Sn dimethyldineodacanoate tin DBBE-Sn di-n-butyl bis(2...properties of micro-capsules by thermogravimetric analysis (TGA). As shown in figure 2.17, no weight change occurred up to the boiling point of...Elemental analysis of separated prepolymer phase and control samples. ..............24 Table 2.4: The size values of phase separated PDMS droplets

Characterising the structural properties of polymer separators for lithium-ion batteries in 3D using phase contrast X-ray microscopy

NASA Astrophysics Data System (ADS)

Finegan, Donal P.; Cooper, Samuel J.; Tjaden, Bernhard; Taiwo, Oluwadamilola O.; Gelb, Jeff; Hinds, Gareth; Brett, Dan J. L.; Shearing, Paul R.

2016-11-01

Separators are an integral component for optimising performance and safety of lithium-ion batteries; therefore, a clear understanding of how their microstructure affects cell performance and safety is crucial. Phase contrast X-ray microscopy is used here to capture the microstructures of commercial monolayer, tri-layer, and ceramic-coated lithium-ion battery polymer separators. Spatial variations in key structural parameters, including porosity, tortuosity factor and pore size distribution, are determined through the application of 3D quantification techniques and stereology. The architectures of individual layers in multi-layer membranes are characterised, revealing anisotropy in porosity, tortuosity factor and mean pore size of the three types of separator. Detailed structural properties of the individual layers of multi-layered membranes are then related with their expected effect on safety and rate capability of cells.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

DOE PAGES

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

2018-01-09

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

Effect of various electrokinetic treatment regimes on solids surface properties and thermal behavior of oil sediments.

PubMed

Kariminezhad, Esmaeel; Elektorowicz, Maria

2018-04-10

The electrokinetic process has shown its ability to separate the different material phases. However, not much is known about the effect of the electric fields on the surface properties of solids in the oil sediments and their behavior under different electrical regimes. In this study, the effect of four different types of electrical current on the surface properties of oil sediments was investigated, namely constant direct current (CDC), pulsed direct current (PDC), incremental direct current (IDC) and decremental direct current (DDC). X-ray photoelectron spectroscopy (XPS) analyses showed a decrease in the concentration of carbon from 99% in centrifuged samples to 63% on the surface of the solids in the PDC-treated oil sediment. Wettability alteration and contact angle studies showed an enhance in hydrophilicity of the solids following electrokinetic treatment. A significant change in carbon and oxygen-containing functionalities at the surface solids of the DDC-treated sediment was also observed. Thermogravimetric analyses (TGA) confirmed the ability of electrokinetic treatment in separating the phases by shifting the thermogram profiles towards lower temperatures. The findings showed that the electrokinetic process exerts its effect by altering the surface properties of the sediment solids and destabilizing water-in-oil emulsions to facilitate phase separation of this complex waste. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydrodynamic effects on phase separation morphologies in evaporating thin films of polymer solutions

NASA Astrophysics Data System (ADS)

Zoumpouli, Garyfalia A.; Yiantsios, Stergios G.

2016-08-01

We examine effects of hydrodynamics on phase separation morphologies developed during drying of thin films containing a volatile solvent and two dissolved polymers. Cahn-Hilliard and Flory-Huggins theories are used to describe the free energy of the phase separating systems. The thin films, considered as Newtonian fluids, flow in response to Korteweg stresses arising due to concentration non-uniformities that develop during solvent evaporation. Numerical simulations are employed to investigate the effects of a Peclet number, defined in terms of system physical properties, as well as the effects of parameters characterizing the speed of evaporation and preferential wetting of the solutes at the gas interface. For systems exhibiting preferential wetting, diffusion alone is known to favor lamellar configurations for the separated phases in the dried film. However, a mechanism of hydrodynamic instability of a short length scale is revealed, which beyond a threshold Peclet number may deform and break the lamellae. The critical Peclet number tends to decrease as the evaporation rate increases and to increase with the tendency of the polymers to selectively wet the gas interface. As the Peclet number increases, the instability moves closer to the gas interface and induces the formation of a lateral segregation template that guides the subsequent evolution of the phase separation process. On the other hand, for systems with no preferential wetting or any other property asymmetries between the two polymers, diffusion alone favors the formation of laterally separated configurations. In this case, concentration perturbation modes that lead to enhanced Korteweg stresses may be favored for sufficiently large Peclet numbers. For such modes, a second mechanism is revealed, which is similar to the solutocapillary Marangoni instability observed in evaporating solutions when interfacial tension increases with the concentration of the non-volatile component. This mechanism may lead to multiple length scales in the laterally phase separated configurations.

Separating the effects of repulsive and attractive forces on the phase diagram, interfacial, and critical properties of simple fluids

NASA Astrophysics Data System (ADS)

Fuentes-Herrera, M.; Moreno-Razo, J. A.; Guzmán, O.; López-Lemus, J.; Ibarra-Tandi, B.

2016-06-01

Molecular simulations in the canonical and isothermal-isobaric ensembles were performed to study the effect of varying the shape of the intermolecular potential on the phase diagram, critical, and interfacial properties of model fluids. The molecular interactions were modeled by the Approximate Non-Conformal (ANC) theory potentials. Unlike the Lennard-Jones or Morse potentials, the ANC interactions incorporate parameters (called softnesses) that modulate the steepness of the potential in their repulsive and attractive parts independently. This feature allowed us to separate unambiguously the role of each region of the potential on setting the thermophysical properties. In particular, we found positive linear correlation between all critical coordinates and the attractive and repulsive softness, except for the critical density and the attractive softness which are negatively correlated. Moreover, we found that the physical properties related to phase coexistence (such as span of the liquid phase between the critical and triple points, variations in the P-T vaporization curve, interface width, and surface tension) are more sensitive to changes in the attractive softness than to the repulsive one. Understanding the different roles of attractive and repulsive forces on phase coexistence may contribute to developing more accurate models of liquids and their mixtures.

Separating the effects of repulsive and attractive forces on the phase diagram, interfacial, and critical properties of simple fluids.

PubMed

Fuentes-Herrera, M; Moreno-Razo, J A; Guzmán, O; López-Lemus, J; Ibarra-Tandi, B

2016-06-07

Molecular simulations in the canonical and isothermal-isobaric ensembles were performed to study the effect of varying the shape of the intermolecular potential on the phase diagram, critical, and interfacial properties of model fluids. The molecular interactions were modeled by the Approximate Non-Conformal (ANC) theory potentials. Unlike the Lennard-Jones or Morse potentials, the ANC interactions incorporate parameters (called softnesses) that modulate the steepness of the potential in their repulsive and attractive parts independently. This feature allowed us to separate unambiguously the role of each region of the potential on setting the thermophysical properties. In particular, we found positive linear correlation between all critical coordinates and the attractive and repulsive softness, except for the critical density and the attractive softness which are negatively correlated. Moreover, we found that the physical properties related to phase coexistence (such as span of the liquid phase between the critical and triple points, variations in the P-T vaporization curve, interface width, and surface tension) are more sensitive to changes in the attractive softness than to the repulsive one. Understanding the different roles of attractive and repulsive forces on phase coexistence may contribute to developing more accurate models of liquids and their mixtures.

Effects of Phytoplankton Growth Phase on the Formation and Properties of Marine Snow

NASA Astrophysics Data System (ADS)

Montgomery, Q. W.; Proctor, K. W.; Prairie, J. C.

2016-02-01

Marine snow aggregates often dominate carbon export from the upper mixed layer to the deep ocean. Thus, understanding the formation and the properties of these aggregates is essential to the study of the biological pump. Aggregate formation is determined by both the encounter rate and the stickiness of the particles that they are composed of. Stickiness of phytoplankton has been linked to production of transparent exopolymer particles (TEP), which has been previously shown to vary in concentration throughout different parts of the phytoplankton growth cycle. The objective of this study is to determine the effects of the growth phase of the diatom Thalassiosira weissflogii to both TEP production and the properties of the resulting aggregates produced. Cultures of T. weissflogii were stopped at separate phases of the phytoplankton growth curve and incubated in rotating cylindrical tanks to form aggregates. Aggregate properties such as size, density, and porosity were measured at the end of each period of roller incubation. Preliminary results describe little variation in the size of the aggregates formed from different parts of the growth phase, but show a significant effect of growth phase on aggregate density. Density is an important factor in the settling of marine aggregates. Therefore, variations in aggregate density during different growth phases may have large implications for the efficiency of the biological pump during different stages of a phytoplankton bloom. Further examination will be performed on the potential effects of TEP abundance on the properties of the aggregates formed at separate growth phases and the resulting implications for carbon flux.

Controlling Microstructure-Transport Interplay in Highly Phase-Separated Perfluorosulfonated Aromatic Multiblock Ionomers via Molecular Architecture Design.

PubMed

Nguyen, Huu-Dat; Assumma, Luca; Judeinstein, Patrick; Mercier, Regis; Porcar, Lionel; Jestin, Jacques; Iojoiu, Cristina; Lyonnard, Sandrine

2017-01-18

Proton-conducting multiblock polysulfones bearing perfluorosulfonic acid side chains were designed to encode nanoscale phase-separation, well-defined hydrophilic/hydrophobic interfaces, and optimized transport properties. Herein, we show that the superacid side chains yield highly ordered morphologies that can be tailored by best compromising ion-exchange capacity and block lengths. The obtained microstructures were extensively characterized by small-angle neutron scattering (SANS) over an extended range of hydration. Peculiar swelling behaviors were evidenced at two different scales and attributed to the dilution of locally flat polymer particles. We evidence the direct correlation between the quality of interfaces, the topology and connectivity of ionic nanodomains, the block superstructure long-range organization, and the transport properties. In particular, we found that the proton conductivity linearly depends on the microscopic expansion of both ionic and block domains. These findings indicate that neat nanoscale phase-separation and block-induced long-range connectivity can be optimized by designing aromatic ionomers with controlled architectures to improve the performances of polymer electrolyte membranes.

In situ reinforced polymers using low molecular weight compounds

NASA Astrophysics Data System (ADS)

Yordem, Onur Sinan

2011-12-01

The primary objective of this research is to generate reinforcing domains in situ during the processing of polymers by using phase separation techniques. Low molecular weight compounds were mixed with polymers where the process viscosity is reduced at process temperatures and mechanical properties are improved once the material system is cooled or reacted. Thermally induced phase separation and thermotropic phase transformation of low molar mass compounds were used in isotactic polypropylene (iPP) and poly(ether ether ketone) (PEEK) resins. Reaction induced phase separation was utilized in thermosets to generate anisotropic reinforcements. A new strategy to increase fracture toughness of materials was introduced. Simultaneously, enhancement in stiffness and reduction in process viscosity were also attained. Materials with improved rheological and mechanical properties were prepared by using thermotropic phase transformations of metal soaps in polymers (calcium stearate/iPP). Morphology and thermal properties were studied using WAXS, DSC and SEM. Mechanical and rheological investigation showed significant reduction in process viscosity and substantial improvement in fracture toughness were attained. Effects of molecular architecture of metal soaps were investigated in PEEK (calcium stearate/PEEK and sodium stearate/PEEK). The selected compounds reduced the process viscosity due to the high temperature co-continuous morphology of metal soaps. Unlike the iPP system that incorporates spherical particles, interaction between PEEK and metal soaps resulted in two discrete and co-continuous phases of PEEK and the metal stearates. DMA and melt rheology exhibited that sodium stearate/PEEK composites are stiffer. Effective moduli of secondary metal stearate phase were calculated using different composite theories, which suggested bicontinuous morphology to the metal soaps in PEEK. Use of low molecular weight crystallizable solvents was investigated in reactive systems. Formation of anisotropic reinforcements was evaluated using dimethyl sulfone (DMS) as the crystallizable diluent and diglycidyl ether of bisphenol-A (DGEBA)/m-phenylene diamine (mPDA) material system as the epoxy thermoset. Miscible blends of DMS and DGEBA/mPDA form homogenous mixtures that undergo polymerization induced phase separation, once the DGEBA oligomers react with mPDA. The effect of the competition between the crystallization and phase separation of DMS resulted in nano-wires to micro-scale fiber-like crystals that were generated by adjusting the reaction temperature and DMS concentration.

Advances in covalent organic frameworks in separation science.

PubMed

Qian, Hai-Long; Yang, Cheng-Xiong; Wang, Wen-Long; Yang, Cheng; Yan, Xiu-Ping

2018-03-23

Covalent organic frameworks (COFs) are a new class of multifunctional crystalline organic polymer constructed with organic monomers via robust covalent bonds. The unique properties such as convenient modification, low densities, large specific surface areas, good stability and permanent porosity make COFs great potential in separation science. This review shows the state-of-the art for the application of COFs and their composites in analytical separation science. COFs and their composites have been explored as promising sorbents for solid phase extraction, potential coatings for solid phase microextraction, and novel stationary phases for gas chromatography, high-performance liquid chromatography and capillary electrochromatography. The prospects of COFs for separation science are also presented, which can offer an outlook and reference for further study on the applications of COFs. Copyright © 2018 Elsevier B.V. All rights reserved.

Studies on aqueous two phase polymer systems useful for partitioning of biological materials

NASA Technical Reports Server (NTRS)

Brooks, D. E.; Bamberger, S.

1982-01-01

The two phase systems that result when aqueous solutions of dextran and poly(ethylene glycol) (PEG) are mixed above a critical concentration of a few percent provide a useful medium for the separation of biological cell subpopulations via partition between the top, PEG-rich phase and the liquid-liquid phase boundary. Interfacial tensions of such systems have been measured by the rotating drop technique and found to range between 0.1-100 micro-N/m. The tension was found to depend on the length of the tie line describing the system on a phase diagram, via a power law relationship which differed depending on the concentration of Na phosphate buffer present. The electrokinetic properties of drops of one phase suspended in the other were studied for a variety of systems. It was found that the droplet electrophoretic mobility increased monotonically with phosphate concentration and drop diameter but exhibited the opposite sign from that anticipated from phosphate partition measurements. It was possible to take advantage of these electrokinetic properties and dramatically enhance the speed of phase separation through application of relatively small electric fields.

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

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

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

1996-05-01

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

Resonant pairing between fermions with unequal masses

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

Wu, Shin-Tza; Pao, C.-H.; Yip, S.-K.

We study via mean-field theory the pairing between fermions of different masses, especially at the unitary limit. At equal populations, the thermodynamic properties are identical with the equal mass case provided an appropriate rescaling is made. At unequal populations, for sufficiently light majority species, the system does not phase separate. For sufficiently heavy majority species, the phase separated normal phase have a density larger than that of the superfluid. For atoms in harmonic traps, the density profiles for unequal mass fermions can be drastically different from their equal-mass counterparts.

Temperature-responsive chromatography for the separation of biomolecules.

PubMed

Kanazawa, Hideko; Okano, Teruo

2011-12-09

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

Cellulosic Biomass-Reinforced Polyvinylidene Fluoride Separators with Enhanced Dielectric Properties and Thermal Tolerance.

PubMed

Li, Lei; Yu, Miao; Jia, Chao; Liu, Jianxin; Lv, Yanyan; Liu, Yanhua; Zhou, Yi; Liu, Chuanting; Shao, Ziqiang

2017-06-21

Safety issues are critical barriers to large-scale energy storage applications of lithium-ion batteries (LIBs). Using an ameliorated, thermally stable, shutdown separator is an effective method to overcome the safety issues. Herein, we demonstrate a novel, cellulosic biomass-material-blended polyvinylidene fluoride separator that was prepared using a simple nonsolvent-induced phase separation technique. This process formed a microporous composite separator with reduced crystallinity, uniform pore size distribution, superior thermal tolerance, and enhanced electrolyte wettability and dielectric and mechanical properties. In addition, the separator has a superior capacity retention and a better rate capability compared to the commercialized microporous polypropylene membrane. This fascinating membrane was fabricated via a relatively eco-friendly and cost-effective method and is an alternative, promising separator for high-power LIBs.

Structure Evolution of Graphene Oxide during Thermally Driven Phase Transformation: Is the Oxygen Content Really Preserved?

PubMed Central

Sun, Pengzhan; Wang, Yanlei; Liu, He; Wang, Kunlin; Wu, Dehai; Xu, Zhiping; Zhu, Hongwei

2014-01-01

A mild annealing procedure was recently proposed for the scalable enhancement of graphene oxide (GO) properties with the oxygen content preserved, which was demonstrated to be attributed to the thermally driven phase separation. In this work, the structure evolution of GO with mild annealing is closely investigated. It reveals that in addition to phase separation, the transformation of oxygen functionalities also occurs, which leads to the slight reduction of GO membranes and furthers the enhancement of GO properties. These results are further supported by the density functional theory based calculations. The results also show that the amount of chemically bonded oxygen atoms on graphene decreases gradually and we propose that the strongly physisorbed oxygen species constrained in the holes and vacancies on GO lattice might be responsible for the preserved oxygen content during the mild annealing procedure. The present experimental results and calculations indicate that both the diffusion and transformation of oxygen functional groups might play important roles in the scalable enhancement of GO properties. PMID:25372142

Effect of Alcohols on the Phase Behavior and Emulsification of a Sucrose Fatty Acid Ester/Water/Edible Oil System.

PubMed

Matsuura, Tsutashi; Ogawa, Akihiro; Ohara, Yukari; Nishina, Shogo; Nakanishi, Maho; Gohtani, Shoichi

2018-02-01

The effect of alcohols (ethanol, 1-propanol, propylene glycol, glycerin, sucrose) on the phase behavior and emulsification of sucrose stearic acid ester (SSE)/water/edible vegetable oil (EVO) systems was investigated. Adding sucrose, propylene glycol, and glycerin narrowed the oil-separated two-phase region in the phase diagram of the SSE/water/EVO systems, whereas adding ethanol and 1-propanol expanded the oil-separated two-phase region. Changing the course of emulsification in the phase diagram showed that the size of the oil-droplet particle typically decreased in a system with a narrowed oil-separated region. The emulsification properties of the systems varied with respect to changes in the phase diagram. The microstructure of the systems was examined using small-angle X-ray scattering, and the ability to retain the oil in the lamellar structure of the SSEs was suggested as an important role in emulsification, because the mechanism of the systems was the same as that for the liquid crystal emulsification method.

Live cell plasma membranes do not exhibit a miscibility phase transition over a wide range of temperatures.

PubMed

Lee, Il-Hyung; Saha, Suvrajit; Polley, Anirban; Huang, Hector; Mayor, Satyajit; Rao, Madan; Groves, Jay T

2015-03-26

Lipid/cholesterol mixtures derived from cell membranes as well as their synthetic reconstitutions exhibit well-defined miscibility phase transitions and critical phenomena near physiological temperatures. This suggests that lipid/cholesterol-mediated phase separation plays a role in the organization of live cell membranes. However, macroscopic lipid-phase separation is not generally observed in cell membranes, and the degree to which properties of isolated lipid mixtures are preserved in the cell membrane remain unknown. A fundamental property of phase transitions is that the variation of tagged particle diffusion with temperature exhibits an abrupt change as the system passes through the transition, even when the two phases are distributed in a nanometer-scale emulsion. We support this using a variety of Monte Carlo and atomistic simulations on model lipid membrane systems. However, temperature-dependent fluorescence correlation spectroscopy of labeled lipids and membrane-anchored proteins in live cell membranes shows a consistently smooth increase in the diffusion coefficient as a function of temperature. We find no evidence of a discrete miscibility phase transition throughout a wide range of temperatures: 14-37 °C. This contrasts the behavior of giant plasma membrane vesicles (GPMVs) blebbed from the same cells, which do exhibit phase transitions and macroscopic phase separation. Fluorescence lifetime analysis of a DiI probe in both cases reveals a significant environmental difference between the live cell and the GPMV. Taken together, these data suggest the live cell membrane may avoid the miscibility phase transition inherent to its lipid constituents by actively regulating physical parameters, such as tension, in the membrane.

A theoretical and experimental study of turbulent particle-laden jets

NASA Technical Reports Server (NTRS)

Shuen, J. S.; Solomon, A. S. P.; Zhang, Q. F.; Faeth, G. M.

1983-01-01

Mean and fluctuating velocities of both phases, particle mass fluxes, particle size distributions in turbulent particle-laden jets were measured. The following models are considered: (1) a locally homogeneous flow (LHF) model, where slip between the phases was neglected; (2) a deterministic separated flow (DSF) model, where slip was considered but effects of particle dispersion by turbulence were ignored; and (3) a stochastic separated flow (SSF) model. The SSF model performed reasonably well with no modifications in the prescriptions for eddy properties from its original calibration. A modified k- model, incorporating direct contributions of interphase transport on turbulence properties (turbulence modulation), was developed within the framework of the SSF model.

Functionalized low defect graphene nanoribbons and polyurethane composite film for improved gas barrier and mechanical performances.

PubMed

Xiang, Changsheng; Cox, Paris J; Kukovecz, Akos; Genorio, Bostjan; Hashim, Daniel P; Yan, Zheng; Peng, Zhiwei; Hwang, Chih-Chau; Ruan, Gedeng; Samuel, Errol L G; Sudeep, Parambath M; Konya, Zoltan; Vajtai, Robert; Ajayan, Pulickel M; Tour, James M

2013-11-26

A thermoplastic polyurethane (TPU) composite film containing hexadecyl-functionalized low-defect graphene nanoribbons (HD-GNRs) was produced by solution casting. The HD-GNRs were well distributed within the polyurethane matrix, leading to phase separation of the TPU. Nitrogen gas effective diffusivity of TPU was decreased by 3 orders of magnitude with only 0.5 wt % HD-GNRs. The incorporation of HD-GNRs also improved the mechanical properties of the composite films, as predicted by the phase separation and indicated by tensile tests and dynamic mechanical analyses. The improved properties of the composite film could lead to potential applications in food packaging and lightweight mobile gas storage containers.

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

PubMed

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

2015-11-01

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

Anisotropic properties of phase separation in two-component dipolar Bose-Einstein condensates

NASA Astrophysics Data System (ADS)

Wang, Wei; Li, Jinbin

2018-03-01

Using Crank-Nicolson method, we calculate ground state wave functions of two-component dipolar Bose-Einstein condensates (BECs) and show that, due to dipole-dipole interaction (DDI), the condensate mixture displays anisotropic phase separation. The effects of DDI, inter-component s-wave scattering, strength of trap potential and particle numbers on the density profiles are investigated. Three types of two-component profiles are present, first cigar, along z-axis and concentric torus, second pancake (or blood cell), in xy-plane, and two non-uniform ellipsoid, separated by the pancake and third two dumbbell shapes.

Atomic Force Microscopy Studies of Functional and Dysfunctional Pulmonary Surfactant Films. I. Micro- and Nanostructures of Functional Pulmonary Surfactant Films and the Effect of SP-A

PubMed Central

Zuo, Yi Y.; Keating, Eleonora; Zhao, Lin; Tadayyon, Seyed M.; Veldhuizen, Ruud A. W.; Petersen, Nils O.; Possmayer, Fred

2008-01-01

Monolayers of a functional pulmonary surfactant (PS) can reach very low surface tensions well below their equilibrium value. The mechanism by which PS monolayers reach such low surface tensions and maintain film stability remains unknown. As shown previously by fluorescence microscopy, phospholipid phase transition and separation seem to be important for the normal biophysical properties of PS. This work studied phospholipid phase transitions and separations in monolayers of bovine lipid extract surfactant using atomic force microscopy. Atomic force microscopy showed phospholipid phase separation on film compression and a monolayer-to-multilayer transition at surface pressure 40–50 mN/m. The tilted-condensed phase consisted of domains not only on the micrometer scale, as detected previously by fluorescence microscopy, but also on the nanometer scale, which is below the resolution limits of conventional optical methods. The nanodomains were embedded uniformly within the liquid-expanded phase. On compression, the microdomains broke up into nanodomains, thereby appearing to contribute to tilted-condensed and liquid-expanded phase remixing. Addition of surfactant protein A altered primarily the nanodomains and promoted the formation of multilayers. We conclude that the nanodomains play a predominant role in affecting the biophysical properties of PS monolayers and the monolayer-to-multilayer transition. PMID:18212010

Preparation and Characterization of Hydrophilically Modified PVDF Membranes by a Novel Nonsolvent Thermally Induced Phase Separation Method

PubMed Central

Hu, Ningen; Xiao, Tonghu; Cai, Xinhai; Ding, Lining; Fu, Yuhua; Yang, Xing

2016-01-01

In this study, a nonsolvent thermally-induced phase separation (NTIPS) method was first proposed to fabricate hydrophilically-modified poly(vinylidene fluoride) (PVDF) membranes to overcome the drawbacks of conventional thermally-induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods. Hydrophilically-modified PVDF membranes were successfully prepared by blending in hydrophilic polymer polyvinyl alcohol (PVA) at 140 °C. A series of PVDF/PVA blend membranes was prepared at different total polymer concentrations and blend ratios. The morphological analysis via SEM indicated that the formation mechanism of these hydrophilically-modified membranes was a combined NIPS and TIPS process. As the total polymer concentration increased, the tensile strength of the membranes increased; meanwhile, the membrane pore size, porosity and water flux decreased. With the PVDF/PVA blend ratio increased from 10:0 to 8:2, the membrane pore size and water flux increased. The dynamic water contact angle of these membranes showed that the hydrophilic properties of PVDF/PVA blend membranes were prominently improved. The higher hydrophilicity of the membranes resulted in reduced membrane resistance and, hence, higher permeability. The total resistance Rt of the modified PVDF membranes decreased significantly as the hydrophilicity increased. The irreversible fouling related to pore blocking and adsorption fouling onto the membrane surface was minimal, indicating good antifouling properties. PMID:27869711

Preparation and Characterization of Hydrophilically Modified PVDF Membranes by a Novel Nonsolvent Thermally Induced Phase Separation Method.

PubMed

Hu, Ningen; Xiao, Tonghu; Cai, Xinhai; Ding, Lining; Fu, Yuhua; Yang, Xing

2016-11-18

In this study, a nonsolvent thermally-induced phase separation (NTIPS) method was first proposed to fabricate hydrophilically-modified poly(vinylidene fluoride) (PVDF) membranes to overcome the drawbacks of conventional thermally-induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods. Hydrophilically-modified PVDF membranes were successfully prepared by blending in hydrophilic polymer polyvinyl alcohol (PVA) at 140 °C. A series of PVDF/PVA blend membranes was prepared at different total polymer concentrations and blend ratios. The morphological analysis via SEM indicated that the formation mechanism of these hydrophilically-modified membranes was a combined NIPS and TIPS process. As the total polymer concentration increased, the tensile strength of the membranes increased; meanwhile, the membrane pore size, porosity and water flux decreased. With the PVDF/PVA blend ratio increased from 10:0 to 8:2, the membrane pore size and water flux increased. The dynamic water contact angle of these membranes showed that the hydrophilic properties of PVDF/PVA blend membranes were prominently improved. The higher hydrophilicity of the membranes resulted in reduced membrane resistance and, hence, higher permeability. The total resistance R t of the modified PVDF membranes decreased significantly as the hydrophilicity increased. The irreversible fouling related to pore blocking and adsorption fouling onto the membrane surface was minimal, indicating good antifouling properties.

Can visco-elastic phase separation, macromolecular crowding and colloidal physics explain nuclear organisation?

PubMed

Iborra, Francisco J

2007-04-12

The cell nucleus is highly compartmentalized with well-defined domains, it is not well understood how this nuclear order is maintained. Many scientists are fascinated by the different set of structures observed in the nucleus to attribute functions to them. In order to distinguish functional compartments from non-functional aggregates, I believe is important to investigate the biophysical nature of nuclear organisation. The various nuclear compartments can be divided broadly as chromatin or protein and/or RNA based, and they have very different dynamic properties. The chromatin compartment displays a slow, constrained diffusional motion. On the other hand, the protein/RNA compartment is very dynamic. Physical systems with dynamical asymmetry go to viscoelastic phase separation. This phase separation phenomenon leads to the formation of a long-lived interaction network of slow components (chromatin) scattered within domains rich in fast components (protein/RNA). Moreover, the nucleus is packed with macromolecules in the order of 300 mg/ml. This high concentration of macromolecules produces volume exclusion effects that enhance attractive interactions between macromolecules, known as macromolecular crowding, which favours the formation of compartments. In this paper I hypothesise that nuclear compartmentalization can be explained by viscoelastic phase separation of the dynamically different nuclear components, in combination with macromolecular crowding and the properties of colloidal particles. I demonstrate that nuclear structure can satisfy the predictions of this hypothesis. I discuss the functional implications of this phenomenon.

Sodium triflate decreases interaggregate repulsion and induces phase separation in cationic micelles.

PubMed

Lima, Filipe S; Cuccovia, Iolanda M; Buchner, Richard; Antunes, Filipe E; Lindman, Björn; Miguel, Maria G; Horinek, Dominik; Chaimovich, Hernan

2015-03-10

Dodecyltrimethylammonium triflate (DTATf) micelles possess lower degree of counterion dissociation (α), lower hydration, and higher packing of monomers than other micelles of similar structure. Addition of sodium triflate ([NaTf] > 0.05 M) to DTATf solutions promotes phase separation. This phenomenon is commonly observed in oppositely charged surfactant mixtures, but it is rare for ionic surfactants and relatively simple counterions. While the properties of DTATf have already been reported, the driving forces for the observed phase separation with added salt remain unclear. Thus, we propose an interpretation for the observed phase separation in cationic surfactant solutions. Addition of up to 0.03 M NaTf to micellar DTATf solutions led to a limited increase of the aggregation number, to interface dehydration, and to a progressive decrease in α. The viscosity of DTATf solutions of higher concentration ([DTATf] ≥ 0.06 M) reached a maximum with increasing [NaTf], though the aggregation number slightly increased, and no shape change occurred. We hypothesize that this maximum results from a decrease in interaggregate repulsion, as a consequence of increased ion binding. This reduction in micellar repulsion without simultaneous infinite micellar growth is, probably, the major driving force for phase separation at higher [NaTf].

Cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase for the enantioseparation of drugs in supercritical fluid chromatography: comparison with HPLC.

PubMed

Kalíková, Květa; Martínková, Monika; Schmid, Martin G; Tesařová, Eva

2018-03-01

A cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase was studied as a tool for the enantioselective separation of 21 selected analytes with different pharmaceutical and physicochemical properties. The enantioseparations were performed using supercritical fluid chromatography. The effect of the mobile phase composition was studied. Four different additives (diethylamine, triethylamine, isopropylamine, and trifluoroacetic acid) and isopropylamine combined with trifluoroacetic acid were tested and their influence on enantioseparation was compared. The influence of two different mobile phase co-solvents (methanol and propan-2-ol) combined with all the additives was also evaluated. The best mobile phase compositions for the separation of the majority of enantiomers were CO 2 /methanol/isopropylamine 80:20:0.1 v/v/v or CO 2 /propan-2-ol/isopropylamine/trifluoroacetic acid 80:20:0.05:0.05 v/v/v/v. The best results were obtained from the group of basic β-blockers. A high-performance liquid chromatography separation system composed of the same stationary phase and mobile phase of similar properties prepared as a mixture of hexane/propan-2-ol/additive 80:20:0.1 v/v/v was considered for comparison. Supercritical fluid chromatography was found to yield better results, i.e. better enantioresolution for shorter analysis times than high-performance liquid chromatography. However, examples of enantiomers better resolved under the optimized conditions in high-performance liquid chromatography were also found. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

Bioinspired phase-separated disordered nanostructures for thin photovoltaic absorbers.

PubMed

Siddique, Radwanul H; Donie, Yidenekachew J; Gomard, Guillaume; Yalamanchili, Sisir; Merdzhanova, Tsvetelina; Lemmer, Uli; Hölscher, Hendrik

2017-10-01

The wings of the black butterfly, Pachliopta aristolochiae , are covered by micro- and nanostructured scales that harvest sunlight over a wide spectral and angular range. Considering that these properties are particularly attractive for photovoltaic applications, we analyze the contribution of these micro- and nanostructures, focusing on the structural disorder observed in the wing scales. In addition to microspectroscopy experiments, we conduct three-dimensional optical simulations of the exact scale structure. On the basis of these results, we design nanostructured thin photovoltaic absorbers of disordered nanoholes, which combine efficient light in-coupling and light-trapping properties together with a high angular robustness. Finally, inspired by the phase separation mechanism of self-assembled biophotonic nanostructures, we fabricate these bioinspired absorbers using a scalable, self-assembly patterning technique based on the phase separation of binary polymer mixture. The nanopatterned absorbers achieve a relative integrated absorption increase of 90% at a normal incident angle of light to as high as 200% at large incident angles, demonstrating the potential of black butterfly structures for light-harvesting purposes in thin-film solar cells.

Bioinspired phase-separated disordered nanostructures for thin photovoltaic absorbers

PubMed Central

Siddique, Radwanul H.; Donie, Yidenekachew J.; Gomard, Guillaume; Yalamanchili, Sisir; Merdzhanova, Tsvetelina; Lemmer, Uli; Hölscher, Hendrik

2017-01-01

The wings of the black butterfly, Pachliopta aristolochiae, are covered by micro- and nanostructured scales that harvest sunlight over a wide spectral and angular range. Considering that these properties are particularly attractive for photovoltaic applications, we analyze the contribution of these micro- and nanostructures, focusing on the structural disorder observed in the wing scales. In addition to microspectroscopy experiments, we conduct three-dimensional optical simulations of the exact scale structure. On the basis of these results, we design nanostructured thin photovoltaic absorbers of disordered nanoholes, which combine efficient light in-coupling and light-trapping properties together with a high angular robustness. Finally, inspired by the phase separation mechanism of self-assembled biophotonic nanostructures, we fabricate these bioinspired absorbers using a scalable, self-assembly patterning technique based on the phase separation of binary polymer mixture. The nanopatterned absorbers achieve a relative integrated absorption increase of 90% at a normal incident angle of light to as high as 200% at large incident angles, demonstrating the potential of black butterfly structures for light-harvesting purposes in thin-film solar cells. PMID:29057320

Retention properties of novel beta-CD bonded stationary phases in reversed-phase HPLC mode.

PubMed

Zhao, Yanyan; Guo, Zhimou; Zhang, Yongping; Xue, Xingya; Xu, Qing; Li, Xiuling; Liang, Xinmiao; Zhang, Yukui

2009-05-15

With the given special structures, the CD bonded stationary phases are expected to have complementary retention properties with conventional C18 stationary phase, which will be helpful to enhance the polar selectivity in RP mode separation. In this work, two beta-cyclodextrin (beta-CD) bonded stationary phases for reversed-phase HPLC, including 1, 12-dodecyldiol linked beta-CD stationary phase (CD1) and olio (ethylene glycol) (OEG) linked beta-CD stationary phase (CD2), have been synthesized via click chemistry. The resulting materials were characterized with FT-IR and elemental analysis, which proved the successful immobilization of ligands. The similarities and differences in retention characteristics between the CD and C18 stationary phases have been elucidated by using comparative linear solvation energy relationships (LSERs). The force related to solute McGowan volume has no significant difference, while the hydrogen bonding and dipolar interactions between solutes and CD stationary phases are stronger than between solutes and C18, which is attributed to the special structures (CD and triazole groups) of CD stationary phases. Chemical origins are interpreted by comparison between CD1 and CD2. Similar dispersive interactions of CD1 and CD2 are attributed to their similar length of spacer arms. CD2 which contains OEG spacer arm has relative weaker HBD acidity but stronger HBA basicity. CD stationary phases display no serious different methylene selectivity and higher polar selectivity than in the case of C18. Higher acid selectivity and lower basic selectivity are observed on CD2 than on CD1. Distinctive retention properties and good complementary separation selectivity to C18 make the novel CD bonded stationary phases available for more application in RPLC.

Nanoparticles of conjugated polymers prepared from phase-separated films of phospholipids and polymers for biomedical applications.

PubMed

Yoon, Jungju; Kwag, Jungheon; Shin, Tae Joo; Park, Joonhyuck; Lee, Yong Man; Lee, Yebin; Park, Jonghyup; Heo, Jung; Joo, Chulmin; Park, Tae Jung; Yoo, Pil J; Kim, Sungjee; Park, Juhyun

2014-07-09

Phase separation in films of phospholipids and conjugated polymers results in nanoassemblies because of a difference in the physicochemical properties between the hydrophobic polymers and the polar lipid heads, together with the comparable polymer side-chain lengths to lipid tail lengths, thus producing nanoparticles of conjugated polymers upon disassembly in aqueous media by the penetration of water into polar regions of the lipid heads. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ternary Polymeric Composites Exhibiting Bulk and Surface Quadruple-Shape Memory Properties.

PubMed

Buffington, Shelby Lois; Posnick, Benjamin M; Paul, Justine Elizabeth; Mather, Patrick T

2018-06-19

We report the design and characterization of a multiphase quadruple shape memory composite capable of switching between 4 programmed shapes, three temporary and one permanent. Our approach combined two previously reported fabrication methods by embedding an electrospun mat of PCL in a miscible blend of epoxy monomers and PMMA as a composite matrix. As epoxy polymerization occurred the matrix underwent phase separation between the epoxy and PMMA materials. This created a multiphase composite with PCL fibers and a two-phase matrix composed of phase-separated epoxy and PMMA. The resulting composite demonstrated three separate thermal transitions and amenability to mechanical programming of three separate temporary shapes in addition to one final, equilibrium shape. In addition, quadruple surface shape memory abilities are successfully demonstrated. The versatility of this approach offers a large degree of design flexibility for multi-shape memory materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polysaccharide-derived mesoporous materials (Starbon®) for sustainable separation of complex mixtures.

PubMed

Zuin, Vânia G; Budarin, Vitaliy L; De Bruyn, Mario; Shuttleworth, Peter S; Hunt, Andrew J; Pluciennik, Camille; Borisova, Aleksandra; Dodson, Jennifer; Parker, Helen L; Clark, James H

2017-09-21

The recovery and separation of high value and low volume extractives are a considerable challenge for the commercial realisation of zero-waste biorefineries. Using solid-phase extractions (SPE) based on sustainable sorbents is a promising method to enable efficient, green and selective separation of these complex extractive mixtures. Mesoporous carbonaceous solids derived from renewable polysaccharides are ideal stationary phases due to their tuneable functionality and surface structure. In this study, the structure-separation relationships of thirteen polysaccharide-derived mesoporous materials and two modified types as sorbents for ten naturally-occurring bioactive phenolic compounds were investigated. For the first time, a comprehensive statistical analysis of the key molecular and surface properties influencing the recovery of these species was carried out. The obtained results show the possibility of developing tailored materials for purification, separation or extraction, depending on the molecular composition of the analyte. The wide versatility and application span of these polysaccharide-derived mesoporous materials offer new sustainable and inexpensive alternatives to traditional silica-based stationary phases.

Processing FeB03 glass-ceramics in space

NASA Technical Reports Server (NTRS)

Li, C. T.

1976-01-01

The possibility of preparing FeBO3 glass-ceramic in space is explored. A transparent glass-ceramic of FeBO3, due to its unique properties could be an excellent material for magneto-optic applications which currently utilize high price materials such as single crystals of Ga-YIG. The unique magneto-optic properties of FeBO3 were found to come from glass-ceramic but not from the glass form. It was anticipated and later confirmed that the FeBO3 glass-ceramics could not be prepared on earth. Phase separation and iron valence reduction, were identified as the two terrestrial manufacturing obstacles. Since the phase separation problem could be overcome by space processing, the preparation of FeBO3 glass-ceramic in space appears attractive.

Microrheology and microstructure of water-in-water emulsions containing sodium caseinate and locust bean gum.

PubMed

Moschakis, Thomas; Chantzos, Nikos; Biliaderis, Costas G; Dickinson, Eric

2018-05-23

The mechanical response on the microscale of phase-separated water-in-water emulsions containing sodium caseinate (SCN) and locust bean gum (LBG) has been monitored by confocal laser scanning microscopy and particle tracking microrheology. Mixed biopolymer systems exhibiting phase-separated micro-regions were enriched in either protein or polysaccharide in the continuous or dispersed phase, depending on the weight ratio of the two biopolymers. Measurements of the tracking of charged probe particles revealed that the local rheological properties of protein-rich regions were considerably lower than that of LBG-rich domains for all the biopolymer ratios examined. At pH 7 in the absence of added salt, the viscosity of the protein-rich regions was little affected by an increase in overall LBG concentration, which is consistent with the phase separation mechanism in the mixed solution of charged (SCN) and uncharged (LBG) biopolymers being dominated by the relative entropy of the counter-ions associated with the charged protein molecules. Addition of salt was found to produce an enhancement in the level of thermodynamic incompatibility, leading to faster and more pronounced phase separation, and altering the micro-viscosity of protein-rich regions. At high ionic strength, it was also noted that there was a pronounced accumulation of incorporated probe particles at the liquid-liquid interface. The microrheological properties of the SCN-rich regions were found to be substantially pH-dependent in the range 7 > pH > 5.4. By adjusting the acidification conditions and the biopolymer ratio, discrete protein-based microspheres were generated with potential applications as a functional food ingredient.

Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe

NASA Astrophysics Data System (ADS)

Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.

2018-04-01

The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.

Manipulating electronic phase separation in strongly correlated oxides with an ordered array of antidots

DOE PAGES

Zhang, Kai; Du, Kai; Liu, Hao; ...

2015-07-20

The interesting transport and magnetic properties in manganites depend sensitively on the nucleation and growth of electronic phase-separated domains. In this paper, by fabricating antidot arrays in La 0.325Pr 0.3Ca 0.375MnO 3 (LPCMO) epitaxial thin films, we create ordered arrays of micrometer-sized ferromagnetic metallic (FMM) rings in the LPCMO films that lead to dramatically increased metal–insulator transition temperatures and reduced resistances. The FMM rings emerge from the edges of the antidots where the lattice symmetry is broken. Based on our Monte Carlo simulation, these FMM rings assist the nucleation and growth of FMM phase domains increasing the metal–insulator transition withmore » decreasing temperature or increasing magnetic field. Finally, this study points to a way in which electronic phase separation in manganites can be artificially controlled without changing chemical composition or applying external field.« less

Characterization of Polysulfone Membranes Prepared with Thermally Induced Phase Separation Technique

NASA Astrophysics Data System (ADS)

Tiron, L. G.; Pintilie, Ș C.; Vlad, M.; Birsan, I. G.; Baltă, Ș

2017-06-01

Abstract Membrane technology is one of the most used water treatment technology because of its high removal efficiency and cost effectiveness. Preparation techniques for polymer membranes show an important aspect of membrane properties. Generally, polysulfone (PSf) and polyethersulfone (PES) are used for the preparation of ultrafiltration (UF) membranes. Polysulfone (PSf) membranes have been widely used for separation and purification of different solutions because of their excellent chemical and thermal stability. Polymeric membranes were obtained by phase inversion method. The polymer solution introduced in the nonsolvent bath (distilled water) initiate the evaporation of the solvent from the solution, this phenomenon has a strong influence on the transport properties. The effect of the coagulation bath temperature on the membrane properties is of interest for this study. Membranes are characterized by pure water flux, permeability, porosity and retention of methylene blue. The low temperature of coagulation bath improve the membrane’s rejection and its influence was most notable.

The effect of polyether functional polydimethylsiloxane on surface and thermal properties of waterborne polyurethane

NASA Astrophysics Data System (ADS)

Zheng, Guikai; Lu, Ming; Rui, Xiaoping

2017-03-01

Waterborne polyurethanes (WPU) modified with polyether functional polydimethylsiloxane (PDMS) were synthesized by pre-polymerization method using isophorone diisocyanate (IPDI) and 1,4-butanediol (BDO) as hard segments and polybutylene adipate glycol (PBA) and polyether functional PDMS as soft segments. The effect of polyether functional PDMS on phase separation, thermal properties, surface properties including surface composition, morphology and wettability were investigated by FTIR, contact angle measurements, ARXPS, SEM-EDS, AFM, TG and DSC. The results showed that the compatibility between urethane hard segment and PDMS modified with polyether was good, and there was no distinct phase separation in both bulk and surface of WPU films. The degradation temperature and low temperature flexibility increased with increasing amounts of polyether functional PDMS. The enrichment of polyether functional PDMS with low surface energy on the surface imparted excellent hydrophobicity to WPU films.

Preparation and evaluation of diblock copolymer-grafted silica by sequential surface initiated-atom transfer radical polymerization for reverse-phase/ion-exchange mixed-mode chromatography.

PubMed

Bo, Chun Miao; Wang, Chaozhan; Wei, Yin Mao

2017-12-01

A novel approach that involved the grafting of diblock copolymer with two types of monomer onto substrate by sequential surface initiated-atom transfer radical polymerization was proposed to prepare a mixed-mode chromatographic stationary phase. The distinguishing feature of this method is that it can be applied in the preparation of various mixed-mode stationary phases. In this study, a new reverse-phase/ion-exchange stationary phase was prepared by grafting hydrophobic styrene and cationic sodium 4-styrenesulfonate by the proposed approach onto silica surface. The chromatographic properties of the prepared stationary phase were evaluated by the separation of benzene derivatives, anilines, and β-agonists, and by the effect of pH values and acetonitrile content on the retention. Compared with typical RP columns, the prepared stationary phase achieved the better resolution and higher selectivity at a shorter separation time and lower organic content. Moreover, the application of the prepared column was proved by separating widely distributed polar and charged compounds simultaneously. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Air separation and oxygen storage properties of hexagonal rare-earth manganites

NASA Astrophysics Data System (ADS)

Abughayada, Castro

This dissertation presents evaluation results of hexagonal Y1-x RxMnO3+delta (R = Er, Y, Dy, Pr, La, Tb and Ho) rare-earth manganites for prospective air separation applications. In these materials, oxygen content is sensitively dependent on the surrounding conditions of temperature and/or oxygen partial pressure, and therefore they exhibit the ability to selectively absorb, store, and release significant amounts of separated oxygen from air. This study presents a full characterization of their thermogravimetric characteristics and air separation capabilities. With the expected potential impact of oxygen content on the physical properties of these materials, the scope of this work is expanded to explore other relevant properties such as magnetic, transport, and dilatometric characteristics. Single-phase polycrystalline samples of these materials were achieved in the hexagonal P63cm phase through solid state reaction at elevated temperatures. Further annealings under reducing conditions were required for samples with large rare-earth cations in order to suppress the competing perovskite structure and form in the anticipated hexagonal phase. Thermogravimetric measurements in oxygen atmospheres demonstrated that samples with the larger R ionic radii show rapid and reversible incorporation of significant amounts of excess oxygen (0.41 > delta > 0) at an unusual low temperature range ~190-325 °C. The reversible oxygen storage characteristics of HoMnO3+delta and related materials shown by the fast incorporation and release of interstitial oxygen at easily accessible elevated temperatures of ~300 °C demonstrate the feasibility and potential for low-cost thermal swing adsorption TSA process for oxygen separation and enrichment from air. Neutron and X-ray powder diffraction measurements confirmed the presence of three line compounds RMnO3+delta, the oxygen stoichiometric P6 3cm (delta = 0 for all R), the intermediate oxygen content superstructure phase R3c (delta ~ 0.28 for R = Ho, Dy, Dy0.5Y0.5, and Dy0.3Y0.7) constructed by tripling the c-axis of the original unit cell, and the highly oxygen-loaded Pca21 phase (delta = 0.40 for all R). In-situ synchrotron diffraction showed thermal stability of these single phases and their coexistence ranges, demonstrating that the stability of the delta = 0.28 phase increases with the ionic size of the R ion. The magnetic properties of the multiferroic RMnO3+delta were found to be dependent on the oxygen content of these compounds. Below the magnetic ordering temperatures, samples with higher oxygen content showed slightly decreased magnetization relative to the less oxygenated ones. Dilatometry measurements suggest that the thermal expansion coefficient TEC of the oxygen-loaded Pca21 phase is slightly larger than that of the stoichiometric P63cm phase. The calculated Pca21 to P63cm chemical expansion coefficient 14.38 x 10-3 [mole-O]-1 was found to be within the expected range for the hexagonal Y0.97La0.03MnO3+delta sample.

Spacelab experiment definition study on phase transition and critical phenomena in fluids: Interim report on experimental justification

NASA Technical Reports Server (NTRS)

Moldover, M. R.; Hocken, M. R.; Gammon, R. W.; Sengers, J. V.

1976-01-01

Pure fluids and fluid mixtures near critical points are identified and are related to the progress of several disciplines. Consideration is given to thermodynamic properties, transport properties, and the complex nonlinear phenomena which occur when fluids undergo phase transitions in the critical region. The distinction is made between practical limits which may be extended by advances in technology and intrinsic ones which arise from the modification of fluid properties by the earth's gravitational field. The kinds of experiments near critical points which could best exploit the low gravity environment of an orbiting laboratory are identified. These include studies of the index of refraction, constant volume specific heat, and phase separation.

Sedimentation of a two-dimensional colloidal mixture exhibiting liquid-liquid and gas-liquid phase separation: a dynamical density functional theory study.

PubMed

Malijevský, Alexandr; Archer, Andrew J

2013-10-14

We present dynamical density functional theory results for the time evolution of the density distribution of a sedimenting model two-dimensional binary mixture of colloids. The interplay between the bulk phase behaviour of the mixture, its interfacial properties at the confining walls, and the gravitational field gives rise to a rich variety of equilibrium and non-equilibrium morphologies. In the fluid state, the system exhibits both liquid-liquid and gas-liquid phase separation. As the system sediments, the phase separation significantly affects the dynamics and we explore situations where the final state is a coexistence of up to three different phases. Solving the dynamical equations in two-dimensions, we find that in certain situations the final density profiles of the two species have a symmetry that is different from that of the external potentials, which is perhaps surprising, given the statistical mechanics origin of the theory. The paper concludes with a discussion on this.

Nano-phase separation and structural ordering in silica-rich mixed network former glasses.

PubMed

Liu, Hao; Youngman, Randall E; Kapoor, Saurabh; Jensen, Lars R; Smedskjaer, Morten M; Yue, Yuanzheng

2018-06-13

We investigate the structure, phase separation, glass transition, and crystallization in a mixed network former glass series, i.e., B2O3-Al2O3-SiO2-P2O5 glasses with varying SiO2/B2O3 molar ratio. All the studied glasses exhibit two separate glassy phases: droplet phase (G1) with the size of 50-100 nm and matrix phase (G2), corresponding to a lower calorimetric glass transition temperature (Tg1) and a higher one (Tg2), respectively. Both Tg values decrease linearly with the substitution of B2O3 for SiO2, but the magnitude of the decrease is larger for Tg1. Based on nuclear magnetic resonance and Raman spectroscopy results, we infer that the G1 phase is rich in boroxol rings, while the G2 phase mainly involves the B-O-Si network. Both phases contain BPO4- and AlPO4-like units. Ordered domains occur in G2 upon isothermal and dynamic heating, driven by the structural heterogeneity in the as-prepared glasses. The structural ordering lowers the activation energy of crystal growth, thus promoting partial crystallization of G2. These findings are useful for understanding glass formation and phase separation in mixed network former oxide systems, and for tailoring their properties.

Enhanced thermoelectric properties of phase-separating bismuth selenium telluride thin films via a two-step method

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

Takashiri, Masayuki, E-mail: takashiri@tokai-u.jp; Kurita, Kensuke; Hagino, Harutoshi

2015-08-14

A two-step method that combines homogeneous electron beam (EB) irradiation and thermal annealing has been developed to enhance the thermoelectric properties of nanocrystalline bismuth selenium telluride thin films. The thin films, prepared using a flash evaporation method, were treated with EB irradiation in a N{sub 2} atmosphere at room temperature and an acceleration voltage of 0.17 MeV. Thermal annealing was performed under Ar/H{sub 2} (5%) at 300 °C for 60 min. X-ray diffraction was used to determine that compositional phase separation between bismuth telluride and bismuth selenium telluride developed in the thin films exposed to higher EB doses and thermal annealing. We proposemore » that the phase separation was induced by fluctuations in the distribution of selenium atoms after EB irradiation, followed by the migration of selenium atoms to more stable sites during thermal annealing. As a result, thin film crystallinity improved and mobility was significantly enhanced. This indicates that the phase separation resulting from the two-step method enhanced, rather than disturbed, the electron transport. Both the electrical conductivity and the Seebeck coefficient were improved following the two-step method. Consequently, the power factor of thin films that underwent the two-step method was enhanced to 20 times (from 0.96 to 21.0 μW/(cm K{sup 2}) that of the thin films treated with EB irradiation alone.« less

On hierarchical solutions to the BBGKY hierarchy

NASA Technical Reports Server (NTRS)

Hamilton, A. J. S.

1988-01-01

It is thought that the gravitational clustering of galaxies in the universe may approach a scale-invariant, hierarchical form in the small separation, large-clustering regime. Past attempts to solve the Born-Bogoliubov-Green-Kirkwood-Yvon (BBGKY) hierarchy in this regime have assumed a certain separable hierarchical form for the higher order correlation functions of galaxies in phase space. It is shown here that such separable solutions to the BBGKY equations must satisfy the condition that the clustered component of the solution has cluster-cluster correlations equal to galaxy-galaxy correlations to all orders. The solutions also admit the presence of an arbitrary unclustered component, which plays no dyamical role in the large-clustering regime. These results are a particular property of the specific separable model assumed for the correlation functions in phase space, not an intrinsic property of spatially hierarchical solutions to the BBGKY hierarchy. The observed distribution of galaxies does not satisfy the required conditions. The disagreement between theory and observation may be traced, at least in part, to initial conditions which, if Gaussian, already have cluster correlations greater than galaxy correlations.

Military Wives' Transition and Coping: Deployment and the Return Home

PubMed Central

Marnocha, Suzanne

2012-01-01

The objective of this qualitative study is to explore the experiences of wives of deployed soldiers. Semistructured interviews were used to answer the research questions. Meleis' Transitions Theory was used to guide the understanding of the wives' experiences. Phase One: news of deployment, property of awareness, themes of emotional chaos and making preparations. Phase Two: during deployment, property of engagement, themes of taking the reins and placing focus elsewhere, along with the property of change and difference, with themes of emotional and physical turmoil, staying strong, and reaching out. Phase Three: after deployment, property of time span, themes of absence makes the heart grow fonder and reestablishing roles. The study concluded that the wife often feels forgotten during deployment. Nurses can give better care by understanding how the different phases of deployment and separation affect the wife's coping ability and her physical and emotional health. PMID:22844613

Organised surfactant assemblies in analytical atomic spectrometry

NASA Astrophysics Data System (ADS)

Sanz-Medel, Alfredo; Fernandez de la Campa, Maria del Rosario; Gonzalez, Elisa Blanco; Fernandez-Sanchez, Maria Luisa

1999-02-01

The use of surfactant-based organised assemblies in analytical atomic spectroscopy is extensively and critically reviewed along three main lines: first, the ability of organised media to enhance detection of atomic spectroscopic methods by favourable manipulation of physical and chemical properties of the sample solution second, the extension of separation mechanisms by resorting to organised media and third a discussion of synergistic combinations of liquid chromatography separations and atomic detectors via the use of vesicular mobile phases. Changes in physical properties of sample solutions aspirated in atomic spectrometry by addition of surfactants can be advantageously used in at least four different ways: (i) to improve nebulisation efficiency; (ii) to enhance wettability of solid surfaces used for atomisation; (iii) to improve compatibility between aqueous and organic phases; and (iv) to achieve good dispersion of small particles in "slurry" techniques. Controversial results and statements published so far are critically discussed. The ability of surfactant-based organised assemblies, such as micelles and vesicles, to organise reactants at the molecular level has also been applied to enhance the characteristics of chemical generation of volalite species of metals and semi-metals (e.g., hydride or ethylide generation of As, Pb, Cd, Se, Sn, and cold vapour Hg generation) used in atomic methods. Enhancements in efficiency/transport of volatile species, increases in the reaction kinetics, stabilisation of some unstable species and changes in the selectivity of the reactions by surfactants are dealt with. Non-chromatographic cloud-point separations to design pre-concentration procedures with subsequent metal determination by atomic methods are addressed along with chromatographic separations of expanded scope by addition of surfactants to the conventional aqueous mobile phases of reversed-phase high-performance liquid chromatography. Finally, the synergistic effect of using vesicles to improve both the separation capabilities of reversed-phase HPLC and the detectability of atomic detectors by on-line vesicular hydride generation is described. In particular, the possible separation mechanisms responsible for micellar and vesicular mobile phases in reversed-phase chromatographies are analysed and compared. The possible effect of modification of stationary phases by monomers of the surfactants should also be taken into account. The application of such on-line couplings to develop new hybrid approaches to tackle modern problems of trace element speciation for As, Hg, Se, and Cd completes this revision of the present interface between analytical atomic spectroscopy and surfactant-based organised assemblies.

Influence of defect distribution on the thermoelectric properties of FeNbSb based materials.

PubMed

Guo, Shuping; Yang, Kaishuai; Zeng, Zhi; Zhang, Yongsheng

2018-05-21

Doping and alloying are important methodologies to improve the thermoelectric performance of FeNbSb based materials. To fully understand the influence of point defects on the thermoelectric properties, we have used density functional calculations in combination with the cluster expansion and Monte Carlo methods to examine the defect distribution behaviors in the mesoscopic FeNb1-xVxSb and FeNb1-xTixSb systems. We find that V and Ti exhibit different distribution behaviors in FeNbSb at low temperature: forming the FeNbSb-FeVSb phase separations in the FeNb1-xVxSb system but two thermodynamically stable phases in FeNb1-xTixSb. Based on the calculated effective mass and band degeneracy, it seems the doping concentration of V or Ti in FeNbSb has little effect on the electrical properties, except for one of the theoretically predicted stable Ti phases (Fe6Nb5Ti1Sb6). Thus, an essential methodology to improve the thermoelectric performance of FeNbSb should rely on phonon scattering to decrease the thermal conductivity. According to the theoretically determined phase diagrams of Fe(Nb,V)Sb and Fe(Nb,Ti)Sb, we propose the (composition, temperature) conditions for the experimental synthesis to improve the thermoelectric performance of FeNbSb based materials: lowering the experimental preparation temperature to around the phase boundary to form a mixture of the solid solution and phase separation. The point defects in the solid solution effectively scatter the short-wavelength phonons and the (coherent or incoherent) interfaces introduced by the phase separation can additionally scatter the middle-wavelength phonons to further decrease the thermal conductivity. Moreover, the induced interfaces could enhance the Seebeck coefficient as well, through the energy filtering effect. Our results give insight into the understanding of the impact of the defect distribution on the thermoelectric performance of materials and strengthen the connection between theoretical predictions and experimental measurements.

Monolithic poly[(trimethylsilyl-4-methylstyrene)-co- bis(4-vinylbenzyl)dimethylsilane] stationary phases for the fast separation of proteins and oligonucleotides.

PubMed

Jakschitz, Thomas A E; Huck, Christian W; Lubbad, Said; Bonn, Günther K

2007-04-13

In this paper the synthesis, optimisation and application of a silane based monolithic copolymer for the rapid separation of proteins and oligonucleotides is described. The monolith was prepared by thermal initiated in situ copolymerisation of trimethylsilyl-4-methylstyrene (TMSiMS) and bis(4-vinylbenzyl)dimethylsilane (BVBDMSi) in a silanised 200 microm I.D. fused silica column. Different ratios of monomer and crosslinker, as well as different ratios of micro- (toluene) and macro-porogen (2-propanol) were used for optimising the physical properties of the stationary phase regarding separation efficiency. The prepared monolithic stationary phases were characterised by measurement of permeability with different solvents, determination of pore size distribution by mercury intrusion porosimetry (MIP). Morphology was studied by scanning electron microscopy (SEM). Applying optimised conditions, a mixture comprised of five standard proteins ribunuclease A, cytochrome c, alpha-lactalbumine, myoglobine and ovalbumine was separated within 1 min by ion-pair reversed-phase liquid chromatography (IP-RPLC) obtaining half-height peak widths between 1.8 and 2.4 s. Baseline separation of oligonucleotides d(pT)(12-18) was achieved within 1.8 min obtaining half-height peak widths between 3.6 and 5.4 s. The results demonstrate the high potential of this stationary phase for fast separation of high-molecular weight biomolecules such as oligonucleotides and proteins.

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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2016-01-04

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

Correlative Energy-Dispersive X-Ray Spectroscopic Tomography and Atom Probe Tomography of the Phase Separation in an Alnico 8 Alloy.

PubMed

Guo, Wei; Sneed, Brian T; Zhou, Lin; Tang, Wei; Kramer, Matthew J; Cullen, David A; Poplawsky, Jonathan D

2016-12-01

Alnico alloys have long been used as strong permanent magnets because of their ferromagnetism and high coercivity. Understanding their structural details allows for better prediction of the resulting magnetic properties. However, quantitative three-dimensional characterization of the phase separation in these alloys is still challenged by the spatial quantification of nanoscale phases. Herein, we apply a dual tomography approach, where correlative scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopic (EDS) tomography and atom probe tomography (APT) are used to investigate the initial phase separation process of an alnico 8 alloy upon non-magnetic annealing. STEM-EDS tomography provides information on the morphology and volume fractions of Fe-Co-rich and Νi-Al-rich phases after spinodal decomposition in addition to quantitative information of the composition of a nanoscale volume. Subsequent analysis of a portion of the same specimen by APT offers quantitative chemical information of each phase at the sub-nanometer scale. Furthermore, APT reveals small, 2-4 nm Fe-rich α 1 phases that are nucleated in the Ni-rich α 2 matrix. From this information, we show that phase separation of the alnico 8 alloy consists of both spinodal decomposition and nucleation and growth processes. The complementary benefits and challenges associated with correlative STEM-EDS and APT are discussed.

Correlative Energy-Dispersive X-Ray Spectroscopic Tomography and Atom Probe Tomography of the Phase Separation in an Alnico 8 Alloy

DOE PAGES

Guo, Wei; Sneed, Brian T.; Zhou, Lin; ...

2016-12-21

Alnico alloys have long been used as strong permanent magnets because of their ferromagnetism and high coercivity. Understanding their structural details allows for better prediction of the resulting magnetic properties. However, quantitative three-dimensional characterization of the phase separation in these alloys is still challenged by the spatial quantification of nanoscale phases. Herein, we apply a dual tomography approach, where correlative scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopic (EDS) tomography and atom probe tomography (APT) are used to investigate the initial phase separation process of an alnico 8 alloy upon non-magnetic annealing. STEM-EDS tomography provides information on the morphology andmore » volume fractions of Fe–Co-rich and Νi–Al-rich phases after spinodal decomposition in addition to quantitative information of the composition of a nanoscale volume. Subsequent analysis of a portion of the same specimen by APT offers quantitative chemical information of each phase at the sub-nanometer scale. Furthermore, APT reveals small, 2–4 nm Fe-rich α 1 phases that are nucleated in the Ni-rich α 2 matrix. From this information, we show that phase separation of the alnico 8 alloy consists of both spinodal decomposition and nucleation and growth processes. Lastly, we discuss the complementary benefits and challenges associated with correlative STEM-EDS and APT.« less

Functional Domains of NEAT1 Architectural lncRNA Induce Paraspeckle Assembly through Phase Separation.

PubMed

Yamazaki, Tomohiro; Souquere, Sylvie; Chujo, Takeshi; Kobelke, Simon; Chong, Yee Seng; Fox, Archa H; Bond, Charles S; Nakagawa, Shinichi; Pierron, Gerard; Hirose, Tetsuro

2018-06-21

A class of long noncoding RNAs (lncRNAs) has architectural functions in nuclear body construction; however, specific RNA domains dictating their architectural functions remain uninvestigated. Here, we identified the domains of the architectural NEAT1 lncRNA that construct paraspeckles. Systematic deletion of NEAT1 portions using CRISPR/Cas9 in haploid cells revealed modular domains of NEAT1 important for RNA stability, isoform switching, and paraspeckle assembly. The middle domain, containing functionally redundant subdomains, was responsible for paraspeckle assembly. Artificial tethering of the NONO protein to a NEAT1_2 mutant lacking the functional subdomains rescued paraspeckle assembly, and this required the NOPS dimerization domain of NONO. Paraspeckles exhibit phase-separated properties including susceptibility to 1,6-hexanediol treatment. RNA fragments of the NEAT1_2 subdomains preferentially bound NONO/SFPQ, leading to phase-separated aggregates in vitro. Thus, we demonstrate that the enrichment of NONO dimers on the redundant NEAT1_2 subdomains initiates construction of phase-separated paraspeckles, providing mechanistic insights into lncRNA-based nuclear body formation. Copyright © 2018 Elsevier Inc. All rights reserved.

Retention and effective diffusion of model metabolites on porous graphitic carbon.

PubMed

Lunn, Daniel B; Yun, Young J; Jorgenson, James W

2017-12-29

The study of metabolites in biological samples is of high interest for a wide range of biological and pharmaceutical applications. Reversed phase liquid chromatography is a common technique used for the separation of metabolites, but it provides little retention for polar metabolites. An alternative to C18 bonded phases, porous graphitic carbon has the ability to provide significant retention for both non-polar and polar analytes. The goal of this work is to study the retention and effective diffusion properties of porous graphitic carbon, to see if it is suitable for the wide injection bands and long run times associated with long, packed capillary-scale separations. The retention of a set of standard metabolites was studied for both stationary phases over a wide range of mobile phase conditions. This data showed that porous graphitic carbon benefits from significantly increased retention (often >100 fold) under initial gradient conditions for these metabolites, suggesting much improved ability to focus a wide injection band at the column inlet. The effective diffusion properties of these columns were studied using peak-parking experiments with the standard metabolites under a wide range of retention conditions. Under the high retention conditions, which can be associated with retention after injection loading for gradient separations, D eff /D m ∼0.1 for both the C18-bonded and porous graphitic carbon columns. As C18 bonded particles are widely, and successfully utilized for long gradient separations without issue of increasing peak width from longitudinal diffusion, this suggests that porous graphitic carbon should be amenable for long runtime gradient separations as well. Copyright © 2017 Elsevier B.V. All rights reserved.

Observation of Internal Photoinduced Electron and Hole Separation in Hybrid Two-Dimentional Perovskite Films.

PubMed

Liu, Junxue; Leng, Jing; Wu, Kaifeng; Zhang, Jun; Jin, Shengye

2017-02-01

Two-dimensional (2D) organolead halide perovskites are promising for various optoelectronic applications. Here we report a unique spontaneous charge (electron/hole) separation property in multilayered (BA) 2 (MA) n-1 Pb n I 3n+1 (BA = CH 3 (CH 2 ) 3 NH 3 + , MA = CH 3 NH 3 + ) 2D perovskite films by studying the charge carrier dynamics using ultrafast transient absorption and photoluminescence spectroscopy. Surprisingly, the 2D perovskite films, although nominally prepared as "n = 4", are found to be mixture of multiple perovskite phases, with n = 2, 3, 4 and ≈ ∞, that naturally align in the order of n along the direction perpendicular to the substrate. Driven by the band alignment between 2D perovskites phases, we observe consecutive photoinduced electron transfer from small-n to large-n phases and hole transfer in the opposite direction on hundreds of picoseconds inside the 2D film of ∼358 nm thickness. This internal charge transfer efficiently separates electrons and holes to the upper and bottom surfaces of the films, which is a unique property beneficial for applications in photovoltaics and other optoelectronics devices.

Phthalimide Copolymer Solar Cells

NASA Astrophysics Data System (ADS)

Xin, Hao; Guo, Xugang; Ren, Guoqiang; Kim, Felix; Watson, Mark; Jenekhe, Samson

2010-03-01

Photovoltaic properties of bulk heterojunction solar cells based on phthalimide donor-acceptor copolymers have been investigated. Due to the strong π-π stacking of the polymers, the state-of-the-art thermal annealing approach resulted in micro-scale phase separation and thus negligible photocurrent. To achieve ideal bicontinuous morphology, different strategies including quickly film drying and mixed solvent for film processing have been explored. In these films, nano-sale phase separation was achieved and a power conversion efficiency of 3.0% was obtained. Absorption and space-charge limited current mobility measurements reveal similar light harvesting and hole mobilities in all the films, indicating that the morphology is the dominant factor determining the photovoltaic performance. Our results demonstrate that for highly crystalline and/or low-solubility polymers, finding a way to prevent polymer aggregation and large scale phase separation is critical to realizing high performance solar cells.

Nanoscale ferromagnetism in phase-separated manganites

NASA Astrophysics Data System (ADS)

Mori, S.; Horibe, Y.; Asaka, T.; Matsui, Y.; Chen, C. H.; Cheong, S. W.

2007-03-01

Magnetic domain structures in phase-separated manganites were investigated by low-temperature Lorentz electron microscopy, in order to understand some unusual physical properties such as a colossal magnetoresistance (CMR) effect and a metal-to-insulator transition. In particular, we examined a spatial distribution of the charge/orbital-ordered (CO/OO) insulator state and the ferromagnetic (FM) metallic one in phase-separated manganites; Cr-doped Nd0.5Ca0.5MnO3 and ( La1-xPrx)CaMnO3 with x=0.375, by obtaining both the dark-field images and Lorentz electron microscopic ones. It is found that an unusual coexistence of the CO/OO and FM metallic states below a FM transition temperature in the two compounds. The present experimental results clearly demonstrated the coexisting state of the two distinct ground states in manganites.

Preparation and retention mechanism study of graphene and graphene oxide bonded silica microspheres as stationary phases for high performance liquid chromatography.

PubMed

Zhang, Xiaoqiong; Chen, Sha; Han, Qiang; Ding, Mingyu

2013-09-13

Graphene oxide (GO) bonded stationary phase for high performance liquid chromatography (HPLC) was fabricated by coating GO sheets onto aminosilica microspheres via covalent coupling. Graphene (G) functionalized HPLC stationary phase was then prepared through hydrazine reduction of GO bonded silica (GO@SiO2) composite, which was the first example of using graphene as stationary-phase component for HPLC. Effective separations of the tested neutral and polar compounds on both GO@SiO2 and graphene bonded silica (G@SiO2) columns were achieved under the optimal experimental conditions. Compared with commercial C18 column, the different chromatographic performances of GO and graphene bonded columns were ascribed to their unique retention mechanisms. The polyaromatic scaffold of GO and graphene gives π-π stacking property and hydrophobic effect, and other retention mechanisms, such as π-π electron-donor-acceptor (EDA) interaction for the separation of nitroaromatic compounds and hydrogen bonding for hydroxyl and amino compounds, may also be taken into consideration. Experimental results indicated that the mixed-mode retention mechanism can facilitate the separation of analytes with similar hydrophobicity, which is a unique property compared with C18 column. Additionally, G@SiO2 showed higher affinity to aromatic analytes in contrast with GO@SiO2 and its retention mechanism was not consistent with the typical reversed phase behavior. The separation of aromatic compounds on G@SiO2 column relies primarily on the π-π stacking interaction and then the hydrophobicity, while the two interactions have equal shares on GO@SiO2 column. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

The Influence of Mo, Cr and B Alloying on Phase Transformation and Mechanical Properties in Nb Added High Strength Dual Phase Steels

NASA Astrophysics Data System (ADS)

Girina, O.; Fonstein, N.; Yakubovsky, O.; Panahi, D.; Bhattacharya, D.; Jansto, S.

The influence of Nb, Mo, Cr and B on phase transformations and mechanical properties are studied in a 0.15C-2.0Mn-0.3Si-0.020Ti dual phase steel separately and in combination. The formation and decomposition of austenite together with recrystallization of ferrite are evaluated by dilatometry and constructed CCT-diagrams in laboratory processed cold rolled material cooled after full austenitization and from intercritical temperature range. The effect of alloying elements on formation of austenite through their effect on initial hot rolled structure is taken into account. The interpretation of phase transformations during heating and cooling is supported by metallography. The effect of alloying elements on mechanical properties and structure are evaluated by annealing simulations. It has been shown that mechanical properties are strongly influenced by alloying additions such as Nb, Mo, Cr and B through their effect on ferrite formation during continuous cooling and corresponding enrichment of remaining austenite by carbon. Depending on combined effect of these alloying elements, different phase transformations can be promoted during cooling. This allows controlling of final microstructural constituents and mechanical properties.

High-aspect-ratio, silicon oxide-enclosed pillar structures in microfluidic liquid chromatography.

PubMed

Taylor, Lisa C; Lavrik, Nickolay V; Sepaniak, Michael J

2010-11-15

The present paper discusses the ability to separate chemical species using high-aspect-ratio, silicon oxide-enclosed pillar arrays. These miniaturized chromatographic systems require smaller sample volumes, experience less flow resistance, and generate superior separation efficiency over traditional packed bed liquid chromatographic columns, improvements controlled by the increased order and decreased pore size of the systems. In our distinctive fabrication sequence, plasma-enhanced chemical vapor deposition (PECVD) of silicon oxide is used to alter the surface and structural properties of the pillars for facile surface modification while improving the pillar mechanical stability and increasing surface area. The separation behavior of model compounds within our pillar systems indicated an unexpected hydrophobic-like separation mechanism. The effects of organic modifier, ionic concentration, and pressure-driven flow rate were studied. A decrease in the organic content of the mobile phase increased peak resolution while detrimentally effecting peak shape. A resolution of 4.7 (RSD = 3.7%) was obtained for nearly perfect Gaussian shaped peaks, exhibiting plate heights as low as 1.1 and 1.8 μm for fluorescein and sulforhodamine B, respectively. Contact angle measurements and DART mass spectrometry analysis indicate that our employed elastomeric soft bonding technique modifies pillar properties, creating a fortuitous stationary phase. This discovery provides evidence supporting the ability to easily functionalize PECVD oxide surfaces by gas-phase reactions.

Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

PubMed

Poole, Colin F; Lenca, Nicole

2014-08-29

Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present. Copyright © 2014 Elsevier B.V. All rights reserved.

Scattering properties of normal and cancerous tissues from human stomach based on phase-contrast microscope

NASA Astrophysics Data System (ADS)

Zhang, Hui; Li, Zhifang; Li, Hui

2012-12-01

In order to study scattering properties of normal and cancerous tissues from human stomach, we collect images for human gastric specimens by using phase-contrast microscope. The images were processed by the way of mathematics morphology. The equivalent particle size distribution of tissues can be obtained. Combining with Mie scattering theory, the scattering properties of tissues can be calculated. Assume scattering of light in biological tissue can be seen as separate scattering events by different particles, total scattering properties can be equivalent to as scattering sum of particles with different diameters. The results suggest that scattering coefficient of the cancerous tissue is significantly higher than that of normal tissue. The scattering phase function is different especially in the backscattering area. Those are significant clinical benefits to diagnosis cancerous tissue

A novel octadecylsilane functionalized graphene oxide/silica composite stationary phase for high performance liquid chromatography.

PubMed

Liang, Xiaojing; Wang, Shuai; Liu, Shujuan; Liu, Xia; Jiang, Shengxiang

2012-08-01

An octadecylsilane functionalized graphene oxide/silica stationary phase was fabricated by assembling graphene oxide onto the silica particles through an amide bond and subsequent immobilization of octadecylsilane. The chromatographic properties of the stationary phase were investigated by reversed-phase chromatography with alkylbenzenes, polycyclic aromatic hydrocarbons, amines, and phenolic compounds as the analytes. All the compounds achieved good separation on the column. The comparison between a C18 commercial column and the new stationary phase indicated that the existence of π-electron system of graphene oxide allows π-π interaction between analyte and octadecylsilane functionalized graphene oxide/silica stationary phase except for hydrophobic interaction, while only hydrophobic interaction presented between analyte and C18 commercial column. This suggests that some analytes can be better separated on the octadecylsilane functionalized graphene oxide/silica column. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating hygroscopic behavior and phase separation of organic/inorganic mixed phase aerosol particles with FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Cziczo, D. J.

2013-12-01

Atmospheric aerosol particles can be composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have very well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. For example, the deliquescence relative humidity of pure ammonium sulfate is about 80% and its efflorescence point is about 35%. This behavior of ammonium sulfate is important to atmospheric chemistry because some reactions, such as the hydrolysis of nitrogen pentoxide, occur on aqueous but not crystalline surfaces. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosol are not typically a single inorganic salt, instead they often contain organic as well as inorganic species. Mixed inorganic/organic aerosol particles, while abundant in the atmosphere, have not been studied as extensively. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. This project investigates the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O:C ratios, including glycerol, 1,2,6-hexanetriol, 1,4-butanediol and 1,5-pentanediol have been investigated. This project aims to study gas-phase exchange in these aerosol systems to determine if exchange is impacted when phase separation occurs.

Analysis of solvent induced porous PMMA-Bioglass monoliths by the phase separation method--mechanical and in vitro biocompatible studies.

PubMed

Durgalakshmi, D; Balakumar, S

2015-01-14

Mimicking three dimensional microstructural scaffolds with their requisite mechanical properties in relation to human bone is highly needed for implant applications. Various biocompatible polymers and bioactive glasses were synthesized to achieve these properties. In the present study, we have fabricated highly porous and bioactive PMMA-Bioglass scaffolds by the phase separation method. Chloroform, acetone and an ethanol-water mixture were used as the different solvent phases in preparing the scaffolds. Large interconnecting pores of sizes ∼100 to 250 μm were observed in the scaffolds and a porosity percentage up to 54% was also achieved by this method. All samples showed a brittle fracture with the highest modulus of 91 MPa for the ethanol-water prepared scaffolds. The bioactivities of the scaffolds were further studied by immersing them in simulated body fluid for 28 days. Scanning electron microscopy, X-ray diffraction and Raman spectra confirmed the formation of bioactive hydroxyl calcium apatite on the surfaces of the scaffolds.

Dynamical phase separation using a microfluidic device: experiments and modeling

NASA Astrophysics Data System (ADS)

Aymard, Benjamin; Vaes, Urbain; Radhakrishnan, Anand; Pradas, Marc; Gavriilidis, Asterios; Kalliadasis, Serafim; Complex Multiscale Systems Team

2017-11-01

We study the dynamical phase separation of a binary fluid by a microfluidic device both from the experimental and from the modeling points of view. The experimental device consists of a main channel (600 μm wide) leading into an array of 276 trapezoidal capillaries of 5 μm width arranged on both sides and separating the lateral channels from the main channel. Due to geometrical effects as well as wetting properties of the substrate, and under well chosen pressure boundary conditions, a multiphase flow introduced into the main channel gets separated at the capillaries. Understanding this dynamics via modeling and numerical simulation is a crucial step in designing future efficient micro-separators. We propose a diffuse-interface model, based on the classical Cahn-Hilliard-Navier-Stokes system, with a new nonlinear mobility and new wetting boundary conditions. We also propose a novel numerical method using a finite-element approach, together with an adaptive mesh refinement strategy. The complex geometry is captured using the same computer-aided design files as the ones adopted in the fabrication of the actual device. Numerical simulations reveal a very good qualitative agreement between model and experiments, demonstrating also a clear separation of phases.

Liquid crystalline composites toward organic photovoltaic application (Conference Presentation)

NASA Astrophysics Data System (ADS)

Shimizu, Yo; Sosa-Vargas, Lydia; Shin, Woong; Higuchi, Yumi; Itani, Hiromichi; Kawano, Koki; Dao, Quang Duy; Fujii, Akihiko; Ozaki, Masanori

2017-02-01

Liquid crystalline semiconductor is an interesting category of organic electronic materials and also has been extensively studied in terms of "Printed Electronics". For the wider diversity in research toward new applications, one can consider how to use a combination of miscibility and phase separation in liquid crystals. Here we report discotic liquid crystals in making a composite of which structural order is controlled in nano-scale toward photovoltaic applications. Discotic columnar LCs were studied on their resultant molecular order and carrier transport properties. Liquid crystals of phthalocyanine and its analogues which exhibit columnar mesomorphism with high carrier mobility (10-1 cm2/Vs) were examined with making binary phase diagrams and the correlation to carrier transport properties by TOF measurements was discussed. The shape-analogues in chemical structure shows a good miscibility even for the different lattice-type of columnar arrangement and the carrier mobility is mostly decrease except for a case of combination with a metal-free and the metal complex. For the mixtures with non-mesogenic C60 derivatives, one sees a phase-separated structure due to its immiscibility, though the columnar order is remained in a range of component ratio.Especially, in a range of the ratio, it was observed the phase separated C60 derivatives are fused into the matrix of columnar bundles, indicating C60 derivatives could be diffused in columnar arrays in molecular level.

[Anomalous Properties of Water and Aqueous Solutions at Low Temperatures].

PubMed

Matsumoto, Masakazu

2015-01-01

Water has many anomalous properties below the room temperature. The temperature range overlaps with that of the Earth's atmosphere and also with that natural life forms favor. We review the origin of the anomalous properties of water and aqueous solutions in association with the hypothetical second critical point and liquid-liquid phase separation of water hidden in the supercooled state of liquid water.

Approaches for enantioselective resolution of pharmaceuticals by miniaturised separation techniques with new chiral phases based on nanoparticles and monolithis.

PubMed

Sierra, Isabel; Marina, Maria Luisa; Pérez-Quintanilla, Damián; Morante-Zarcero, Sonia; Silva, Mariana

2016-10-01

This article discusses new developments in the preparation of nanoparticles and monoliths with emphasis upon their application as the stationary and pseudo-stationary phases for miniaturised liquid phase separation techniques, which have occurred in the last 10 years (from 2006 to the actuality). References included in this review represent current trends and state of the art in the application of these materials to the analysis, by EKC, CEC and miniaturised chromatography, of chiral compounds with environmental interest such as pharmaceuticals. Due to their extraordinary properties, columns prepared with these new chiral stationary or pseudo-stationary phases, based on materials such as gold nanoparticles, metal-organic frameworks, ordered mesoporous silicas, carbonaceous materials, polymeric-based and silica-based monoliths or molecularly imprinted materials, can usually show some improvements in the separation selectivity, column efficiency and chemical stability in comparison with conventional chiral columns available commercially. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure-property relationships in semicrystalline copolymers and ionomers

NASA Astrophysics Data System (ADS)

Wakabayashi, Katsuyuki

Many outstanding physical properties of ethylene/(meth)acrylic acid (E/(M)AA) copolymers and ionomers are associated with their nanometer-scale morphology, which consists of ethylene crystallites, amorphous segments, and acid/ionic functional groups. The goal of this dissertation is a fundamental understanding of the interplay between these structural motifs and the consequent effects on the material properties. We identify small-strain modulus as a key mechanical property and investigate its dependence upon material structure through X-ray scattering, calorimetry, and mechanical property measurements. We first treat E/(M)AA copolymers as composites of polyethylene crystallites and amorphous regions, and establish a quantitative combining rule to describe the copolymer modulus. At temperatures above the Tg of the copolymers, a monotonic increase in modulus with crystallinity is quantitatively described by the Davies equation for two-phase composites, which serves as the basis for separating the effects of amorphous and crystalline phases throughout this dissertation. The room-temperature modulus of E/(M)AA copolymers is concurrently affected by ethylene crystallinity and proximity to the amorphous phase Tg, which rises through room temperature with increasing comonomer content. In E/(M)AA ionomers, phase separation and aggregation of ionic groups provide additional stiffness and toughness. Ionomers are modeled as composites of crystallites and ionically crosslinked rubber, whose amorphous phase modulus far above the ionomer Tg is satisfactorily described by simple rubber elasticity theory. Thermomechanical analyses probe the multi-step relaxation behavior of E/(M)AA ionomers and lead to the development of a new semicrystalline ionomer morphological model, wherein secondary crystallites and ionic aggregates together form rigid percolated pathways throughout the amorphous phase. Metal soaps are oligomeric analogs of E/(M)AA ionomers, which can be blended into ionomers to achieve high ion content and in turn desirable physical properties. We assess the compatibility of various types of metal soaps with E/(M)AA ionomers, and investigate how the soap modifies the ionomers' structure and properties. The mechanical properties and phase behavior of these hybrids, which are found to differ significantly depending on the neutralizing cation type and crystallinizability of the metal soap, are traced back to various levels of molecular coassembly involving the hydrocarbon chains and/or the ionic groups of both entities.

Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography.

PubMed

Zhang, Kai; Cai, Song-Liang; Yan, Yi-Lun; He, Zi-Hao; Lin, Hui-Mei; Huang, Xiao-Ling; Zheng, Sheng-Run; Fan, Jun; Zhang, Wei-Guang

2017-10-13

Covalent organic frameworks (COFs), as an emerging class of crystalline porous organic polymers, have great potential for applications in chromatographic separation owning to their fascinating crystalline structures and outstanding properties. However, development of COF materials as novel stationary phases in high performance liquid chromatography (HPLC) is just in its infancy. Herein, we report the design and construction of a new hydrazone-linked chiral COF, termed BtaMth COF, from a chiral hydrazide building block (Mth) and present a one-pot synthetic method for the fabrication of BtaMth@SiO 2 composite for HPLC separation of isomers. The as-synthesized BtaMth chiral COF displays good crystallinity, high porosity, as well as excellent chemical stability. Meanwhile, the fabricated HPLC column by using BtaMth@SiO 2 composite as the new stationary phase exhibits high resolution performances for the separation of positional isomers including nitrotoluene and nitrochlorobenzene, as well as cis-trans isomers including beta-cypermethrin and metconazole. Additionally, some effects such as the composition of the mobile phase and column temperature for HPLC separations on the BtaMth@SiO 2 packed column also have been studied in detail. The successful applications indicate the great potentials of hydrazone-linked chiral COF-silica composite as novel stationary phase for the efficient HPLC separation. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of crystallographic orientations of grains on the global mechanical properties of steel sheets by depth sensing indentation

NASA Astrophysics Data System (ADS)

Burik, P.; Pesek, L.; Kejzlar, P.; Andrsova, Z.; Zubko, P.

2017-01-01

The main idea of this work is using a physical model to prepare a virtual material with required properties. The model is based on the relationship between the microstructure and mechanical properties. The macroscopic (global) mechanical properties of steel are highly dependent upon microstructure, crystallographic orientation of grains, distribution of each phase present, etc... We need to know the local mechanical properties of each phase separately in multiphase materials. The grain size is a scale, where local mechanical properties are responsible for the behavior. Nanomechanical testing using depth sensing indentation (DSI) provides a straightforward solution for quantitatively characterizing each of phases in microstructure because it is very powerful technique for characterization of materials in small volumes. The aim of this experimental investigation is: (i) to prove how the mixing rule works for local mechanical properties (indentation hardness HIT) in microstructure scale using the DSI technique on steel sheets with different microstructure; (ii) to compare measured global properties with properties achieved by mixing rule; (iii) to analyze the effect of crystallographic orientations of grains on the mixing rule.

Theoretical analysis of optical properties of dielectric coatings dependence on substrate subsurface defects

NASA Astrophysics Data System (ADS)

Shen, Jian; Liu, Shouhua; Shen, Zicai; Shao, Jianda; Fan, Zhengxiu

2006-03-01

A model for refractive index of stratified dielectric substrate was put forward according to theories of inhomogeneous coatings. The substrate was divided into surface layer, subsurface layer and bulk layer along the normal direction of its surface. Both the surface layer (separated into N1 sublayers of uniform thickness) and subsurface layer (separated into N2 sublayers of uniform thickness), whose refractive indices have different statistical distributions, are equivalent to inhomogeneous coatings, respectively. And theoretical deduction was carried out by employing characteristic matrix method of optical coatings. An example of mathematical calculation for optical properties of dielectric coatings had been presented. The computing results indicate that substrate subsurface defects can bring about additional bulk scattering and change propagation characteristic in thin film and substrate. Therefore, reflectance, reflective phase shift and phase difference of an assembly of coatings and substrate deviate from ideal conditions. The model will provide some beneficial theory directions for improving optical properties of dielectric coatings via substrate surface modification.

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.

Electronic Phase Separation in the Slightly Underdoped Iron Pnictide Superconductor Ba{sub 1-x}K{sub x}Fe{sub 2}As{sub 2}

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

Park, J. T.; Inosov, D. S.; Sun, G. L.

2009-03-20

Here we present a combined study of the slightly underdoped novel pnictide superconductor Ba{sub 1-x}K{sub x}Fe{sub 2}As{sub 2} by means of x-ray powder diffraction, neutron scattering, muon-spin rotation ({mu}SR), and magnetic force microscopy (MFM). Static antiferromagnetic order sets in below T{sub m}{approx_equal}70 K as inferred from the neutron scattering and zero-field-{mu}SR data. Transverse-field {mu}SR below T{sub c} shows a coexistence of magnetically ordered and nonmagnetic states, which is also confirmed by MFM imaging. We explain such coexistence by electronic phase separation into antiferromagnetic and superconducting- or normal-state regions on a lateral scale of several tens of nanometers. Our findings indicatemore » that such mesoscopic phase separation can be considered an intrinsic property of some iron pnictide superconductors.« less

Polymer composites and porous materials prepared by thermally induced phase separation and polymer-metal hybrid methods

NASA Astrophysics Data System (ADS)

Yoon, Joonsung

The primary objective of this research is to investigate the morphological and mechanical properties of composite materials and porous materials prepared by thermally induced phase separation. High melting crystallizable diluents were mixed with polymers so that the phase separation would be induced by the solidification of the diluents upon cooling. Theoretical phase diagrams were calculated using Flory-Huggins solution thermodynamics which show good agreement with the experimental results. Porous materials were prepared by the extraction of the crystallized diluents after cooling the mixtures (hexamethylbenzene/polyethylene and pyrene/polyethylene). Anisotropic structures show strong dependence on the identity of the diluents and the composition of the mixtures. Anisotropic crystal growth of the diluents was studied in terms of thermodynamics and kinetics using DSC, optical microscopy and SEM. Microstructures of the porous materials were explained in terms of supercooling and dendritic solidification. Dual functionality of the crystallizable diluents for composite materials was evaluated using isotactic polypropylene (iPP) and compatible diluents that crystallize upon cooling. The selected diluents form homogeneous mixtures with iPP at high temperature and lower the viscosity (improved processability), which undergo phase separation upon cooling to form solid particles that function as a toughening agent at room temperature. Tensile properties and morphology of the composites showed that organic crystalline particles have the similar effect as rigid particles to increase toughness; de-wetting between the particle and iPP matrix occurs at the early stage of deformation, followed by unhindered plastic flow that consumes significant amount of fracture energy. The effect of the diluents, however, strongly depends on the identity of the diluents that interact with the iPP during solidification step, which was demonstrated by comparing tetrabromobisphenol-A and phthalic anhydride. A simple method to prepare composite surfaces that can change the wettability in response to the temperature change was proposed and evaluated. Composite surfaces prepared by nanoporous alumina templates filled with polymers showed surface morphology and wettability that depend on temperature. This effect is attributed to the significant difference in thermal conductivity and the thermal expansion coefficient between the alumina and the polymers. The reversibility in thermal response depends on the properties of the polymers.

Holographic microscopy studies of emulsions

NASA Technical Reports Server (NTRS)

Witherow, W. K.

1981-01-01

A holographic microscopy system that records and observes the dynamic properties of separation of dispersed immiscible fluids is described. The holographic construction system and reconstruction system that were used to obtain particle size and distribution information from the holograms are discussed. The holographic microscopy system is used to observed the phase separating processes in immiscible fluids that were isothermally cooled into the two phase region. Nucleation, growth rates, coalescence, and particle motion are successfully demonstrated with this system. Thus a holographic particle sizing system with a resolution of 2 micrometers and a field of view of 100 cu cm was developed that provides the capability of testing the theories of separating immiscible fluids for particle number densities in the range of 10 to 10 to the 7th power particles.

Determining Individual Phase Flow Properties in a Quench and Partitioning Steel with In Situ High-Energy X-Ray Diffraction and Multiphase Elasto-Plastic Self-Consistent Method

NASA Astrophysics Data System (ADS)

Hu, Xiaohua; Choi, Kyoo Sil; Sun, Xin; Ren, Yang; Wang, Yangdong

2016-12-01

The micromechanical properties of the constituent phases were characterized for advanced high-strength steels (AHSS) produced by a quenching and partitioning (Q&P) process with in situ tensile loading under synchrotron-based, high-energy X-ray diffraction. The constituent phases present are retained austenite and three martensites (tempered, untampered, and freshly formed martensites). For the material investigated, the 200 and 220 lattice strains of the retained austenite phase were calculated by examining the changes of the X-ray diffraction peak positions during deformation. The 200 and 211 lattice strains of the various martensitic phases with similar crystal structures were determined by separating their overlapped diffraction peaks. Apart from tempered and untempered martensite, the diffraction peaks of freshly formed martensite as a result of austenite-to-martensite transformation can also be separated due to a high initial austenite volume fraction. The phase stresses are first estimated with an empirical relationship through the X-ray diffraction elastic constants. A multiphase elasto-plastic self-consistent model is next used for more accurate determination of the constitutive behaviors of the various phases by comparing the predicted lattice strain distributions and global stress-strain curves with the measured ones. The determined constitutive laws will be used for microstructure-based modeling for sheet formability of the Q&P AHSS steel.

The assembly and properties of protobiological structures - The beginnings of cellular peptide synthesis

NASA Technical Reports Server (NTRS)

Fox, S. W.; Nakashima, T.

1980-01-01

New data indicate that lysine-rich proteinoids have the ability to catalyze the synthesis of peptide bonds from a variety of amino acids and ATP. This capacity is evident in aqueous solution, in suspension of phase-separated complexes of lysine-rich proteinoid with acidic proteinoids, and in suspension of phase-separated particles composed of lysine-rich proteinoids with polynucleotides. Since the proteinoid complexes can contain other catalytic activities, including ability to catalyze internucleotide bond formation, it is inferred that the first protocells on earth already had a number of biological types of activity.

Hydrophilic organic/salt-containing aqueous two-phase solvent system for counter-current chromatography: a novel technique for separation of polar compounds.

PubMed

Liu, Dan; Zou, Xiaowei; Gao, Mingzhe; Gu, Ming; Xiao, Hongbin

2014-08-22

Hydrophilic organic/salt-containing aqueous two-phase system composing of ethanol, water and ammonium sulfate for separation polar compounds was investigated on multilayer coil associated with J-type HSCCC devices. Compared to the classical polar solvent system based on 1-butanol-water or PEG1000-ammonium sulfate-water, the water content of upper phase in ethanol-ammonium sulfate-water systems was from 53.7% to 32.8% (wt%), closed to PEG1000-ammonium sulfate-water aqueous two-phase systems and higher than 1-butanol-water (22.0%, wt%). Therefore, the polarity of ethanol-ammonium sulfate-water is in the middle of 1-butanol-water and PEG-ammonium sulfate-water system, which is quite good for separating polar compounds like phenols, nucleosides and amino acids with low partition coefficient in 1-octanol-water system. The retention of stationary phase in four elution mode on type-J counter-current chromatography devices with multilayer coil column changed from 26% to 71%. Hydrodynamic trend possess both intermediate and hydrophilic solvent system property, which closely related to the composition of solvent system. The applicability of this system was demonstrated by successful separation of adenosine, uridine guanosine and cytidine. Copyright © 2014 Elsevier B.V. All rights reserved.

Colossal magnetoresistance accompanied with magnetorelaxor behavior in phase-separated Ca1-xCexMnO3 thin films and CaMnO3/Ca0.92Ce0.08MnO3 superlattices

NASA Astrophysics Data System (ADS)

Xiang, P.-H.; Yamada, H.; Sawa, A.; Akoh, H.

2010-03-01

We report on the transport properties of electron-doped manganite Ca1-xCexMnO3 (CCMO, 0≤x≤0.08) films and superlattices composed of insulating layers CaMnO3 (CMO) and Ca0.92Ce0.08MnO3 (CCMO8), deposited on nearly lattice-matched NdAlO3 substrates. The CCMO (x =0.06 and 0.07) films show colossal magnetoresistance (CMR) accompanied with magnetorelaxor behavior, which can be ascribed to the phase separation of canted G-type antiferromagnetic metal and C-type antiferromagnetic insulator. The (CMO)m/(CCMO8)n superlattices with 4≤m, n ≤8 (unit cells) resemble the solid-solution CCMO (x =0.06 and 0.07) films in CMR and magnetorelaxor behavior, suggesting that the phase separation takes place in the superlattices. The CMR and magnetorelaxor behavior of the (CMO)m/(CCMO8)n superlattices strongly depend on the thicknesses of constituent CMO and CCMO8 layers. The origin of the phase separation in the superlattices is discussed in terms of the charge transfer and the phase competition at the interfaces.

[Separation of purines, pyrimidines, pterins and flavonoids on magnolol-bonded silica gel stationary phase by high performance liquid chromatography].

PubMed

Chen, Hong; Li, Laishen; Zhang, Yang; Zhou, Rendan

2012-10-01

A new magnolol-bonded silica gel stationary phase (MSP) was used to separate the basic drugs including four purines, eight pyrimidines, four pterins and five flavonoids as polar representative samples by high performance liquid chromatography (HPLC). To clarify the separation mechanism, a commercial ODS column was also tested under the same chromatographic conditions. The high selectivities and fast baseline separations of the above drugs were achieved by using simple mobile phases on MSP. Although there is no end-caped treatment, the peak shapes of basic drugs containing nitrogen such as purines, pyrimidines and pterins were rather symmetrical on MSP, which indicated the the magnolol as ligand with multi-sites could shield the side effect of residual silanol groups on the surface of silica gel. Although somewhat different in the separation resolution, it was found that the elution orders of some drugs were generally similar on both MSP and ODS. The hydrophobic interaction should play a significant role in the separations of the above basic drugs, which was attributed to their reversed-phase property in the nature. However, MSP could provide the additional sites for many polar solutes, which was a rational explanation for the high selectivity of MSP. For example, in the separation of purines, pyrimidines and pterins on MSP, hydrogen-bonding and dipole-dipole interactions played leading roles besides hydrophobic interaction. Some solute molecules (such as mercaptopurine, vitexicarpin) and MSP can form the strong pi-pi stacking in the separation process. All enhanced the retention and improved the separation selectivity of MSP, which facilitated the separation of the basic drugs.

First principles study on structural, lattice dynamical and thermal properties of BaCeO3

NASA Astrophysics Data System (ADS)

Zhang, Qingping; Ding, Jinwen; He, Min

2017-09-01

BaCeO3 exhibits impressive application potentials on solid oxide fuel cell electrolyte, hydrogen separation membrane and photocatalyst, owing to its unique ionic and electronic properties. In this article, the electronic structures, phonon spectra and thermal properties of BaCeO3 in orthorhombic, rhombohedral and cubic phases are investigated based on density functional theory. Comparisons with reported experimental results are also presented. The calculation shows that orthorhombic structure is both energetically and dynamically stable under ground state, which is supported by the experiment. Moreover, charge transfer between cations and anions accompanied with phase transition is observed, which is responsible for the softened phonon modes in rhombohedral and cubic phases. Besides, thermal properties are discussed. Oxygen atoms contribute most to the specific heat. The calculated entropy and specific heat at constant pressure fit well with the experimental ones within the measured temperature range.

Opalescence in monoclonal antibody solutions and its correlation with intermolecular interactions in dilute and concentrated solutions.

PubMed

Raut, Ashlesha S; Kalonia, Devendra S

2015-04-01

Opalescence indicates physical instability of a formulation because of the presence of aggregates or liquid-liquid phase separation in solution and has been reported for monoclonal antibody (mAb) formulations. Increased solution opalescence can be attributed to attractive protein-protein interactions (PPIs). Techniques including light scattering, AUC, or membrane osmometry are routinely employed to measure PPIs in dilute solutions, whereas opalescence is seen at relatively higher concentrations, where both long- and short-range forces contribute to overall PPIs. The mAb molecule studied here shows a unique property of high opalescence because of liquid-liquid phase separation. In this study, opalescence measurements are correlated to PPIs measured in diluted and concentrated solutions using light scattering (kD ) and high-frequency rheology (G'), respectively. Charges on the molecules were calculated using zeta potential measurements. Results indicate that high opalescence and phase separation are a result of the attractive interactions in solution; however, the presence of attractive interactions do not always imply phase separation. Temperature dependence of opalescence suggests that thermodynamic contribution to opalescence is significant and Tcloud can be utilized as a potential tool to assess attractive interactions in solution. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

A novel bio-safe phase separation process for preparing open-pore biodegradable polycaprolactone microparticles.

PubMed

Salerno, Aurelio; Domingo, Concepción

2014-09-01

Open-pore biodegradable microparticles are object of considerable interest for biomedical applications, particularly as cell and drug delivery carriers in tissue engineering and health care treatments. Furthermore, the engineering of microparticles with well definite size distribution and pore architecture by bio-safe fabrication routes is crucial to avoid the use of toxic compounds potentially harmful to cells and biological tissues. To achieve this important issue, in the present study a straightforward and bio-safe approach for fabricating porous biodegradable microparticles with controlled morphological and structural features down to the nanometer scale is developed. In particular, ethyl lactate is used as a non-toxic solvent for polycaprolactone particles fabrication via a thermal induced phase separation technique. The used approach allows achieving open-pore particles with mean particle size in the 150-250 μm range and a 3.5-7.9 m(2)/g specific surface area. Finally, the combination of thermal induced phase separation and porogen leaching techniques is employed for the first time to obtain multi-scaled porous microparticles with large external and internal pore sizes and potential improved characteristics for cell culture and tissue engineering. Samples were characterized to assess their thermal properties, morphology and crystalline structure features and textural properties. Copyright © 2014 Elsevier B.V. All rights reserved.

Fabrication of electrically bistable organic semiconducting/ferroelectric blend films by temperature controlled spin coating.

PubMed

Hu, Jinghang; Zhang, Jianchi; Fu, Zongyuan; Weng, Junhui; Chen, Weibo; Ding, Shijin; Jiang, Yulong; Zhu, Guodong

2015-03-25

Organic semiconducting/ferroelectric blend films attracted much attention due to their electrical bistability and rectification properties and thereof the potential in resistive memory devices. During film deposition from the blend solution, spinodal decomposition induced phase separation, resulting in discrete semiconducting phase whose electrical property could be modulated by the continuous ferroelectric phase. However, blend films processed by common spin coating method showed extremely rough surfaces, even comparable to the film thickness, which caused large electrical leakage and thus compromised the resistive switching performance. To improve film roughness and thus increase the productivity of these resistive devices, we developed temperature controlled spin coating technique to carefully adjust the phase separation process. Here we reported our experimental results from the blend films of ferroelectric poly(vinylidene fluoride-trifluoroethylene (P(VDF-TrFE)) and semiconducting poly(3-hexylthiophene) (P3HT). We conducted a series of experiments at various deposition temperatures ranging from 20 to 90 °C. The resulting films were characterized by AFM, SEM, and VPFM to determine their structure and roughness. Film roughness first decreased and then increased with the increase of deposition temperature. Electrical performance was also characterized and obviously improved insulating property was obtained from the films deposited between 50 and 70 °C. By temperature control during film deposition, it is convenient to efficiently fabricate ferroelectric/semiconducting blend films with good electrical bistability.

Silica particles encapsulated poly(styrene-divinylbenzene) monolithic stationary phases for micro-high performance liquid chromatography.

PubMed

Bakry, R; Stöggl, W M; Hochleitner, E O; Stecher, G; Huck, C W; Bonn, G K

2006-11-03

In the paper we demonstrate a new approach for the preparation and application of continuous silica bed columns that involve encapsulation (entrapment) of functionalized silica microparticles, which can be used as packing material in micro high performance liquid chromatography (micro-HPLC) and capillary electrochromatography (CEC). Like traditional packed columns, these capillaries possess characterized silica particles that offer high phase ratio and narrow pore size distribution leading to high retention and separation efficiency, respectively. More importantly, immobilization of the microparticles stabilizes the separation bed and eliminates the need for retaining frits. The developed capillary columns were fabricated in exactly the same way as a packed capillary column (slurry packing) but with an additional entrapment step. This immobilization of the packed bed was achieved by in situ polymerization of styrene and divinylbenzene in presence of decanol as a porogen and azobisisobutyronitrile as thermal initiator. Silica particles with different particle sizes and pore sizes ranging from 60 to 4000 A were studied. In addition different modified silica was used, including C-18 reversed phase, anion exchange and chiral stationary phases. Efficient separation of polyphenolic compounds, peptides, proteins and even DNA mutation were achieved using the developed technique depending on the properties of the silica particles used (particles pore size). For example, using 3 microm ProntoSIL C-18 particles with 300 A pore size, separation efficiencies in the range of 120,000-200,000 plates/m were obtained for protein separation, in a 6 cm x 200 microm i.d. capillary column. Using encapsulated silica C-18 with 1000 A pore size, separation of DNA homo and hetero duplexes were achieved under denaturing HPLC conditions for mutation detection. In addition, nucleotides were separated using anion exchange material encapsulated with poly(styrene-divinylbenzene) (PS/DVB), which indicated that the chromatographic properties of the silica packing material were still active after polymerization. The prepared capillary columns were found to be stable and could easily be operated continuously up to a pressure of 350 bar without column damage and capillary can be cut to any desired length.

Graphene-Reinforced Aluminum Matrix Composites: A Review of Synthesis Methods and Properties

NASA Astrophysics Data System (ADS)

Chen, Fei; Gupta, Nikhil; Behera, Rakesh K.; Rohatgi, Pradeep K.

2018-06-01

Graphene-reinforced aluminum (Gr-Al) matrix nanocomposites (NCs) have attracted strong interest from both research and industry in high-performance weight-sensitive applications. Due to the vastly different bonding characteristics of the Al matrix (metallic) and graphene (in-plane covalent + inter-plane van der Waals), the graphene phase has a general tendency to agglomerate and phase separate in the metal matrix, which is detrimental for the mechanical and chemical properties of the composite. Thus, synthesis of Gr-Al NCs is extremely challenging. This review summarizes the different methods available to synthesize Gr-Al NCs and the resulting properties achieved in these NCs. Understanding the effect of processing parameters on the realized properties opens up the possibility of tailoring the synthesis methods to achieve the desired properties for a given application.

Graphene-Reinforced Aluminum Matrix Composites: A Review of Synthesis Methods and Properties

NASA Astrophysics Data System (ADS)

Chen, Fei; Gupta, Nikhil; Behera, Rakesh K.; Rohatgi, Pradeep K.

2018-03-01

Graphene-reinforced aluminum (Gr-Al) matrix nanocomposites (NCs) have attracted strong interest from both research and industry in high-performance weight-sensitive applications. Due to the vastly different bonding characteristics of the Al matrix (metallic) and graphene (in-plane covalent + inter-plane van der Waals), the graphene phase has a general tendency to agglomerate and phase separate in the metal matrix, which is detrimental for the mechanical and chemical properties of the composite. Thus, synthesis of Gr-Al NCs is extremely challenging. This review summarizes the different methods available to synthesize Gr-Al NCs and the resulting properties achieved in these NCs. Understanding the effect of processing parameters on the realized properties opens up the possibility of tailoring the synthesis methods to achieve the desired properties for a given application.

Recent highlights in electro-driven separations- selected applications of alkylthiol gold nanoparticles in capillary electrophoresis and capillary electro-chromatography.

PubMed

Guihen, Elizabeth

2017-09-01

To date, alkylthiol gold nanoparticles (AuNPs) have been widely used in electro-chromatographic separation techniques as a viable alternative to traditional stationary phases. This is mainly due to their stability, chemical inertness, ease of functionality, increased phase ratio, ability to form self-assembled monolayers. They also yield versatile stationary phases with highly specific targeted functionalities. At the nanoscale region, the chemical and physical properties of a molecule display different attributes to that of the parent molecules or material, hence these features can be harnessed in electro-driven chromatographic separations. Application areas illustrating the use of AuNPs in separation science continue to grow and expand to cover many different kinds of analysis. The last decade has witnessed a successful trend in miniaturisation of chemical separation systems toward the micro and nanoscale ranges. Nanoparticle-based stationary phases fit well with performing chemical separations on microfluidic and capillary platforms. In this review the theory of the use of alkylthiol gold nanoparticles in electro-chromatographic driven separation methods will be discussed. This will be followed by details of recent and selected applications showing alkylthiol gold nanoparticles in capillary electrophoretic and open-tubular electro-chromatographic separations. This review will focus solely on alkylthiol based gold nanoparticles, therefore other kinds of chemical moieties bonded to gold nanoparticles are outside the scope of this review. Finally the future outlook of this exciting technology will be outlined in some detail in the final section. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanistic Studies Of Combustion And Structure Formation During Combustion Synthesis Of Advanced Materials: Phase Separation Mechanism For Bio-Alloys

NASA Technical Reports Server (NTRS)

Varma, A.; Lau, C.; Mukasyan, A.

2003-01-01

Among all implant materials, Co-Cr-Mo alloys demonstrate perhaps the most useful balance of resistance to corrosion, fatigue and wear, along with strength and biocompatibility [1]. Currently, these widely used alloys are produced by conventional furnace technology. Owing to high melting points of the main alloy elements (e.g. Tm.p.(Co) 1768 K), high-temperature furnaces and long process times (several hours) are required. Therefore, attempts to develop more efficient and flexible methods for production of such alloys with superior properties are of great interest. The synthesis of materials using combustion phenomena is an advanced approach in powder metallurgy [2]. The process is characterized by unique conditions involving extremely fast heating rates (up to 10(exp 6 K/s), high temperatures (up to 3500 K), and short reaction times (on the order of seconds). As a result, combustion synthesis (CS) offers several attractive advantages over conventional metallurgical processing and alloy development technologies. The foremost is that solely the heat of chemical reaction (instead of an external source) supplies the energy for the synthesis. Also, simple equipment, rather than energy-intensive high-temperature furnaces, is sufficient. This work was devoted to experiments on CS of Co-based alloys by utilizing thermite (metal oxide-reducing metal) reactions, where phase separation subsequently produces materials with tailored compositions and properties. Owing to high reaction exothermicity, the CS process results in a significant increase of temperature (up to 3000 C), which is higher than melting points of all products. Since the products differ in density, phase separation may be a gravitydriven process: the heavy (metallic phase) settles while the light (slag) phase floats. The goal was to determine if buoyancy is indeed the major mechanism that controls phase segregation.

A theoretical and experimental study of turbulent nonevaporating sprays

NASA Technical Reports Server (NTRS)

Solomon, A. S. P.; Shuen, J. S.; Zhang, Q. F.; Faeth, G. M.

1984-01-01

Measurements and analysis limited to the dilute portions of turbulent nonevaporating sprays injected into a still air environment were completed. Mean and fluctuating velocities and Reynolds stress were measured in the continuous phase. Liquid phase measurements included liquid mass fluxes, drop sizes and drop size and velocity correlation. Initial conditions needed for model evaluation were measured at a location as close to the injector exit as possible. The test sprays showed significant effects of slip and turbulent dispersion of the discrete phase. The measurements were used to evaluate three typical models of these processes: (1) a locally homogenous flow (LHF) model, where slip between the phases were neglected; (2) a deterministic separated flow (DSF) model, where slip was considered but effects of drop dispersion by turbulence were ignored; and (3) a stochastic separated flow (SSF) model, where effects of interphase slip and turbulent dispersion were considered using random-walk computations for drop motion. The LHF and DSF models did not provide very satisfactory predictions for the present measurements. In contrast, the SSF model performed reasonably well with no modifications in the prescription of eddy properties from its original calibration. Some effects of drops on turbulence properties were observed near the dense regions of the sprays.

A theoretical and experimental study of turbulent evaporating sprays

NASA Technical Reports Server (NTRS)

Solomon, A. S. P.; Shuen, J. S.; Zhang, Q. F.; Faeth, G. M.

1984-01-01

Measurements and analysis limited to the dilute portions of turbulent evaporating sprays, injected into a still air environment were completed. Mean and fluctuating velocities and Reynolds stress were measured in the continuous phase. Liquid phase measurements included liquid mass fluxes, drop sizes and drop size and velocity correlation. Initial conditions needed for model evaluation were measured at a location as close to the injector exit as possible. The test sprays showed significant effects of slip and turbulent dispersion of the discrete phase. The measurements were used to evaluate three typical models of these processes: (1) a locally homogeneous flow (LHF) model, where slip between the phases were neglected; (2) a deterministic separated flow (DSF) model, where slip was considered but effects of drop dispersion by turbulence were ignored; and (3) a stochastic separated flow (SSF) model, where effects of interphase slip and turbulent dispersion were considered using random-walk computations for drop motion. For all three models, a k-epsilon model as used to find the properties of the continuous phase. The LHF and DSF models did not provide very satisfactory predictions for the present measurements. In contrast, the SSF model performed reasonably well--with no modifications in the prescription of eddy properties from its original calibration.

Low-temperature magnetic ordering in the perovskites Pr 1-xA xCoO 3 (A=Ca, Sr)

NASA Astrophysics Data System (ADS)

Deac, Iosif G.; Tetean, Romulus; Balasz, Istvan; Burzo, Emil

2010-05-01

The magnetic and electrical properties of polycrystalline Pr 1-xA xCoO 3 cobaltites with A=Ca, Sr and 0≤ x≤0.5 were studied in the temperature range 4 K≤ T≤1000 K and field up to 7 T. The X-ray analyses show the presence of only one phase having monoclinic or orthorhombic symmetry. The magnetic measurements indicate that the Ca-doped samples have at low temperatures, similar properties to the frustrated magnetic materials. PrCoO 3 is a paramagnetic insulator in the range from 4 to 1000 K. The Sr-doped cobaltites exhibit two phase transitions: a paramagnetic-ferromagnetic (or magnetic phase separated state) phase transition at about 240 K and a second one at about 100 K. The magnetic measurements suggest the presence of magnetic clusters and a change in the nature of magnetic coupling between Co ions at low temperatures. A semiconducting type behavior and high negative magnetoresistance was found for the Ca-doped samples, while the Sr-doped ones were metallic and with negligible magnetoresistance. The results are analyzed in the frame of a phase separation scenario in the presence of the spin-state transitions of Co ions.

Manipulation of electronic phases in Au-nanodots-decorated manganite films by laser illumination

NASA Astrophysics Data System (ADS)

Li, Hui; Zhang, Kaixuan; Wang, Dongli; Xu, Han; Zhou, Haibiao; Fan, Xiaodong; Cheng, Guanghui; Cheng, Long; Lu, Qingyou; Li, Lin; Zeng, Changgan

2018-06-01

Precise manipulation of the electronic phases in strongly correlated oxides offers an avenue to control the macroscopic functionalities, thereby sparking enormous research interests in condensed matter physics. In the present paper, phase-separated La0.33Pr0.34Ca0.33MnO3 (LPCMO) thin films with a fraction of the ferromagnetic metallic phase close to the percolation threshold are successfully prepared, in which the nonvolatile and erasable switching between different electronic states is realized through cooperative effects of Au-nanodots capping and laser illumination. The deposition of Au nanodots on LPCMO thin films leads to the occurrence of a thermally inaccessible nonpercolating state at low temperatures, manifested as the absence of insulator-metal transition as temperature decreases. Such a nonpercolating state can be substantially tuned back to a percolating state by laser illumination in a nonvolatile and erasable way, accompanied by gigantic resistance drops in a wide temperature range. The formation of local oxygen vacancies near Au nanodots and thereby the modulation of mesoscopic electronic texture should be the key factor for the realization of flexible modulation of global transport properties in LPCMO thin films. Our findings pave a way toward the manipulation of physical properties of the electronically phase-separated systems and the design of optically controlled electronic devices.

Enhanced dielectric and piezoelectric responses in Zn 1 -xMg xO thin films near the phase separation boundary

DOE PAGES

Kang, Xiaoyu; Shetty, Smitha; Garten, Lauren; ...

2017-01-23

Dielectric and piezoelectric properties for Zn 1-xMg xO (ZMO) thin films are reported as a function of MgO composition up to and including the phase separation region. Zn 1-xMg xO (0.25 ≤ x ≤ 0.5) thin films with c-axis textures were deposited by pulsed laser deposition on platinized sapphire substrates. The films were phase pure wurtzite for MgO concentrations up to 40%; above that limit, a second phase with rocksalt structure evolves with strong {100} texture. With increasing MgO concentration, the out-of-plane ( d33,f) and in-plane ( e31,f) piezoelectric coefficients increase by 360% and 290%, respectively. The increase in piezoelectricmore » coefficients is accompanied by a 35% increase in relative permittivity. Loss tangent values fall monotonically with increasing MgO concentration, reaching a minimum of 0.001 for x ≥ 0.30, at which point the band gap is reported to be 4 eV. As a result, the enhanced piezoelectric response, the large band gap, and the low dielectric loss make Zn 1-xMg xO an interesting candidate for thin film piezoelectric devices, and demonstrate that compositional phase transformations provide opportunities for property engineering.« less

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

Guo, Wei; Sneed, Brian T.; Zhou, Lin

Alnico alloys have long been used as strong permanent magnets because of their ferromagnetism and high coercivity. Understanding their structural details allows for better prediction of the resulting magnetic properties. However, quantitative three-dimensional characterization of the phase separation in these alloys is still challenged by the spatial quantification of nanoscale phases. Herein, we apply a dual tomography approach, where correlative scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopic (EDS) tomography and atom probe tomography (APT) are used to investigate the initial phase separation process of an alnico 8 alloy upon non-magnetic annealing. STEM-EDS tomography provides information on the morphology andmore » volume fractions of Fe–Co-rich and Νi–Al-rich phases after spinodal decomposition in addition to quantitative information of the composition of a nanoscale volume. Subsequent analysis of a portion of the same specimen by APT offers quantitative chemical information of each phase at the sub-nanometer scale. Furthermore, APT reveals small, 2–4 nm Fe-rich α 1 phases that are nucleated in the Ni-rich α 2 matrix. From this information, we show that phase separation of the alnico 8 alloy consists of both spinodal decomposition and nucleation and growth processes. Lastly, we discuss the complementary benefits and challenges associated with correlative STEM-EDS and APT.« less

Convergence of Artificial Protein Polymers and Intrinsically Disordered Proteins.

PubMed

Dzuricky, Michael; Roberts, Stefan; Chilkoti, Ashutosh

2018-05-01

A flurry of research in recent years has revealed the molecular origins of many membraneless organelles to be the liquid phase separation of intrinsically disordered proteins (IDPs). Consequently, protein disorder has emerged as an important driver of intracellular compartmentalization by providing specialized microenvironments chemically distinct from the surrounding medium. Though the importance of protein disorder and its relationship to intracellular phase behavior are clear, a detailed understanding of how such phase behavior can be predicted and controlled remains elusive. While research in IDPs has largely focused on the implications of structural disorder on cellular function and disease, another field, that of artificial protein polymers, has focused on the de novo design of protein polymers with controllable material properties. A subset of these polymers, specifically those derived from structural proteins such as elastin and resilin, are also disordered sequences that undergo liquid-liquid phase separation. This phase separation has been used in a variety of biomedical applications, and researchers studying these polymers have developed methods to precisely characterize and tune their phase behavior. Despite their disparate origins, both fields are complementary as they study the phase behavior of intrinsically disordered polypeptides. This Perspective hopes to stimulate collaborative efforts by highlighting the similarities between these two fields and by providing examples of how such collaboration could be mutually beneficial.

Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kelly, Jesse C.

Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in electrochemical energy storage devices, while preserving the performance, lifetimes, and versatility that large-format systems require. Initial work focused on the development of a model system that demonstrated the concept of RPEs in an electrochemical device. Aqueous electrolyte solutions of polymers exhibiting properties that change in response to temperature were developed for applications in EDLCs and supercapacitors. These "smart materials" provide a means to control electrochemical systems where polymer phase separation at high temperatures affects electrolyte properties and inhibits device performance. Aqueous RPEs were synthesized using N-isopropylacrylamide, which governs the thermal properties, and fractions of acrylic acid or vinyl sulfonic acids, which provide ions to the solution. The molecular properties of these aqueous RPEs, specifically the ionic composition, were shown to influence the temperature-dependent electrolyte properties and the extent to which these electrolytes control the energy storage characteristics of a supercapacitor device. Materials with high ionic content provided the highest room temperature conductivity and electrochemical activity; however, RPEs with low ionic content provided the highest "on-off" ratio in electrochemical activity at elevated temperatures. Overall, solution pH and conductivity were altered by an order of magnitude and device performance (ability to store charge) decreased by over 70%. After demonstration of a model responsive electrolyte in an aqueous system, ionic liquid (IL) based electrolytes were developed as a means of controlling the electrochemical performance in the non-aqueous environments that batteries, specifically Li-ion, require. Here, two systems were developed: (1) an electrolyte comprising poly(ethylene oxide) (PEO), the IL, [EMIM][BF4], and a lithium salt and (2) an electrolyte comprising poly(benzyl methacrylate) (PBzMA), the IL, [EMIM][TFSI], and a lithium salt. In each system, the polymer-IL phase separation inhibited device operation at elevated temperatures. For the PEO/IL electrolyte, the thermally induced liquid-liquid phase separation was shown to decrease the ionic conductivity, thereby affecting the concentration of ions at the electrode. Additionally, an increasing charge transfer resistance associated with the phase separated polymer coating the porous electrode was shown to limit electrochemical activity significantly. For the PBzMA/IL electrolyte, the solid-liquid phase separation did not show a change in conductivity, but did cause a drastic increase in charge transfer resistance, effectively shutting off Li-ion battery operation at high temperatures. Such responsive mixtures provide a transformative approach to regulating electrochemical processes, which is necessary to achieve inherently safe operation in large format energy storage with EDLCs, supercapacitors and Li-ion batteries.

Application of Carbon Nanotubes in Chiral and Achiral Separations of Pharmaceuticals, Biologics and Chemicals

PubMed Central

Hemasa, Ayman L.; Maher, William A.; Ghanem, Ashraf

2017-01-01

Carbon nanotubes (CNTs) possess unique mechanical, physical, electrical and absorbability properties coupled with their nanometer dimensional scale that renders them extremely valuable for applications in many fields including nanotechnology and chromatographic separation. The aim of this review is to provide an updated overview about the applications of CNTs in chiral and achiral separations of pharmaceuticals, biologics and chemicals. Chiral single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) have been directly applied for the enantioseparation of pharmaceuticals and biologicals by using them as stationary or pseudostationary phases in chromatographic separation techniques such as high-performance liquid chromatography (HPLC), capillary electrophoresis (CE) and gas chromatography (GC). Achiral MWCNTs have been used for achiral separations as efficient sorbent objects in solid-phase extraction techniques of biochemicals and drugs. Achiral SWCNTs have been applied in achiral separation of biological samples. Achiral SWCNTs and MWCNTs have been also successfully used to separate achiral mixtures of pharmaceuticals and chemicals. Collectively, functionalized CNTs have been indirectly applied in separation science by enhancing the enantioseparation of different chiral selectors whereas non-functionalized CNTs have shown efficient capabilities for chiral separations by using techniques such as encapsulation or immobilization in polymer monolithic columns. PMID:28718832

Continuous, high-flux and efficient oil/water separation assisted by an integrated system with opposite wettability

NASA Astrophysics Data System (ADS)

Li, Jian; Long, Yifei; Xu, Changcheng; Tian, Haifeng; Wu, Yanxia; Zha, Fei

2018-03-01

To resolve the drawbacks that single-mesh involved for oil/water separation, such as batch processing mode, only one phase was purified and the quick decrease in flux et al., herein, a two-way separation T-tube device was designed by integrating a pair of meshes with opposite wettability, i.e., underwater superoleophobic and superhydrophobic/superoleophilic properties. Such integrated system can continuously separate both oil and water phase from the oil/water mixtures simultaneously through one-step procedure with high flux (above 3.675 L m-2 s-1) and high separation efficiency larger than 99.8% regardless of the heavy oil or light oil involved in the mixture. Moreover, the as-prepared two meshes still maintained high separation efficiency larger than above 98.9% even after 50 cycle-usages. It worthy mentioned that this two-way separation mode essentially solves the oil liquid accumulation problem that is the single separation membrane needs to tolerate a large hydrostatic pressure caused by the accumulated liquid. We deeply believe this two-way separation system would provide a new strategy for realizing practical applications in oil spill clean-up via a continuous mode.

Observational constraints on the multiphase ISM

NASA Astrophysics Data System (ADS)

Wolfire, Mark G.

2015-03-01

In recent years we have seen a wealth of new observations and analysis that sheds light on the distribution and physical properties of various ISM phases. In particular the thermal pressure from C I (Jenkins & Tripp 2011) shows the bulk of the CNM phase with a log normal pressure distribution. It appears that thermal instability is important for phase separation, but with with a thermal pressure variation about the mean driven by turbulence. In additional, there is evidence from C I, H2, and complex molecules, of both higher and lower pressure environments. An additional ``phase`` that is of increasing interest for high z, low metallicity galaxies is the C+/H2 gas that is not traced by H I or CO. This review presents the observational evidence for the existence and physical properties of these various ISM phases.

Multifunctional nanocomposite hollow fiber membranes by solvent transfer induced phase separation.

PubMed

Haase, Martin F; Jeon, Harim; Hough, Noah; Kim, Jong Hak; Stebe, Kathleen J; Lee, Daeyeon

2017-11-01

The decoration of porous membranes with a dense layer of nanoparticles imparts useful functionality and can enhance membrane separation and anti-fouling properties. However, manufacturing of nanoparticle-coated membranes requires multiple steps and tedious processing. Here, we introduce a facile single-step method in which bicontinuous interfacially jammed emulsions are used to form nanoparticle-functionalized hollow fiber membranes. The resulting nanocomposite membranes prepared via solvent transfer-induced phase separation and photopolymerization have exceptionally high nanoparticle loadings (up to 50 wt% silica nanoparticles) and feature densely packed nanoparticles uniformly distributed over the entire membrane surfaces. These structurally well-defined, asymmetric membranes facilitate control over membrane flux and selectivity, enable the formation of stimuli responsive hydrogel nanocomposite membranes, and can be easily modified to introduce antifouling features. This approach forms a foundation for the formation of advanced nanocomposite membranes comprising diverse building blocks with potential applications in water treatment, industrial separations and as catalytic membrane reactors.

Tailorable Surface Morphology of 3D Scaffolds by Combining Additive Manufacturing with Thermally Induced Phase Separation.

PubMed

Di Luca, Andrea; de Wijn, Joost R; van Blitterswijk, Clemens A; Camarero-Espinosa, Sandra; Moroni, Lorenzo

2017-08-01

The functionalization of biomaterials substrates used for cell culture is gearing towards an increasing control over cell activity. Although a number of biomaterials have been successfully modified by different strategies to display tailored physical and chemical surface properties, it is still challenging to step from 2D substrates to 3D scaffolds with instructive surface properties for cell culture and tissue regeneration. In this study, additive manufacturing and thermally induced phase separation are combined to create 3D scaffolds with tunable surface morphology from polymer gels. Surface features vary depending on the gel concentration, the exchanging temperature, and the nonsolvent used. When preosteoblasts (MC-3T3 cells) are cultured on these scaffolds, a significant increase in alkaline phosphatase activity is measured for submicron surface topography, suggesting a potential role on early cell differentiation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Degradation behavior of Mg-based biomaterials containing different long-period stacking ordered phases

NASA Astrophysics Data System (ADS)

Peng, Qiuming; Guo, Jianxin; Fu, Hui; Cai, Xuecheng; Wang, Yanan; Liu, Baozhong; Xu, Zhigang

2014-01-01

Long-period stacking ordered (LPSO) phases play an essential role in the development of magnesium alloys because they have a direct effect on mechanical and corrosion properties of the alloys. The LPSO structures are mostly divided to 18R and 14H. However, to date there are no consistent opinions about their degradation properties although both of them can improve mechanical properties. Herein we have successfully obtained two LPSO phases separately in the same Mg-Dy-Zn system and comparatively investigated the effect of different LPSO phases on degradation behavior in 0.9 wt.% NaCl solution. Our results demonstrate that a fine metastable 14H-LPSO phase in grain interior is more effective to improve corrosion resistance due to the presence of a homogeneous oxidation film and rapid film remediation ability. The outstanding corrosion resistant Mg-Dy-Zn based alloys with a metastable 14H-LPSO phase, coupled with low toxicity of alloying elements, are highly desirable in the design of novel Mg-based biomaterials, opening up a new avenue in the area of bio-Mg.

Degradation behavior of Mg-based biomaterials containing different long-period stacking ordered phases

PubMed Central

Peng, Qiuming; Guo, Jianxin; Fu, Hui; Cai, Xuecheng; Wang, Yanan; Liu, Baozhong; Xu, Zhigang

2014-01-01

Long-period stacking ordered (LPSO) phases play an essential role in the development of magnesium alloys because they have a direct effect on mechanical and corrosion properties of the alloys. The LPSO structures are mostly divided to 18R and 14H. However, to date there are no consistent opinions about their degradation properties although both of them can improve mechanical properties. Herein we have successfully obtained two LPSO phases separately in the same Mg-Dy-Zn system and comparatively investigated the effect of different LPSO phases on degradation behavior in 0.9 wt.% NaCl solution. Our results demonstrate that a fine metastable 14H-LPSO phase in grain interior is more effective to improve corrosion resistance due to the presence of a homogeneous oxidation film and rapid film remediation ability. The outstanding corrosion resistant Mg-Dy-Zn based alloys with a metastable 14H-LPSO phase, coupled with low toxicity of alloying elements, are highly desirable in the design of novel Mg-based biomaterials, opening up a new avenue in the area of bio-Mg. PMID:24401851

Isolation, Separation, and Preconcentration of Biologically Active Compounds from Plant Matrices by Extraction Techniques.

PubMed

Raks, Victoria; Al-Suod, Hossam; Buszewski, Bogusław

2018-01-01

Development of efficient methods for isolation and separation of biologically active compounds remains an important challenge for researchers. Designing systems such as organomineral composite materials that allow extraction of a wide range of biologically active compounds, acting as broad-utility solid-phase extraction agents, remains an important and necessary task. Selective sorbents can be easily used for highly selective and reliable extraction of specific components present in complex matrices. Herein, state-of-the-art approaches for selective isolation, preconcentration, and separation of biologically active compounds from a range of matrices are discussed. Primary focus is given to novel extraction methods for some biologically active compounds including cyclic polyols, flavonoids, and oligosaccharides from plants. In addition, application of silica-, carbon-, and polymer-based solid-phase extraction adsorbents and membrane extraction for selective separation of these compounds is discussed. Potential separation process interactions are recommended; their understanding is of utmost importance for the creation of optimal conditions to extract biologically active compounds including those with estrogenic properties.

Exploring the Parameters Controlling the Crystallinity-Conductivity Correlation of PFSA Ionomers

NASA Astrophysics Data System (ADS)

Kusoglu, Ahmet; Shi, Shouwen; Weber, Adam

Perfluorosulfonic-acid (PFSA) ionomers are the most commonly used solid-electrolyte in electrochemical energy devices because of their remarkable conductivity and chemical/mechanical stability, with the latter imparted by their semi-crystalline fluorocarbon backbone. PFSAs owe this unique combination of transport/stability functionalities to their phase-separated morphology of conductive hydrophilic ionic domains and the non-conductive hydrophobic backbone, which are connected via pendant chains. Thus, phase-separation is governed by fractions of backbone and ionic groups, which is controlled by the equivalent weight (EW). Therefore, EW, along with the pendant chain chemistry, directly impact the conductive vs non-conductive regions, and consequently the interrelation between transport and stability. Driven by the need to achieve higher conductivities without disrupting the crystallinity, various pendant-chain chemistries have been developed. In this talk, we will report the results of a systematic investigation on hydration, conductivity, mechanical properties and crystallinity of various types and EWs of PFSA ionomers to (i) develop a structure/property map, and (ii) identify the key parameters controlling morphology and properties. It will be discussed how the pendant-chain and backbone lengths affect the conductivity and crystallinity, respectively. Lastly, the data set will be analyzed to explore universal structure/property relationships for PFSAs.

Spectral variation during one quasi-periodic oscillation cycle in the black hole candidate H1743-322

NASA Astrophysics Data System (ADS)

Sarathi Pal, Partha; Debnath, Dipak; Chakrabarti, Sandip Kumar

2016-07-01

From the nature of energy dependence of the power density spectra, it is believed that the oscillation of the Compton cloud may be related to low frequency quasi-periodic oscillations (LFQPOs). In the context of two component advective flow (TCAF) solution, the centrifugal pressure supported boundary layer of a transonic flow acts as the Compton cloud. This region undergoes resonance oscillation when cooling time scale roughly agrees with infall time scale as matter crosses this region. By carefully separating photons emitted at different phases of a complete oscillation, we establish beyond reasonable doubt that such an oscillation is the cause of LFQPOs. We show that the degree of Comptonization and therefore the spectral properties of the flow oscillate systematically with the phase of LFQPOs. We analysis the properties of a 0.2Hz LFQPO exhibited by a black hole candidate H 1743-322 using the 3-80 keV data from NuSTAR satellite. This object was chosen because of availability of high quality data for a relatively low frequency oscillation, rendering easy phase-wise of separation of the light curve data.

Effect of charge ordering and phase separation on the electrical and magnetoresistive properties of polycrystalline La0.4Eu0.1Ca0.5MnO3

NASA Astrophysics Data System (ADS)

Krichene, A.; Boujelben, W.; Mukherjee, S.; Shah, N. A.; Solanki, P. S.

2018-03-01

We have investigated the effect of charge ordering and phase separation on the electrical and magnetotransport properties of La0.4Eu0.1Ca0.5MnO3 polycrystalline sample. Temperature dependence of resistivity shows a metal-insulator transition at transition temperature Tρ. A hysteretic behavior is observed for zero field resistivity curves with Tρ = 128 K on cooling process and Tρ = 136 K on warming process. Zero field resistivity curves follow Zener polynomial law in the metallic phase with unusual n exponent value ∼9. Presence of resistivity minimum at low temperatures has been ascribed to the coulombic electron-electron scattering process. Resistivity modification due to the magnetic field cycling testifies the presence of the training effect. Magnetization and resistivity appear to be highly correlated. Magnetoresistive study reveals colossal values of negative magnetoresistance reaching about 75% at 132 K under only 2T applied field. Colossal values of magnetoresistance suggest the possibility of using this sample for magnetic field sensing and spintronic applications.

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

Lee, Min Ho; Rhyee, Jong-Soo, E-mail: jsrhyee@khu.ac.kr

We investigated the thermoelectric properties of PbTe/Ag{sub 2}Te bulk composites, synthesized by hand milling, mixing, and hot press sintering. From x-ray diffraction and energy dispersive x-ray spectroscopy measurements, we observed Ag{sub 2}Te phase separation in the PbTe matrix without Ag atom diffusion. In comparison with previously reported pseudo-binary (PbTe){sub 1−x}(Ag{sub 2}Te){sub x} composites, synthesized by high temperature phase separation, the PbTe/Ag{sub 2}Te bulk composites fabricated with a low temperature phase mixing process give rise to p-type conduction of carriers with significantly decreased electrical conductivity. This indicates that Ag atom diffusion in the PbTe matrix changes the sign of the Seebeckmore » coefficient to n-type and also increases the carrier concentration. Effective p-type doping with low temperature phase separation by mixing and hot press sintering can enhance the thermoelectric performance of PbTe/Ag{sub 2}Te bulk composites, which can be used as a p-type counterpart of n-type (PbTe){sub 1−x}(Ag{sub 2}Te){sub x} bulk composites.« less

Effect of liquid crystal birefringence on the opacity and off-axis haze of PDLC films

NASA Astrophysics Data System (ADS)

Pane, S.; Caporusso, M.

1998-02-01

PDLC systems are thin films consisting of a dispersion of liquid crystal micro-droplets in a continuous solid phase of polymer matrix. Application of an electric field on a thin layer of PDLC sandwiched between two transparent on-state. This effect make them useful for a wide variety of applications. Among them, smart windows for architectural is the most popular subject in literature. For this application, the key parameters of performance are the haze and the opacity. There are essentially two technologies used to prepare PDLC films, namely micro-encapsulation and phase separation.In the present work we will show the correlation between the opacity and the off-axis haze in PDLC films prepared with a phase separation technology. We will give the general rule in order to select the liquid crystal properties that allow the preparation of high opacity ad low haze PDLC films. Further study about the control of the parameters which influence the performances of PDLC films prepared with phase separation technology and the difference with the NCAP approach are in progress at our laboratory.

Phase behaviour of disordered proteins underlying low density and high permeability of liquid organelles

NASA Astrophysics Data System (ADS)

Wei, Ming-Tzo; Elbaum-Garfinkle, Shana; Holehouse, Alex S.; Chen, Carlos Chih-Hsiung; Feric, Marina; Arnold, Craig B.; Priestley, Rodney D.; Pappu, Rohit V.; Brangwynne, Clifford P.

2017-11-01

Many intracellular membraneless organelles form via phase separation of intrinsically disordered proteins (IDPs) or regions (IDRs). These include the Caenorhabditis elegans protein LAF-1, which forms P granule-like droplets in vitro. However, the role of protein disorder in phase separation and the macromolecular organization within droplets remain elusive. Here, we utilize a novel technique, ultrafast-scanning fluorescence correlation spectroscopy, to measure the molecular interactions and full coexistence curves (binodals), which quantify the protein concentration within LAF-1 droplets. The binodals of LAF-1 and its IDR display a number of unusual features, including 'high concentration' binodal arms that correspond to remarkably dilute droplets. We find that LAF-1 and other in vitro and intracellular droplets are characterized by an effective mesh size of ∼3-8 nm, which determines the size scale at which droplet properties impact molecular diffusion and permeability. These findings reveal how specific IDPs can phase separate to form permeable, low-density (semi-dilute) liquids, whose structural features are likely to strongly impact biological function.

New stationary phase for hydrophilic interaction chromatography to separate chito-oligosaccharides with degree of polymerization 2-6.

PubMed

Zhai, Xingchen; Zhao, Haitian; Zhang, Min; Yang, Xin; Sun, Jingming; She, Yongxin; Dong, Aijun; Zhang, Hua; Yao, Lei; Wang, Jing

2018-04-01

A new 3‑aminophenylboronic acid-functionalized stationary phase based on silica for hydrophilic interaction liquid chromatography (HILIC) was developed and showed great HILIC characteristics on separation for chito‑oligosaccharides. The material was synthesized by grafting 3‑aminophenylboronic acid group to silica, and it was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), elemental analysis and thermal gravimetric analysis (TGA). Nucleobases and nucleosides were used to evaluate the retention property and to investigate retention mechanism by the models designed for description of partitioning and surface adsorption through adjusting ratio of water in the mobile phase. Parameters affecting chromatography behavior such as ionic strength, buffer pH and column temperature were also investigated. Results have indicated that the retention mechanism was a combination of partitioning and surface adsorption, and the hydrogen bond seemed to be the main force for the retention behavior. Finally, the new 3‑aminophenylboronic acid-functionalized based on silica stationary phase was applied to separate chito-oligosaccharide samples with optimized mobile phase conditions and showed acceptable chromatograms. Copyright © 2018 Elsevier B.V. All rights reserved.

Electronic phase separation at the LaAlO₃/SrTiO₃ interface.

PubMed

Ariando; Wang, X; Baskaran, G; Liu, Z Q; Huijben, J; Yi, J B; Annadi, A; Barman, A Roy; Rusydi, A; Dhar, S; Feng, Y P; Ding, J; Hilgenkamp, H; Venkatesan, T

2011-02-08

There are many electronic and magnetic properties exhibited by complex oxides. Electronic phase separation (EPS) is one of those, the presence of which can be linked to exotic behaviours, such as colossal magnetoresistance, metal-insulator transition and high-temperature superconductivity. A variety of new and unusual electronic phases at the interfaces between complex oxides, in particular between two non-magnetic insulators LaAlO(3) and SrTiO(3), have stimulated the oxide community. However, no EPS has been observed in this system despite a theoretical prediction. Here, we report an EPS state at the LaAlO(3)/SrTiO(3) interface, where the interface charges are separated into regions of a quasi-two-dimensional electron gas, a ferromagnetic phase, which persists above room temperature, and a (superconductor like) diamagnetic/paramagnetic phase below 60 K. The EPS is due to the selective occupancy (in the form of 2D-nanoscopic metallic droplets) of interface sub-bands of the nearly degenerate Ti orbital in the SrTiO(3). The observation of this EPS demonstrates the electronic and magnetic phenomena that can emerge at the interface between complex oxides mediated by the Ti orbital.

Novel stationary phases based on asphaltenes for gas chromatography.

PubMed

Boczkaj, Grzegorz; Momotko, Malwina; Chruszczyk, Dorota; Przyjazny, Andrzej; Kamiński, Marian

2016-07-01

We present the results of investigations on the possibility of the application of the asphaltene fraction isolated from the oxidized residue from vacuum distillation of crude oil as a stationary phase for gas chromatography. The results of the investigation revealed that the asphaltene stationary phases can find use for the separation of a wide range of volatile organic compounds. The experimental values of Rohrschneider/McReynolds constants characterize the asphaltenes as stationary phases of medium polarity and selectivity similar to commercially available phases based on alkyl phthalates. Isolation of asphaltenes from the material obtained under controlled process conditions allows the production of a stationary phase having reproducible sorption properties and chromatographic columns having the same selectivity. Unique selectivity and high thermal stability make asphaltenes attractive as a material for stationary phases for gas chromatography. A low production cost from a readily available raw material (oxidized petroleum bitumens) is an important economic factor in case of application of the asphaltene stationary phases for preparative and process separations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Symmetry-protected topological phases of one-dimensional interacting fermions with spin-charge separation

NASA Astrophysics Data System (ADS)

Montorsi, Arianna; Dolcini, Fabrizio; Iotti, Rita C.; Rossi, Fausto

2017-06-01

The low energy behavior of a huge variety of one-dimensional interacting spinful fermionic systems exhibits spin-charge separation, described in the continuum limit by two sine-Gordon models decoupled in the charge and spin channels. Interaction is known to induce, besides the gapless Luttinger liquid phase, eight possible gapped phases, among which are the Mott, Haldane, charge-/spin-density, and bond-ordered wave insulators, and the Luther Emery liquid. Here we prove that some of these physically distinct phases have nontrivial topological properties, notably the presence of degenerate protected edge modes with fractionalized charge/spin. Moreover, we show that the eight gapped phases are in one-to-one correspondence with the symmetry-protected topological (SPT) phases classified by group cohomology theory in the presence of particle-hole symmetry P. The latter result is also exploited to characterize SPT phases by measurable nonlocal order parameters which follow the system evolution to the quantum phase transition. The implications on the appearance of exotic orders in the class of microscopic Hubbard Hamiltonians, possibly without P symmetry at higher energies, are discussed.

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

Elliott, Douglas C.; Neuenschwander, Gary G.; Hart, Todd R.

Fast pyrolysis of biomass can be used to produce a raw bio-oil product, which can be upgraded by catalytic hydroprocessing to hydrocarbon liquid products. In this study the upgraded products were distilled to recover light naphtha and oils and to produce a distillation resid with useful properties for coker processing and production of renewable, low-sulfur electrode carbon. For this hydroprocessing work, phase separation of the bio-oil was applied as a preparatory step to concentrate the heavier, more phenolic components thus generating a more amenable feedstock for resid production. Low residual oxygen content products were produced by continuous-flow, catalytic hydroprocessing ofmore » the phase separated bio-oil.« less

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

Rohde, Brian J.; Le, Kim Mai; Krishnamoorti, Ramanan

The mechanical properties of two chemically distinct and complementary thermoset polymers were manipulated through development of thermoset blends. The thermoset blend system was composed of an anhydride-cured diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin, contributing high tensile strength and modulus, and polydicyclopentadiene (PDCPD), which has a higher toughness and impact strength as compared to other thermoset polymers. Ultra-small-angle and small-angle X-ray scattering analysis explored the morphology of concurrently cured thermoset blends, revealing a macroscopically phase separated system with a surface fractal structure across blended systems of varying composition. The epoxy resin rich and PDCPD rich phases exhibited distinct glassmore » transitions (Tg’s): the Tg observed at higher temperature was associated with the epoxy resin rich phase and was largely unaffected by the presence of PDCPD, whereas the PDCPD rich phase Tg systematically decreased with increasing epoxy resin content due to inhibition of dicyclopentadiene ring-opening metathesis polymerization. The mechanical properties of these phase-separated blends were in reasonable agreement with predictions by the rule of mixtures for the blend tensile strength, modulus, and fracture toughness. Scanning electron microscopy analysis of the tensile and fracture specimen fracture surfaces showed an increase in energy dissipation mechanisms, such as crazing, shear banding, and surface roughness, as the fraction of the more ductile component, PDPCD, increased. These results present a facile method to tune the mechanical properties of a toughened thermoset network, in which the high modulus and tensile strength of the epoxy resin can be largely retained at high epoxy resin content in the blend, while increasing the fracture toughness.« less

Naturally occurring reverse tilt domains in a high-pretilt alignment nematic liquid crystal

NASA Astrophysics Data System (ADS)

Wang, Ruiting; Atherton, Timothy J.; Zhu, Minhua; Petschek, Rolfe G.; Rosenblatt, Charles

2007-08-01

A cell whose substrates were coated with the polyamic acid SE1211 (Nissan Chemical Industries) and baked at high temperatures was filled with a nematic liquid crystal in the isotropic phase. On cooling into the nematic phase, naturally occurring and temporally and thermally robust reverse tilt domains separated by thin filamentlike walls were observed. The properties of these structures are reported.

Phase separation and mechanical properties of an elastomeric biomaterial from spider wrapping silk and elastin block copolymers.

PubMed

Muiznieks, Lisa D; Keeley, Fred W

2016-10-01

Elastin and silk spidroins are fibrous, structural proteins with elastomeric properties of extension and recoil. While elastin is highly extensible and has excellent recovery of elastic energy, silks are particularly strong and tough. This study describes the biophysical characterization of recombinant polypeptides designed by combining spider wrapping silk and elastin-like sequences as a strategy to rationally increase the strength of elastin-based materials while maintaining extensibility. We demonstrate a thermo-responsive phase separation and spontaneous colloid-like droplet formation from silk-elastin block copolymers, and from a 34 residue disordered region of Argiope trifasciata wrapping silk alone, and measure a comprehensive suite of tensile mechanical properties from cross-linked materials. Silk-elastin materials exhibited significantly increased strength, toughness, and stiffness compared to an elastin-only material, while retaining high failure strains and low energy loss upon recoil. These data demonstrate the mechanical tunability of protein polymer biomaterials through modular, chimeric recombination, and provide structural insights into mechanical design. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 693-703, 2016. © 2016 Wiley Periodicals, Inc.

Controlling phase separation in vanadium dioxide thin films via substrate engineering

NASA Astrophysics Data System (ADS)

Gilbert Corder, Stephanie N.; Jiang, Jianjuan; Chen, Xinzhong; Kittiwatanakul, Salinporn; Tung, I.-Cheng; Zhu, Yi; Zhang, Jiawei; Bechtel, Hans A.; Martin, Michael C.; Carr, G. Lawrence; Lu, Jiwei; Wolf, Stuart A.; Wen, Haidan; Tao, Tiger H.; Liu, Mengkun

2017-10-01

The strong electron-lattice interactions in correlated electron systems provide unique opportunities for altering the material properties with relative ease and flexibility. In this Rapid Communication, we use localized strain control via a focused-ion-beam patterning of Ti O2 substrates to demonstrate that one can selectively engineer the insulator-to-metal transition temperature, the fractional component of the insulating and metallic phases, and the degree of optical anisotropy down to the length scales of the intrinsic phase separation in V O2 thin films without altering the quality of the films. The effects of localized strain control on the strongly correlated electron system are directly visualized by state-of-the-art IR near-field imaging and spectroscopy techniques and x-ray microdiffraction measurements.

Controlling phase separation in vanadium dioxide thin films via substrate engineering

DOE PAGES

Gilbert Corder, Stephanie N.; Jiang, Jianjuan; Chen, Xinzhong; ...

2017-10-23

The strong electron-lattice interactions in correlated electron systems provide unique opportunities for altering the material properties with relative ease and flexibility. Here in this Rapid Communication, we use localized strain control via a focused-ion-beam patterning of TiO 2 substrates to demonstrate that one can selectively engineer the insulator-to-metal transition temperature, the fractional component of the insulating and metallic phases, and the degree of optical anisotropy down to the length scales of the intrinsic phase separation in VO 2 thin films without altering the quality of the films. The effects of localized strain control on the strongly correlated electron system aremore » directly visualized by state-of-the-art IR near-field imaging and spectroscopy techniques and x-ray microdiffraction measurements.« less

Chemical studies of elements with Z ⩾ 104 in gas phase

NASA Astrophysics Data System (ADS)

Türler, Andreas; Eichler, Robert; Yakushev, Alexander

2015-12-01

Chemical investigations of superheavy elements in the gas-phase, i.e. elements with Z ≥ 104, allow assessing the influence of relativistic effects on their chemical properties. Furthermore, for some superheavy elements and their compounds quite unique gas-phase chemical properties were predicted. The experimental verification of these properties yields supporting evidence for a firm assignment of the atomic number. Prominent examples are the high volatility observed for HsO4 or the very weak interaction of Cn with gold surfaces. The unique properties of HsO4 were exploited to discover the doubly-magic even-even nucleus 270Hs and the new isotope 271Hs. The combination of kinematic pre-separation and gas-phase chemistry allowed gaining access to a new class of relatively fragile compounds, the carbonyl complexes of elements Sg through Mt. A not yet resolved issue concerns the interaction of Fl with gold surfaces. While competing experiments agree on the fact that Fl is a volatile element, there are discrepancies concerning its adsorption on gold surfaces with respect to its daughter Cn. The elucidation of these and other questions amounts to the fascination that gas-phase chemical investigations exert on current research at the extreme limits of chemistry today.

Influence of heat treatment and hot extrusion on the microstructure and tensile properties of rare earth modified Mg-Zn based alloy

NASA Astrophysics Data System (ADS)

Sheng, L. Y.; Wang, B. J.; Du, B. N.; Lai, C.; Xi, T. F.

2018-01-01

In the present paper, the Mg-Zn-Y-Nd alloy was prepared by casting, heat treatment and hot extrusion. The microstructure and mechanical properties of the alloys were tested by OM, SEM, TEM and tensile test. The results showed that the Mg3Zn2Y3 phase is the main strengthening phase and forms the eutectic structure with α-Mg matrix in the as cast alloy. The strengthening phases semi-continuously connect and separate the α-Mg matrix into cell structure. The average grain size of the as cast alloy is about 60 μm. The heat treatment promotes the solid solution of the strengthening phase and precipitation of small particles inside grain.Compared with the as cast alloy, the heat treatment increases grain size a little and mechanical properties more than 30%. The hot extrusion refines the grain and strengthening phase, which increase the mechanical properties significantly. Moreover, the great deformation by the hot extrusion results in the ultrafine structure and abundant of crystal defects. The intersection of micro-twins lead to the special region with nanometer size.

Research on the use of space resources

NASA Technical Reports Server (NTRS)

Carroll, W. F. (Editor)

1983-01-01

The second year of a multiyear research program on the processing and use of extraterrestrial resources is covered. The research tasks included: (1) silicate processing, (2) magma electrolysis, (3) vapor phase reduction, and (4) metals separation. Concomitant studies included: (1) energy systems, (2) transportation systems, (3) utilization analysis, and (4) resource exploration missions. Emphasis in fiscal year 1982 was placed on the magma electrolysis and vapor phase reduction processes (both analytical and experimental) for separation of oxygen and metals from lunar regolith. The early experimental work on magma electrolysis resulted in gram quantities of iron (mixed metals) and the identification of significant anode, cathode, and container problems. In the vapor phase reduction tasks a detailed analysis of various process concepts led to the selection of two specific processes designated as ""Vapor Separation'' and ""Selective Ionization.'' Experimental work was deferred to fiscal year 1983. In the Silicate Processing task a thermophysical model of the casting process was developed and used to study the effect of variations in material properties on the cooling behavior of lunar basalt.

A unified classification of stationary phases for packed column supercritical fluid chromatography.

PubMed

West, C; Lesellier, E

2008-05-16

The use of supercritical fluids as chromatographic mobile phases allows to obtain rapid separations with high efficiency on packed columns, which could favour the replacement of numerous HPLC methods by supercritical fluid chromatography (SFC) ones. Moreover, despite some unexpected chromatographic behaviours, general retention rules are now well understood, and mainly depend on the nature of the stationary phase. The use of polar stationary phases improves the retention of polar compounds, when C18-bonded silica favours the retention of hydrocarbonaceous compounds. In this sense, reversed-phase and normal-phase chromatography can be achieved in SFC, as in HPLC. However, these two domains are clearly separated in HPLC due to the opposite polarity of the mobile phases used for each method. In SFC, the same mobile phase can be used with both polar and non-polar stationary phases. Consequently, the need for a novel classification of stationary phases in SFC appears, allowing a unification of the classical reversed- and normal-phase domains. In this objective, the paper presents the development of a five-dimensional classification based on retention data for 94-111 solutes, using 28 commercially available columns representative of three major types of stationary phases. This classification diagram is based on a linear solvation energy relationship, on the use of solvation vectors and the calculation of similarity factors between the different chromatographic systems. This classification will be of great help in the choice of the well-suited stationary phase, either in regards of a particular separation or to improve the coupling of columns with complementary properties.

Quantitative Phase Imaging in a Volume Holographic Microscope

NASA Astrophysics Data System (ADS)

Waller, Laura; Luo, Yuan; Barbastathis, George

2010-04-01

We demonstrate a method for quantitative phase imaging in a Volume Holographic Microscope (VHM) from a single exposure, describe the properties of the system and show experimental results. The VHM system uses a multiplexed volume hologram (VH) to laterally separate images from different focal planes. This 3D intensity information is then used to solve the transport of intensity (TIE) equation and recover phase quantitatively. We discuss the modifications to the technique that were made in order to give accurate results.

Avoiding chaos in Wonderland

NASA Astrophysics Data System (ADS)

Kohring, G. A.

2006-08-01

Wonderland, a compact, integrated economic, demographic and environmental model, is investigated using methods developed for studying critical phenomena. Simulation results show the parameter space separates into two phases, one of which contains the property of long term, sustainable development. By employing information contain in the phase diagram, an optimal strategy involving pollution taxes is developed as a means of moving a system initially in a unsustainable region of the phase diagram into a region of sustainability while ensuring minimal regret with respect to long-term economic growth.

Fast separation of triterpenoid saponins using supercritical fluid chromatography coupled with single quadrupole mass spectrometry.

PubMed

Huang, Yang; Zhang, Tingting; Zhou, Haibo; Feng, Ying; Fan, Chunlin; Chen, Weijia; Crommen, Jacques; Jiang, Zhengjin

2016-03-20

Triterpenoid saponins (TSs) are the most important components of some traditional Chinese medicines (TCMs) and have exhibited valuable pharmacological properties. In this study, a rapid and efficient method was developed for the separation of kudinosides, stauntosides and ginsenosides using supercritical fluid chromatography coupled with single quadrupole mass spectrometry (SFC-MS). The separation conditions for the selected TSs were carefully optimized after the initial screening of eight stationary phases. The best compromise for all compounds in terms of chromatographic performance and MS sensitivity was obtained when water (5-10%) and formic acid (0.05%) were added to the supercritical carbon dioxide/MeOH mobile phase. Beside the composition of the mobile phase, the nature of the make-up solvent for interfacing SFC with MS was also evaluated. Compared to reversed phase liquid chromatography, the SFC approach showed higher resolution and shorter running time. The developed SFC-MS methods were successfully applied to the separation and identification of TSs present in Ilex latifolia Thunb., Panax quinquefolius L. and Panax ginseng C.A. Meyer. These results suggest that this SFC-MS approach could be employed as a useful tool for the quality assessment of natural products containing TSs as active components. Copyright © 2015 Elsevier B.V. All rights reserved.

Process depending morphology and resulting physical properties of TPU

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

Frick, Achim, E-mail: achim.frick@hs-aalen.de; Spadaro, Marcel, E-mail: marcel.spadaro@hs-aalen.de

2015-12-17

Thermoplastic polyurethane (TPU) is a rubber like material with outstanding properties, e.g. for seal applications. TPU basically provides high strength, low frictional behavior and excellent wear resistance. Though, due to segmented structure of TPU, which is composed of hard segments (HSs) and soft segments (SSs), physical properties depend strongly on the morphological arrangement of the phase separated HSs at a certain ratio of HSs to SSs. It is obvious that the TPU deforms differently depending on its bulk morphology. Basically, the morphology can either consist of HSs segregated into small domains, which are well dispersed in the SS matrix ormore » of few strongly phase separated large size HS domains embedded in the SS matrix. The morphology development is hardly ruled by the melt processing conditions of the TPU. Depending on the morphology, TPU provides quite different physical properties with respect to strength, deformation behavior, thermal stability, creep resistance and tribological performance. The paper deals with the influence of important melt processing parameters, such as temperature, pressure and shear conditions, on the resulting physical properties tested by tensile and relaxation experiments. Furthermore the morphology is studied employing differential scanning calorimeter (DSC), transmission light microscopy (TLM), scanning electron beam microscopy (SEM) and transmission electron beam microscopy (TEM) investigations. Correlations between processing conditions and resulting TPU material properties are elaborated. Flow and shear simulations contribute to the understanding of thermal and flow induced morphology development.« less

Polar stationary phases based on poly(oligo ethylene glycol)diacrylates for capillary gas chromatography

NASA Astrophysics Data System (ADS)

Shiryaeva, V. E.; Popova, T. P.; Korolev, A. A.; Kanat'eva, A. Yu.; Kurganov, A. A.

2017-08-01

New stationary phases for capillary columns in GC are synthesized and studied. The phases are prepared by depositing oligo(ethylene glycol)diacrylates on the column walls and subsequent polymerization (crosslinking) in the presence of peroxide initiators. It is shown that stationary phases based on monomers with molecular weights of 10 kDa or higher exhibit separation properties similar to those of conventional stationary phases based on polyethylene glycol (PEG); however, their thermal stability is higher because they have a higher degree of crosslinking and a more ordered structure of the crosslinked polymers than the respective parameters of phases based on native PEG.

Single Sublattice Endotaxial Phase Separation Driven by Charge Frustration in a Complex Oxide

PubMed Central

2013-01-01

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation. PMID:23750709

Carbon nanotube (CNT) and nanofibrillated cellulose (NFC) reinforcement effect on thermoplastic polyurethane (TPU) scaffolds fabricated via phase separation using dimethyl sulfoxide (DMSO) as solvent.

PubMed

Mi, Hao-Yang; Jing, Xin; Salick, Max R; Cordie, Travis M; Turng, Lih-Sheng

2016-09-01

Although phase separation is a simple method of preparing tissue engineering scaffolds, it suffers from organic solvent residual in the scaffold. Searching for nontoxic solvents and developing effective solvent removal methods are current challenges in scaffold fabrication. In this study, thermoplastic polyurethane (TPU) scaffolds containing carbon nanotubes (CNTs) or nanofibrillated cellulose fibers (NFCs) were prepared using low toxicity dimethyl sulfoxide (DMSO) as a solvent. The effects of two solvent removal approaches on the final scaffold morphology were studied. The freeze drying method caused large pores, with small pores on the pore walls, which created connections between the pores. Meanwhile, the leaching and freeze drying method led to interconnected fine pores with smaller pore diameters. The nucleation effect of CNTs and the phase separation behavior of NFCs in the TPU solution resulted in significant differences in the microstructures of the resulting scaffolds. The mechanical performance of the nanocomposite scaffolds with different morphologies was investigated. Generally, the scaffolds with a fine pore structure showed higher compressive properties, and both the CNTs and NFCs improved the compressive properties of the scaffolds, with greater enhancement found in TPU/NFC nanocomposite scaffolds. In addition, all scaffolds showed good sustainability under cyclical load bearing, and the biocompatibility of the scaffolds was verified via 3T3 fibroblast cell culture. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Molybdenum titanium Phase Diagram Evaluated from Ab initio Calculations

DTIC Science & Technology

2016-10-07

thermodynamic properties of this binary system are not well known and two conflicting descriptions of the β-phase stability have been presented in the...computational thermodynamics CALPHAD approach [13] and the Thermo-Calc software [14]. These studies led to two conflicting descriptions of the stability of...energy calculations, with an energy cutoff separating core and valence states of -6 Ry. 2.2. Thermodynamic modeling The formation enthalpy of a

Experimental Program to Stimulate Competitive Research (EPSCoR)

NASA Technical Reports Server (NTRS)

Dingerson, Michael R.

1997-01-01

Report includes: (1) CLUSTER: "Studies in Macromolecular Behavior in Microgravity Environment": The Role of Protein Oligomers in Protein Crystallization; Phase Separation Phenomena in Microgravity; Traveling Front Polymerizations; Investigating Mechanisms Affecting Phase Transition Response and Changes in Thermal Transport Properties in ER-Fluids under Normal and Microgravity Conditions. (2) CLUSTER: "Computational/Parallel Processing Studies": Flows in Local Chemical Equilibrium; A Computational Method for Solving Very Large Problems; Modeling of Cavitating Flows.

Impact of organic coating on optical growth of ammonium sulfate particles.

PubMed

Robinson, Carly B; Schill, Gregory P; Zarzana, Kyle J; Tolbert, Margaret A

2013-01-01

Light extinction by particles in Earth's atmosphere is strongly dependent on particle size, chemical composition, hygroscopic growth properties, and particle mixing state. Here, the influence of an organic coating on particle optical growth was studied. The particle optical growth factor, fRHext, was measured using cavity ring-down aerosol extinction spectroscopy at 532 nm. The particles were composed of ammonium sulfate (AS), 1,2,6-hexanetriol, and mixed particles containing a wet or dry ammonium sulfate core and a 1,2,6-hexanetriol coating. Dry, coated particles were generated by atomization followed by drying. Wet, coated particles were formed via liquid-liquid phase separation (LLPS). LLPS was achieved by deliquescing and then drying the particles to a relative humidity (RH) between the phase separation RH and the efflorescence RH. For the LLPS particles, the fRHext at each RH was between the fRHext of ammonium sulfate and that of 1,2,6-hexanetriol. In contrast, for the mixed dry, coated particles, the fRHext was the same as 1,2,6-hexanetriol particles. At room temperature, the water uptake properties of AS coated with 1,2,6-hexanetriol are largely dictated by the phase of the AS. Thus, the total water uptake depends on the RH history of the particle and the resulting phase of AS.

Structural, magnetic, and magnetocaloric properties of bilayer manganite La1.38Sr1.62Mn2O7

NASA Astrophysics Data System (ADS)

Yang, Yu-E.; Xie, Yunfei; Xu, Lisha; Hu, Dazhi; Ma, Chunlan; Ling, Langsheng; Tong, Wei; Pi, Li; Zhang, Yuheng; Fan, Jiyu

2018-04-01

In this study, we investigated the structural, magnetic phase transition, and magnetocaloric properties of bilayer perovskite manganite La1.38Sr1.62Mn2O7 based on X-ray diffraction, electron paramagnetic resonance, and temperature-/magnetic field-dependent magnetization measurements. The structural characterization results showed the prepared sample had a tetragonal structure with the space group I4/mmm. The Curie temperature was determined as 114 K in the magnetization studies and a second-order paramagnetic-ferromagnetic transition was confirmed by the Arrott plot, which showed that the slopes were positive for all the curves. According to the variation in the electron paramagnetic resonance spectrum, we detected obvious electronic phase separation across a broad temperature range from 220 to 80 K in this magnetic material, thereby indicating that the paramagnetic and ferromagnetic phases coexist above as well as below the Curie temperature. Based on a plot of the isothermal magnetization versus the magnetic applied field, we deduced the maximum magnetic entropy change, which only reached 1.89 J/kg.K under an applied magnetic field of 7.0 T. These theoretical investigations indicated that in addition to the magnetoelastic couplings and electron interaction, electronic phase separation and anisotropic exchange interactions also affect the magnetic entropy changes in this bilayer manganite.

Diamond based adsorbents and their application in chromatography.

PubMed

Peristyy, Anton A; Fedyanina, Olga N; Paull, Brett; Nesterenko, Pavel N

2014-08-29

The idea of using diamond and diamond containing materials in separation sciences has attracted a strong interest in the past decade. The combination of a unique range of properties, such as chemical inertness, mechanical, thermal and hydrolytic stability, excellent thermal conductivity with minimal thermal expansion and intriguing adsorption properties makes diamond a promising material for use in various modes of chromatography. This review summarises the recent research on the preparation of diamond and diamond based stationary phases, their properties and chromatographic performance. Special attention is devoted to the dominant retention mechanisms evident for particular diamond containing phases, and their subsequent applicability to various modes of chromatography, including chromatography carried out under conditions of high temperature and pressure. Copyright © 2014 Elsevier B.V. All rights reserved.

Analytical and semipreparative chiral separation of cis-itraconazole on cellulose stationary phases by high-performance liquid chromatography.

PubMed

Kurka, Ondřej; Kučera, Lukáš; Bednář, Petr

2016-07-01

cis-Itraconazole is a chiral antifungal drug administered as a racemate. The knowledge of properties of individual cis-itraconazole stereoisomers is vital information for medicine and biosciences as different stereoisomers of cis-itraconazole may possess different affinity to certain biological pathways in the human body. For this purpose, either chiral synthesis of enantiomers or chiral separation of racemate can be used. This paper presents a two-step high-performance liquid chromatography approach for the semipreparative isolation of four stereoisomers (two enantiomeric pairs) of itraconazole using polysaccharide stationary phases and volatile organic mobile phases without additives in isocratic mode. The approach used involves the separation of the racemate into three fractions (i.e. two pure stereoisomers and one mixed fraction containing the remaining two stereoisomers) in the first run and consequent separation of the collected mixed fraction in the second one. For this purpose, combination of cellulose tris-(4-methylbenzoate) and cellulose tris-(3,5-dimehylphenylcarbamate) columns with complementary selectivity for cis-itraconazole provided full separation of all four stereoisomers (with purity of each isomer > 97%). The stereoisomers were collected, their optical rotation determined and their identity confirmed based on the results of a previously published study. Pure separated stereoisomers are subjected to further biological studies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PROPERTIES OF INTERFACES AND TRANSPORT ACROSS THEM

EPA Science Inventory

Much of the biological activity in cell cytoplasm occurs in compartments which are thought to form by phase separation, and many of the functions of these compartments occur by the transport or exchange of molecules across interfaces. Thus, a fundamentally based discussion of th...

A simple subcritical chromatographic test for an extended ODS high performance liquid chromatography column classification.

PubMed

Lesellier, Eric; Tchapla, Alain

2005-12-23

This paper describes a new test designed in subcritical fluid chromatography (SFC) to compare the commercial C18 stationary phase properties. This test provides, from a single analysis of carotenoid pigments, the absolute hydrophobicity, the silanol activity and the steric separation factor of the ODS stationary phases. Both the choice of the analytical conditions and the validation of the information obtained from the chromatographic measurements are detailed. Correlations of the carotenoid test results with results obtained from other tests (Tanaka, Engelhard, Sander and Wise) performed both in SFC and HPLC are discussed. Two separation factors, calculated from the retention of carotenoid pigments used as probe, allowed to draw a first classification diagram. Columns, which present identical chromatographic behaviors are located in the same area on this diagram. This location can be related to the stationary phase properties: endcapping treatments, bonding density, linkage functionality, specific area or silica pore diameter. From the first classification, eight groups of columns are distinguished. One group of polymer coated silica, three groups of polymeric octadecyl phases, depending on the pore size and the endcapping treatment, and four groups of monomeric stationary phases. An additional classification of the four monomeric groups allows the comparison of these stationary phases inside each group by using the total hydrophobicity. One hundred and twenty-nine columns were analysed by this simple and rapid test, which allows a comparison of columns with the aim of helping along their choice in HPLC.

Separation of Gadolinium (Gd) using Synergic Solvent Mixed Topo-D2EHPA with Extraction Method.

NASA Astrophysics Data System (ADS)

Effendy, N.; Basuki, K. T.; Biyantoro, D.; Perwira, N. K.

2018-04-01

The main problem to obtain Gd with high purity is the similarity of chemical properties and physical properties with the other rare earth elements (REE) such as Y and Dy, it is necessary to do separation by the extraction process. The purpose of this research to determine the best solvent type, amount of solvent, feed and solvent ratio in the Gd extraction process, to determine the rate order and the value of the rate constant of Gd concentration based on experimental data of aqueous phase concentration as a function of time and to know the effect of temperature on the reaction speed constant. This research was conducted on variation of solvent, amount of solvent, feed and solvent ratio in the extraction process of Gd separation, extraction time to determine the order value and the rate constant of Gd concentration in extraction process based on the aqueous phase concentration data as a function of time, to the rate constant of decreasing concentration of Gd. Based on the calculation results, the solvent composition was obtained with the best feed to separate the rare earth elements Gd in the extraction process is 1 : 4 with 15% concentration of TOPO and 10% concentration of D2EHPA. The separation process of Gd using extraction method by solvent TOPO-D2EHPA 2 : 1 comparison is better than single solvent D2EHPA / TOPO because of the synergistic effect. The rate order of separation process of Gd follows order 1. The Arrhenius Gd equation becomes k = 1.46 x 10-7 exp (-6.96 kcal / mol / RT).

Correlative infrared nanospectroscopic and nanomechanical imaging of block copolymer microdomains

PubMed Central

Pollard, Benjamin

2016-01-01

Summary Intermolecular interactions and nanoscale phase separation govern the properties of many molecular soft-matter systems. Here, we combine infrared vibrational scattering scanning near-field optical microscopy (IR s-SNOM) with force–distance spectroscopy for simultaneous characterization of both nanoscale optical and nanomechanical molecular properties through hybrid imaging. The resulting multichannel images and correlative analysis of chemical composition, spectral IR line shape, modulus, adhesion, deformation, and dissipation acquired for a thin film of a nanophase separated block copolymer (PS-b-PMMA) reveal complex structural variations, in particular at domain interfaces, not resolved in any individual signal channel alone. These variations suggest that regions of multicomponent chemical composition, such as the interfacial mixing regions between microdomains, are correlated with high spatial heterogeneity in nanoscale material properties. PMID:27335750

Phase Separation from Electron Confinement at Oxide Interfaces

NASA Astrophysics Data System (ADS)

Scopigno, N.; Bucheli, D.; Caprara, S.; Biscaras, J.; Bergeal, N.; Lesueur, J.; Grilli, M.

2016-01-01

Oxide heterostructures are of great interest for both fundamental and applicative reasons. In particular, the two-dimensional electron gas at the LaAlO3/SrTiO3 or LaTiO3/SrTiO3 interfaces displays many different properties and functionalities. However, there are clear experimental indications that the interface electronic state is strongly inhomogeneous and therefore it is crucial to investigate possible intrinsic mechanisms underlying this inhomogeneity. Here, the electrostatic potential confining the electron gas at the interface is calculated self-consistently, finding that such confinement may induce phase separation, to avoid a thermodynamically unstable state with a negative compressibility. This provides a robust mechanism for the inhomogeneous character of these interfaces.

Micropore Geometry Manipulation by Macroscopic Deformation Based on Shape Memory Effect in Porous PLLA Membrane and its Enhanced Separation Performance.

PubMed

Zhao, Jingxin; Yang, Qiucheng; Wang, Tao; Wang, Lian; You, Jichun; Li, Yongjin

2017-12-20

An effective strategy to tailor the microporous structures has been developed based on the shape memory effect in porous poly(l-lactic acid) membranes in which tiny crystals and amorphous matrix play the roles of shape-fixed phase and reversible-phase, respectively. Our results indicate that not only PLLA membranes but micropores exhibit shape memory properties. The proportional deformations on two scales have been achieved by uniaxial or biaxial tension, providing a facile way to manipulate continuously the size and the orientation degree of pores on microscale. The enhanced separation performance has been validated by taking polystyrene colloids with varying diameters as an example.

Fast non-aqueous reversed-phase liquid chromatography separation of triacylglycerol regioisomers with isocratic mobile phase. Application to different oils and fats.

PubMed

Tamba Sompila, Arnaud W G; Héron, Sylvie; Hmida, Dorra; Tchapla, Alain

2017-01-15

The distribution of fatty acid species at the sn-1/3 position or the sn-2 position of triacylglycerols (TAGs) in natural fats and oils affects their physical and nutritional properties. In fats and oils, determining the presence of one or two regioisomers and the identification of structure, where they do have one, as well as their separation, became a problem of fundamental importance to solve. A variety of instrumental technics has been proposed, such as MS, chromatography-MS or pure chromatography. A number of studies deal with the optimization of the separation, but very often, they are expensive in time. In the present study, in order to decrease the analysis time while maintaining good chromatographic separation, we tested different monomeric and polymeric stationary phases and different chromatographic conditions (mobile phase composition and analysis temperature) using Non-Aqueous Reversed Phase Liquid Chromatography (NARP-LC). It was demonstrated that mixed polymeric stationary bonded silica with accessible terminal hydroxyl groups leads to very good separation for the pairs of TAGs regioisomers constituted by two saturated and one unsaturated fatty acid (with double bond number: from 1 to 6). A Nucleodur C18 ISIS percolated by isocratic mobile phase (acetonitrile/2-propanol) at 18°C leads to their separations in less than 15min. The difference of retention times between two regioisomers XYX and XXY are large enough to confirm, as application, the presence of POP, SOP, SOS and PLP and no PPO, SPO, SSO and PPL in Theobroma cacao butter. In the same way, this study respectively shows the presence of SOS, SOP and no SSO, PSO in Butyrospermum parkii butter, POP, SOP, SOS and no PPO, PSO and SSO in Carapa oil and finally POP and no PPO in Pistacia Lentiscus oil. Copyright © 2016 Elsevier B.V. All rights reserved.

Swelling equilibrium of dentin adhesive polymers formed on the water-adhesive phase boundary: Experiments and micromechanical model

PubMed Central

Misra, Anil; Parthasarathy, Ranganathan; Ye, Qiang; Singh, Viraj; Spencer, Paulette

2013-01-01

During their application to the wet, oral environment, dentin adhesives can experience phase separation and composition change which can compromise the quality of the hybrid layer formed at the dentin-adhesive interface. The chemical composition of polymer phases formed in the hybrid layer can be represented using a ternary water-adhesive phase diagram. In this paper, these polymer phases have been characterized using a suite of mechanical tests and swelling experiments. The experimental results were evaluated using granular micromechanics based model that incorporates poro-mechanical effects and polymer-solvent thermodynamics. The variation of the model parameters and model-predicted polymer properties has been studied as a function of composition along the phase boundary. The resulting structure-property correlations provide insight into interactions occurring at the molecular level in the saturated polymer system. These correlations can be used for modeling the mechanical behavior of hybrid layer, and are expected to aid in the design and improvement of water-compatible dentin adhesive polymers. PMID:24076070

Unsteady RANS/DES analysis of flow around helicopter rotor blades at forword flight conditions

NASA Astrophysics Data System (ADS)

Zhang, Zhenyu; Qian, Yaoru

2018-05-01

In this paper, the complex flows around forward-flying helicopter blades are numerically investigated. Both the Reynolds-averaged Navier-Stokes (RANS) and the Detached Eddy Simulation (DES) methods are used for the analysis of characteristics like local dynamic flow separation, effects of radial sweeping and reversed flow. The flow was solved by a highly efficient finite volume solver with multi-block structured grids. Focusing upon the complexity of the advance ratio effects, above properties are fully recognized. The current results showed significant agreements between both RANS and DES methods at phases with attached flow phases. Detailed information of separating flow near the withdrawal phases are given by DES results. The flow analysis of these blades under reversed flow reveals a significant interaction between the reversed flow and the span-wise sweeping.

The metal-insulator transition in a phase-separated manganite studied by in situ STS

NASA Astrophysics Data System (ADS)

Snijders, P. C.; Gao, M.; Guo, H.; Ward, T. Z.; Gao, H.-J.; Shen, J.; Gai, Z.

2012-02-01

Electronic phase separation (EPS) is a key feature at the heart of the wide variety of electronic and magnetic properties in complex oxides. One consequence of EPS is that electronic transport experiments in bulk materials or 2D films mostly probe the low resistivity electronic phases due to the percolative path of the current. We study oxygen deficient La5/8-xPrxCa3/8M nO3 (LPCMO) thin films using both in situ scanning tunneling spectroscopy (STS) and ex situ transport experiments. The oxygen deficiency is known to decrease the metal-insulator transition (MIT) temperature or even completely suppress the MIT in conventional transport experiments. We show that in situ STS is able to detect the MIT even in systems where conventional transport experiments do not show an MIT at zero magnetic field.

Recent advances in liquid-phase separations for clinical metabolomics.

PubMed

Kohler, Isabelle; Giera, Martin

2017-01-01

Over the last decades, several technological improvements have been achieved in liquid-based separation techniques, notably, with the advent of fully porous sub-2 μm particles and superficially porous sub-3 μm particles, the comeback of supercritical fluid chromatography, and the development of alternative chromatographic modes such as hydrophilic interaction chromatography. Combined with mass spectrometry, these techniques have demonstrated their added value, substantially increasing separation efficiency, selectivity, and speed of analysis. These benefits are essential in modern clinical metabolomics typically involving the study of large-scale sample cohorts and the analysis of thousands of metabolites showing extensive differences in physicochemical properties. This review presents a brief overview of the recent developments in liquid-phase separation sciences in the context of clinical metabolomics, focusing on increased throughput as well as metabolite coverage. Relevant metabolomics applications highlighting the benefits of ultra-high performance liquid chromatography, core-shell technology, high-temperature liquid chromatography, capillary electrophoresis, supercritical fluid chromatography, and hydrophilic interaction chromatography are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amphiphilic phase-transforming catalysts for transesterification of triglycerides

NASA Astrophysics Data System (ADS)

Nawaratna, Gayan Ivantha

Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be recovered in the form of their polymerized counterparts as a result of condensation polymerization subsequent to completion of the transesterification reaction.

Fabricating fiber Bragg gratings with two phase masks based on reconstruction-equivalent-chirp technique.

PubMed

Gao, Liang; Chen, Xiangfei; Xiong, Jintian; Liu, Shengchun; Pu, Tao

2012-01-30

Based on reconstruction-equivalent-chirp (REC) technique, a novel solution for fabricating low-cost long fiber Bragg gratings (FBGs) with desired properties is proposed and initially studied. A proof-of-concept experiment is demonstrated with two conventional uniform phase masks and a submicron-precision translation stage, successfully. It is shown that the original phase shift (OPS) caused by phase mismatch of the two phase masks can be compensated by the equivalent phase shift (EPS) at the ±1st channels of sampled FBGs, separately. Furthermore, as an example, a π phase-shifted FBG of about 90 mm is fabricated by using these two 50mm-long uniform phase masks based on the presented method.

Polymer amide as an early topology.

PubMed

McGeoch, Julie E M; McGeoch, Malcolm W

2014-01-01

Hydrophobic polymer amide (HPA) could have been one of the first normal density materials to accrete in space. We present ab initio calculations of the energetics of amino acid polymerization via gas phase collisions. The initial hydrogen-bonded di-peptide is sufficiently stable to proceed in many cases via a transition state into a di-peptide with an associated bound water molecule of condensation. The energetics of polymerization are only favorable when the water remains bound. Further polymerization leads to a hydrophobic surface that is phase-separated from, but hydrogen bonded to, a small bulk water complex. The kinetics of the collision and subsequent polymerization are discussed for the low-density conditions of a molecular cloud. This polymer in the gas phase has the properties to make a topology, viz. hydrophobicity allowing phase separation from bulk water, capability to withstand large temperature ranges, versatility of form and charge separation. Its flexible tetrahedral carbon atoms that alternate with more rigid amide groups allow it to deform and reform in hazardous conditions and its density of hydrogen bonds provides adhesion that would support accretion to it of silicon and metal elements to form a stellar dust material.

Nup98 FG domains from diverse species spontaneously phase-separate into particles with nuclear pore-like permselectivity

PubMed Central

Schmidt, Hermann Broder; Görlich, Dirk

2015-01-01

Nuclear pore complexes (NPCs) conduct massive transport mediated by shuttling nuclear transport receptors (NTRs), while keeping nuclear and cytoplasmic contents separated. The NPC barrier in Xenopus relies primarily on the intrinsically disordered FG domain of Nup98. We now observed that Nup98 FG domains of mammals, lancelets, insects, nematodes, fungi, plants, amoebas, ciliates, and excavates spontaneously and rapidly phase-separate from dilute (submicromolar) aqueous solutions into characteristic ‘FG particles’. This required neither sophisticated experimental conditions nor auxiliary eukaryotic factors. Instead, it occurred already during FG domain expression in bacteria. All Nup98 FG phases rejected inert macromolecules and yet allowed far larger NTR cargo complexes to rapidly enter. They even recapitulated the observations that large cargo-domains counteract NPC passage of NTR⋅cargo complexes, while cargo shielding and increased NTR⋅cargo surface-ratios override this inhibition. Their exquisite NPC-typical sorting selectivity and strong intrinsic assembly propensity suggest that Nup98 FG phases can form in authentic NPCs and indeed account for the permeability properties of the pore. DOI: http://dx.doi.org/10.7554/eLife.04251.001 PMID:25562883

Tailoring transport properties of phase-separated manganite films with ordered magnetic nanostructures

DOE PAGES

Vlaminck, V.; Yanez, W.; Hoffman, J.; ...

2016-08-02

Here, the magnetotransport properties of thin manganite films (La 0.7Ca 0.3MnO 3) coupled with arrays of permalloy (Py) nanodots deposited on the surface of the film are studied as a function of temperature, magnetic field, and the size of the dots. In the presence of the magnetic dots, a reduction of the electrical resistivity is observed, especially at the insulator-to-metal transition, as well as a shift of the transition peak towards higher temperatures. This indicates that, due to local interface exchange coupling, highly conductive ferromagnetic domains are nucleated in the manganite film underneath the Py nanodots. The use of amore » simplified resistor network model allows us to estimate the size of the metallic regions induced by exchange coupling. At low temperatures, these regions extend ~70 nm beyond the edge of the nanodots, a length scale comparable to the correlation length of the ferromagnetic clusters in the phase-separated state of La 0.7Ca 0.3MnO 3.« less

Fine-Tuning the Quasi-3D Geometry: Enabling Efficient Nonfullerene Organic Solar Cells Based on Perylene Diimides.

PubMed

Liu, Zhitian; Zhang, Linhua; Shao, Ming; Wu, Yao; Zeng, Di; Cai, Xiang; Duan, Jiashun; Zhang, Xiaolu; Gao, Xiang

2018-01-10

The geometries of acceptors based on perylene diimides (PDIs) are important for improving the phase separation and charge transport in organic solar cells. To fine-tune the geometry, biphenyl, spiro-bifluorene, and benzene were used as the core moiety to construct quasi-three-dimensional nonfullerene acceptors based on PDI building blocks. The molecular geometries, energy levels, optical properties, photovoltaic properties, and exciton kinetics were systematically studied. The structure-performance relationship was discussed as well. Owing to the finest phase separation, the highest charge mobility and smallest nongeminate recombination, the power conversion efficiency of nonfullerene solar cells using PDI derivatives with biphenyl core (BP-PDI 4 ) as acceptor reached 7.3% when high-performance wide band gap donor material poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione))] was blended.

Optically transparent, mechanically durable, nanostructured superhydrophobic surfaces enabled by spinodally phase-separated glass thin films

NASA Astrophysics Data System (ADS)

Aytug, Tolga; Simpson, John T.; Lupini, Andrew R.; Trejo, Rosa M.; Jellison, Gerald E.; Ivanov, Ilia N.; Pennycook, Stephen J.; Hillesheim, Daniel A.; Winter, Kyle O.; Christen, David K.; Hunter, Scott R.; Haynes, J. Allen

2013-08-01

We describe the formation and properties of atomically bonded, optical quality, nanostructured thin glass film coatings on glass plates, utilizing phase separation by spinodal decomposition in a sodium borosilicate glass system. Following deposition via magnetron sputtering, thermal processing and differential etching, these coatings are structurally superhydrophilic (i.e., display anti-fogging functionality) and demonstrate robust mechanical properties and superior abrasion resistance. After appropriate chemical surface modification, the surfaces display a stable, non-wetting Cassie-Baxter state and exhibit exceptional superhydrophobic performance, with water droplet contact angles as large as 172°. As an added benefit, in both superhydrophobic and superhydrophilic states these nanostructured surfaces can block ultraviolet radiation and can be engineered to be anti-reflective with broadband and omnidirectional transparency. Thus, the present approach could be tailored toward distinct coatings for numerous markets, such as residential windows, windshields, specialty optics, goggles, electronic and photovoltaic cover glasses, and optical components used throughout the US military.

Optically transparent, mechanically durable, nanostructured superhydrophobic surfaces enabled by spinodally phase-separated glass thin films.

PubMed

Aytug, Tolga; Simpson, John T; Lupini, Andrew R; Trejo, Rosa M; Jellison, Gerald E; Ivanov, Ilia N; Pennycook, Stephen J; Hillesheim, Daniel A; Winter, Kyle O; Christen, David K; Hunter, Scott R; Haynes, J Allen

2013-08-09

We describe the formation and properties of atomically bonded, optical quality, nanostructured thin glass film coatings on glass plates, utilizing phase separation by spinodal decomposition in a sodium borosilicate glass system. Following deposition via magnetron sputtering, thermal processing and differential etching, these coatings are structurally superhydrophilic (i.e., display anti-fogging functionality) and demonstrate robust mechanical properties and superior abrasion resistance. After appropriate chemical surface modification, the surfaces display a stable, non-wetting Cassie-Baxter state and exhibit exceptional superhydrophobic performance, with water droplet contact angles as large as 172°. As an added benefit, in both superhydrophobic and superhydrophilic states these nanostructured surfaces can block ultraviolet radiation and can be engineered to be anti-reflective with broadband and omnidirectional transparency. Thus, the present approach could be tailored toward distinct coatings for numerous markets, such as residential windows, windshields, specialty optics, goggles, electronic and photovoltaic cover glasses, and optical components used throughout the US military.

Theory of Phase Separation and Polarization for Pure Ionic Liquids.

PubMed

Gavish, Nir; Yochelis, Arik

2016-04-07

Room temperature ionic liquids are attractive to numerous applications and particularly, to renewable energy devices. As solvent free electrolytes, they demonstrate a paramount connection between the material morphology and Coulombic interactions: the electrode/RTIL interface is believed to be a product of both polarization and spatiotemporal bulk properties. Yet, theoretical studies have dealt almost exclusively with independent models of morphology and electrokinetics. Introduction of a distinct Cahn-Hilliard-Poisson type mean-field framework for pure molten salts (i.e., in the absence of any neutral component), allows a systematic coupling between morphological evolution and the electrokinetic phenomena, such as transient currents. Specifically, linear analysis shows that spatially periodic patterns form via a finite wavenumber instability and numerical simulations demonstrate that while labyrinthine type patterns develop in the bulk, lamellar structures are favored near charged surfaces. The results demonstrate a qualitative phenomenology that is observed empirically and thus, provide a physically consistent methodology to incorporate phase separation properties into an electrochemical framework.

Physics Based Model for Cryogenic Chilldown and Loading. Part IV: Code Structure

NASA Technical Reports Server (NTRS)

Luchinsky, D. G.; Smelyanskiy, V. N.; Brown, B.

2014-01-01

This is the fourth report in a series of technical reports that describe separated two-phase flow model application to the cryogenic loading operation. In this report we present the structure of the code. The code consists of five major modules: (1) geometry module; (2) solver; (3) material properties; (4) correlations; and finally (5) stability control module. The two key modules - solver and correlations - are further divided into a number of submodules. Most of the physics and knowledge databases related to the properties of cryogenic two-phase flow are included into the cryogenic correlations module. The functional form of those correlations is not well established and is a subject of extensive research. Multiple parametric forms for various correlations are currently available. Some of them are included into correlations module as will be described in details in a separate technical report. Here we describe the overall structure of the code and focus on the details of the solver and stability control modules.

Manufacturing of biodegradable polyurethane scaffolds based on polycaprolactone using a phase separation method: physical properties and in vitro assay

PubMed Central

Asefnejad, Azadeh; Khorasani, Mohammad Taghi; Behnamghader, Aliasghar; Farsadzadeh, Babak; Bonakdar, Shahin

2011-01-01

Background Biodegradable polyurethanes have found widespread use in soft tissue engineering due to their suitable mechanical properties and biocompatibility. Methods In this study, polyurethane samples were synthesized from polycaprolactone, hexamethylene diisocyanate, and a copolymer of 1,4-butanediol as a chain extender. Polyurethane scaffolds were fabricated by a combination of liquid–liquid phase separation and salt leaching techniques. The effect of the NCO:OH ratio on porosity content and pore morphology was investigated. Results Scanning electron micrographs demonstrated that the scaffolds had a regular distribution of interconnected pores, with pore diameters of 50–300 μm, and porosities of 64%–83%. It was observed that, by increasing the NCO:OH ratio, the average pore size, compressive strength, and compressive modulus increased. L929 fibroblast and chondrocytes were cultured on the scaffolds, and all samples exhibited suitable cell attachment and growth, with a high level of biocompatibility. Conclusion These biodegradable polyurethane scaffolds demonstrate potential for soft tissue engineering applications. PMID:22072874

Novel phase diagram behavior and materials design in heterostructural semiconductor alloys

PubMed Central

Holder, Aaron M.; Siol, Sebastian; Ndione, Paul F.; Peng, Haowei; Deml, Ann M.; Matthews, Bethany E.; Schelhas, Laura T.; Toney, Michael F.; Gordon, Roy G.; Tumas, William; Perkins, John D.; Ginley, David S.; Gorman, Brian P.; Tate, Janet; Zakutayev, Andriy; Lany, Stephan

2017-01-01

Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the critical composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region. PMID:28630928

Novel phase diagram behavior and materials design in heterostructural semiconductor alloys.

PubMed

Holder, Aaron M; Siol, Sebastian; Ndione, Paul F; Peng, Haowei; Deml, Ann M; Matthews, Bethany E; Schelhas, Laura T; Toney, Michael F; Gordon, Roy G; Tumas, William; Perkins, John D; Ginley, David S; Gorman, Brian P; Tate, Janet; Zakutayev, Andriy; Lany, Stephan

2017-06-01

Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the critical composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region.

Novel phase diagram behavior and materials design in heterostructural semiconductor alloys

DOE PAGES

Holder, Aaron M.; Siol, Sebastian; Ndione, Paul F.; ...

2017-06-07

Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the criticalmore » composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Furthermore, thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region.« less

Two-Point Microrheology of Phase-Separated Domains in Lipid Bilayers

PubMed Central

Hormel, Tristan T.; Reyer, Matthew A.; Parthasarathy, Raghuveer

2015-01-01

Though the importance of membrane fluidity for cellular function has been well established for decades, methods for measuring lipid bilayer viscosity remain challenging to devise and implement. Recently, approaches based on characterizing the Brownian dynamics of individual tracers such as colloidal particles or lipid domains have provided insights into bilayer viscosity. For fluids in general, however, methods based on single-particle trajectories provide a limited view of hydrodynamic response. The technique of two-point microrheology, in which correlations between the Brownian dynamics of pairs of tracers report on the properties of the intervening medium, characterizes viscosity at length-scales that are larger than that of individual tracers and has less sensitivity to tracer-induced distortions, but has never been applied to lipid membranes. We present, to our knowledge, the first two-point microrheological study of lipid bilayers, examining the correlated motion of domains in phase-separated lipid vesicles and comparing one- and two-point results. We measure two-point correlation functions in excellent agreement with the forms predicted by two-dimensional hydrodynamic models, analysis of which reveals a viscosity intermediate between those of the two lipid phases, indicative of global fluid properties rather than the viscosity of the local neighborhood of the tracer. PMID:26287625

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

DOE PAGES

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira; ...

2016-01-29

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

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

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Independent active and thermodynamic processes govern the nucleolus assembly in vivo

PubMed Central

Falahati, Hanieh; Wieschaus, Eric

2017-01-01

Membraneless organelles play a central role in the organization of protoplasm by concentrating macromolecules, which allows efficient cellular processes. Recent studies have shown that, in vitro, certain components in such organelles can assemble through phase separation. Inside the cell, however, such organelles are multicomponent, with numerous intermolecular interactions that can potentially affect the demixing properties of individual components. In addition, the organelles themselves are inherently active, and it is not clear how the active, energy-consuming processes that occur constantly within such organelles affect the phase separation behavior of the constituent macromolecules. Here, we examine the phase separation model for the formation of membraneless organelles in vivo by assessing the two features that collectively distinguish it from active assembly, namely temperature dependence and reversibility. We use a microfluidic device that allows accurate and rapid manipulation of temperature and examine the quantitative dynamics by which six different nucleolar proteins assemble into the nucleoli of Drosophila melanogaster embryos. Our results indicate that, although phase separation is the main mode of recruitment for four of the studied proteins, the assembly of the other two is irreversible and enhanced at higher temperatures, behaviors indicative of active recruitment to the nucleolus. These two subsets of components differ in their requirements for ribosomal DNA; the two actively assembling components fail to assemble in the absence of ribosomal DNA, whereas the thermodynamically driven components assemble but lose temporal and spatial precision. PMID:28115706

Anodic etching of GaN based film with a strong phase-separated InGaN/GaN layer: Mechanism and properties

NASA Astrophysics Data System (ADS)

Gao, Qingxue; Liu, Rong; Xiao, Hongdi; Cao, Dezhong; Liu, Jianqiang; Ma, Jin

2016-11-01

A strong phase-separated InGaN/GaN layer, which consists of multiple quantum wells (MQW) and superlattices (SL) layers and can produce a blue wavelength spectrum, has been grown on n-GaN thin film, and then fabricated into nanoporous structures by electrochemical etching method in oxalic acid. Scanning electron microscopy (SEM) technique reveals that the etching voltage of 8 V leads to a vertically aligned nanoporous structure, whereas the films etched at 15 V show branching pores within the n-GaN layer. Due to the low doping concentration of barriers (GaN layers) in the InGaN/GaN layer, we observed a record-low rate of etching (<100 nm/min) and nanopores which are mainly originated from the V-pits in the phase-separated layer. In addition, there exists a horizontal nanoporous structure at the interface between the phase-separated layer and the n-GaN layer, presumably resulting from the high transition of electrons between the barrier and the well (InGaN layer) at the interface. As compared to the as-grown MQW structure, the etched MQW structure exhibits a photoluminescence (PL) enhancement with a partial relaxation of compressive stress due to the increased light-extracting surface area and light-guiding effect. Such a compressive stress relaxation can be further confirmed by Raman spectra.

Properties of interfaces and transport across them.

PubMed

Cabezas, H

2000-01-01

Much of the biological activity in cell cytoplasm occurs in compartments some of which may be formed, as suggested in this book, by phase separation, and many of the functions of such compartments depend on the transport or exchange of molecules across interfaces. Thus a fundamentally based discussion of the properties of phases, interfaces, and diffusive transport across interfaces has been given to further elucidate these phenomena. An operational criterion for the width of interfaces is given in terms of molecular and physical arguments, and the properties of molecules inside phases and interfaces are discussed in terms of molecular arguments. In general, the properties of the interface become important when the molecules diffusing across are smaller than the width of the interface. Equilibrium partitioning, Donnan phenomena, and electrochemical potentials at interfaces are also discussed in detail. The mathematical expressions for modeling transport across interfaces are discussed in detail. These describe a practical and detailed model for transport across interfaces. For molecules smaller than the width of the interface, this includes a detailed model for diffusion inside the interface. Last, the question of the time scale for phase formation and equilibration in biological systems is discussed.

Determinants, analysis and interpretation of the muscle compound action potential (M wave) in humans: implications for the study of muscle fatigue.

PubMed

Rodriguez-Falces, Javier; Place, Nicolas

2018-03-01

The compound muscle action potential (M wave) has been commonly used to assess the peripheral properties of the neuromuscular system. More specifically, changes in the M-wave features are used to examine alterations in neuromuscular propagation that can occur during fatiguing contractions. The utility of the M wave is based on the assumption that impaired neuromuscular propagation results in a decrease in M-wave size. However, there remains controversy on whether the size of the M wave is increased or decreased during and/or after high-intensity exercise. The controversy partly arises from the fact that previous authors have considered the M wave as a whole, i.e., without analyzing separately its first and second phases. However, in a series of studies we have demonstrated that the first and second phases of the M wave behave in a different manner during and after fatiguing contractions. The present review is aimed at five main objectives: (1) to describe the mechanistic factors that determine the M-wave shape; (2) to analyze the various factors influencing M-wave properties; (3) to emphasize the need to analyze separately the first and second M-wave phases to adequately identify and interpret changes in muscle fiber membrane properties; (4) to advance the hypothesis that it is an increase (and not a decrease) of the M-wave first phase which reflects impaired sarcolemmal membrane excitability; and (5) to revisit the involvement of impaired sarcolemmal membrane excitability in the reduction of the force generating capacity.

Modified T-history method for measuring thermophysical properties of phase change materials at high temperature

NASA Astrophysics Data System (ADS)

Omaraa, Ehsan; Saman, Wasim; Bruno, Frank; Liu, Ming

2017-06-01

Latent heat storage using phase change materials (PCMs) can be used to store large amounts of energy in a narrow temperature difference during phase transition. The thermophysical properties of PCMs such as latent heat, specific heat and melting and solidification temperature need to be defined at high precision for the design and estimating the cost of latent heat storage systems. The existing laboratory standard methods, such as differential thermal analysis (DTA) and differential scanning calorimetry (DSC), use a small sample size (1-10 mg) to measure thermophysical properties, which makes these methods suitable for homogeneous elements. In addition, this small amount of sample has different thermophysical properties when compared with the bulk sample and may have limitations for evaluating the properties of mixtures. To avoid the drawbacks in existing methods, the temperature - history (T-history) method can be used with bulk quantities of PCM salt mixtures to characterize PCMs. This paper presents a modified T-history setup, which was designed and built at the University of South Australia to measure the melting point, heat of fusion, specific heat, degree of supercooling and phase separation of salt mixtures for a temperature range between 200 °C and 400 °C. Sodium Nitrate (NaNO3) was used to verify the accuracy of the new setup.

Production of Poly(ε-Caprolactone)/Hydroxyapatite Composite Scaffolds with a Tailored Macro/Micro-Porous Structure, High Mechanical Properties, and Excellent Bioactivity

PubMed Central

Kim, Jong-Woo; Shin, Kwan-Ha; Koh, Young-Hag; Hah, Min Jin; Moon, Jiyoung; Kim, Hyoun-Ee

2017-01-01

We produced poro-us poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite scaffolds for bone regeneration, which can have a tailored macro/micro-porous structure with high mechanical properties and excellent in vitro bioactivity using non-solvent-induced phase separation (NIPS)-based 3D plotting. This innovative 3D plotting technique can create highly microporous PCL/HA composite filaments by inducing unique phase separation in PCL/HA solutions through the non-solvent-solvent exchange phenomenon. The PCL/HA composite scaffolds produced with various HA contents (0 wt %, 10 wt %, 15 wt %, and 20 wt %) showed that PCL/HA composite struts with highly microporous structures were well constructed in a controlled periodic pattern. Similar levels of overall porosity (~78 vol %) and pore size (~248 µm) were observed for all the PCL/HA composite scaffolds, which would be highly beneficial to bone tissue regeneration. Mechanical properties, such as ultimate tensile strength and compressive yield strength, increased with an increase in HA content. In addition, incorporating bioactive HA particles into the PCL polymer led to remarkable enhancements in in vitro apatite-forming ability. PMID:28937605

Volume and Surface Properties of a Bismuth-Containing Separating Nickel Melt

NASA Astrophysics Data System (ADS)

Filippov, K. S.

2017-11-01

The influence of a bismuth impurity on the properties of solid and liquid alloys in the concentration range that obeys Henry's law is considered. The structural and physicochemical properties, specifically, the density and the surface tension, of real melts are studied on relatively pure metals. The changes in the properties of the melts are estimated from changes in the temperature dependences of the density and the surface tension upon heating and cooling and in the concentration dependences of these parameters at a constant temperature. These dependences exhibit a correlation between the volume and surface properties of the melts: the density and the surface tension increase or decrease simultaneously. The introduction of bismuth in the nickel melt is accompanied by the appearance of a relatively strong compression effect (i.e., a decrease in the melt volume). At a certain bismuth content in the melt, the compression effect weakens because of the appearance of an excess phase or its associates and melt separation.

Synthesis and evaluation of porous polymethylsilsesquioxane microspheres as low silanol activity chromatographic stationary phase for basic compound separation.

PubMed

Huo, Zhixia; Wan, Qianhong; Chen, Lei

2018-06-08

Polymethylsilsesquioxanes (PMSQ) are potentially useful materials for liquid chromatography owing to their unique chemical, electrical and mechanical properties. Surprisingly however, no systematic studies on the use of spherical PMSQ particles as chromatographic packing have been reported. Accordingly, we present a comprehensive study aimed to characterize the chromatographic properties of this material in high performance liquid chromatography (HPLC) and to compare them with those observed on methyl (C 1 ) bonded silica phase under comparable conditions. Porous spherical particles were synthesized by a two-step hydrolysis and condensation procedure from methyltrimethoxysilane (MTMS) as a sole precursor. The as-synthesized microspheres possess spherical shape, narrow size distribution, mesoporous structure, high surface area (817 m 2  g -1 ) and reasonable carbon load (16.6%). They can be used directly as the HPLC stationary phase without the need for size classification. The PMSQ phase exhibits typical reversed-phase chromatographic properties with higher methylene selectivity and low silanol activity compared with the C 1 column. The retention mechanism for basic compounds was systematically evaluated by studying the effect of pH, ionic and solvent strength of the mobile phase. Basic compounds displayed lower retention factor and symmetric peak shape on the PMSQ column whereas longer retention and strong tailing peaks were observed on the C 1 column. The difference in retention behavior between the two columns is explained in terms of different principal retention mechanisms. Because of the low silanol activity, retention of basic compounds on the PMSQ column is governed solely by a reversed-phase mechanism. By contrast, multiple interactions including reversed-phase, cation exchange and simultaneous reversed-phase/cationic exchange interaction contribute to the retention on the C 1 column, as previously observed on other silica based reversed-phases. Furthermore, the PMSQ phase exhibited significantly enhanced stability under alkaline conditions compared with its silica-based counterpart. Taken together, the favorable morphology and pore structure combined with the benefits of low silanol activity, high pH stability and prolonged column lifetime make the newly developed PMSQ phase a promising and viable alternative to silica based reversed-phase packings for separation of basic compounds. Copyright © 2018 Elsevier B.V. All rights reserved.

Microscopic Analysis of Current and Mechanical Properties of Nafion® Studied by Atomic Force Microscopy

PubMed Central

Hiesgen, Renate; Helmly, Stefan; Galm, Ines; Morawietz, Tobias; Handl, Michael; Friedrich, K. Andreas

2012-01-01

The conductivity of fuel cell membranes as well as their mechanical properties at the nanometer scale were characterized using advanced tapping mode atomic force microscopy (AFM) techniques. AFM produces high-resolution images under continuous current flow of the conductive structure at the membrane surface and provides some insight into the bulk conducting network in Nafion membranes. The correlation of conductivity with other mechanical properties, such as adhesion force, deformation and stiffness, were simultaneously measured with the current and provided an indication of subsurface phase separations and phase distribution at the surface of the membrane. The distribution of conductive pores at the surface was identified by the formation of water droplets. A comparison of nanostructure models with high-resolution current images is discussed in detail. PMID:24958429

Purification of lignans from Fructus Arctii using off-line two-dimensional supercritical fluid chromatography/reversed-phase liquid chromatography.

PubMed

Yang, Bichao; Xin, Huaxia; Wang, Feier; Cai, Jianfeng; Liu, Yanfang; Fu, Qing; Jin, Yu; Liang, Xinmiao

2017-08-01

As a common traditional Chinese medicine, Fructus Arctii has important clinical medical values. Its main components are lignans, which are difficult to separate and analyze because of the complex composition, similar chemical structures, and close properties. In this study, an off-line two-dimensional supercritical fluid chromatography/reversed-phase liquid chromatography method, as well as an effective sample pretreatment method based on hydrophilic interaction chromatography material, was developed to enrich the minor lignan fractions and obtain high-purity compounds. In total, 12 high-purity compounds were isolated from Fructus Arctii. Their structures were identified by using high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy, which showed that all were lignans and that most of them were isomers. The results demonstrated the effective off-line two-dimensional supercritical fluid chromatography/reversed-phase liquid chromatography method for the purification of lignans from Fructus Arctii. The separation protocol established here will be beneficial for the separation of complex samples from other kinds of natural products. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Curvature-induced microswarming and clustering of self-propelled particles

NASA Astrophysics Data System (ADS)

Bruss, Isaac; Glotzer, Sharon

Non-equilibrium active matter systems exhibit many unique phenomena, such as motility-induced phase separation and swarming. However, little is known about how these behaviors depend on the geometry of the environment. To answer this question, we use Brownian dynamics simulations to study the effects of Gaussian curvature on self-propelled particles by confining them to the surface of a sphere. We find that a modest amount of curvature promotes phase separation by altering the shape of a cluster's boundary. Alternatively, particles on surfaces of high curvature experience reduced phase separation and instead form microswarms, where particles share a common orbit. We show that this novel flocking behavior is distinct from other previously studied examples, in that it is not explicitly incorporated into our model through Vicsek-like alignment rules nor torques. Rather, we find that microswarms emerge solely due to the geometric link between orientation and velocity, a property exclusive to surfaces with non-zero Gaussian curvature. These findings reveal the important role of local environment on the global emergent behavior of non-equilibrium systems. Center for Bio-Inspired Engineering (DOE Award # DE-SC0000989).

Effect of the molecular weight of a neutral polysaccharide on soy protein gelation.

PubMed

Monteiro, Sónia R; Lopes-da-Silva, José A

2017-12-01

The effects of galactomannans with different molecular weights on the heat-induced gelation characteristics of soybean protein were investigated using dynamic small-strain rheometry, under conditions where the proteins carry a net negative charge (pH7). Microstructure of the resulting gels was investigated by confocal laser scanning microscopy. Phase-separated systems were obtained with different morphologies and degree of phase separation, depending on both biopolymer concentrations and polysaccharide molecular weight. In general, a gelling enhancing effect on soy proteins was verified, despite extensive phase-separation processes observed at the higher polysaccharide molecular weight. This effect was demonstrated by an increase of the gelation rate, a decrease in the temperature at the onset of gelation, and an increase of gel stiffness and elastic character, with the length of polysaccharide chains. Overall, the results obtained established that the judicious selection of the galactomannan molecular weight may be used to modify the structure and gelation properties of soy proteins, originating a diversity of rheological characteristics and microstructures that will impact on the design of novel food formulations. Copyright © 2017 Elsevier Ltd. All rights reserved.

π-Extended triptycene-based material for capillary gas chromatographic separations.

PubMed

Yang, Yinhui; Wang, Qinsi; Qi, Meiling; Huang, Xuebin

2017-10-02

Triptycene-based materials feature favorable physicochemical properties and unique molecular recognition ability that offer good potential as stationary phases for capillary gas chromatography (GC). Herein, we report the investigation of utilizing a π-extended triptycene material (denoted as TQPP) for GC separations. As a result, the TQPP capillary column exhibited high column efficiency of 4030 plates m -1 and high-resolution performance for a wide range of analytes, especially structural and positional isomers. Interestingly, the TQPP stationary phase showed unique shape selectivity for alkanes isomers and preferential retention for analytes with halogen atoms and H-bonding nature mainly through their halogen-bonding and H-bonding interactions. In addition, the TQPP column had good repeatability and reproducibility with the RSD values of 0.02-0.34% for run-to-run, 0.09-0.80% for day-to-day and 1.4-5.2% for column-to-column, respectively, and favorable thermal stability up to 280 °C. This work demonstrates the promising future of triptycene-based materials as a new class of stationary phases for GC separations. Copyright © 2017 Elsevier B.V. All rights reserved.

Stabilization of X–Au–X complexes on the Au(111) surface: A theoretical investigation and comparison of X = S, Cl, CH 3S, and SiH 3S

DOE PAGES

Lee, Jiyoung; Boschen, Jeffery S.; Windus, Theresa L.; ...

2017-01-27

Alnico alloys have long been used as strong permanent magnets because of their ferromagnetism and high coercivity. Understanding their structural details allows for better prediction of the resulting magnetic properties. However, quantitative three-dimensional characterization of the phase separation in these alloys is still challenged by the spatial quantification of nanoscale phases. Herein, we apply a dual tomography approach, where correlative scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectroscopic (EDS) tomography and atom probe tomography (APT) are used to investigate the initial phase separation process of an alnico 8 alloy upon non-magnetic annealing. STEM-EDS tomography provides information on the morphology andmore » volume fractions of Fe–Co-rich and Νi–Al-rich phases after spinodal decomposition in addition to quantitative information of the composition of a nanoscale volume. Subsequent analysis of a portion of the same specimen by APT offers quantitative chemical information of each phase at the sub-nanometer scale. Furthermore, APT reveals small, 2–4 nm Fe-rich α 1 phases that are nucleated in the Ni-rich α 2 matrix. From this information, we show that phase separation of the alnico 8 alloy consists of both spinodal decomposition and nucleation and growth processes. The complementary benefits and challenges associated with correlative STEM-EDS and APT are discussed.« less

Properties of a Variable-Delay Polarization Modulator

NASA Technical Reports Server (NTRS)

Chuss, David T.; Wollack, Edward J.; Henry, Ross; Hui, Howard; Juarez, Aaron J.; Krenjy, Megan; Moseley, Harvey; Novak, Giles

2011-01-01

We investigate the polarization modulation properties of a variable-delay polarization modulator (VPM). The VPM modulates polarization via a variable separation between a polarizing grid and a parallel mirror. We find that in the limit where the wavelength is much larger than the diameter of the metal wires that comprise the grid, the phase delay derived from the geometric separation between the mirror and the grid is sufficient to characterize the device. However, outside of this range, additional parameters describing the polarizing grid geometry must be included to fully characterize the modulator response. In this paper, we report test results of a VPM at wavelengths of 350 micron and 3 mm. Electromagnetic simulations of wire grid polarizers were performed and are summarized using a simple circuit model that incorporates the loss and polarization properties of the device.

Evaluation of a new polymeric stationary phase with reversed-phase properties for high temperature liquid chromatography.

PubMed

Vanhoenacker, Gerd; Dos Santos Pereira, Alberto; Kotsuka, Takashi; Cabooter, Deirdre; Desmet, Gert; Sandra, Pat

2010-05-07

The performance of a polymeric stationary phase with reversed-phase properties (ET-RP1) was evaluated for LC separations at elevated temperature. The most significant observation was that the reduced plate height (h) decreased from 3.4 at 25 degrees C (optimal flow 0.5 mL/min) to 2.4 at 150 degrees C (optimal flow 2.5 mL/min) which is comparable to the efficiency obtained with silica-based reversed-phase columns of 4.6mm ID operated at 0.8 mL/min. The phase showed no deterioration after long use at 150 degrees C within the pH range 1-9. Catalytic activity originating from the stationary phase material, e.g. as experienced on zirconium columns operated at elevated temperature, was absent. The performance of ET-RP1 is illustrated with the analysis of some pharmaceutical samples by LC and LC-MS. Operation at elevated temperature also allows to reduce the amount of organic modifier or to replace acetonitrile and methanol by the biodegradable ethanol. Copyright (c) 2009 Elsevier B.V. All rights reserved.

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

Holder, Aaron M.; Siol, Sebastian; Ndione, Paul F.

Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the criticalmore » composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Furthermore, thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region.« less

Investigating phase transition temperatures of size separated gadolinium silicide magnetic nanoparticles

DOE PAGES

Hunagund, Shivakumar G.; Harstad, Shane M.; El-Gendy, Ahmed A.; ...

2018-01-11

Gadolinium silicide (Gd 5Si 4) nanoparticles (NPs) exhibit different properties compared to their parent bulk materials due to finite size, shape, and surface effects. NPs were prepared by high energy ball-milling of the as-cast Gd 5Si 4 ingot and size separated into eight fractions using time sensitive sedimentation in an applied dc magnetic field with average particle sizes ranging from 700 nm to 82 nm. The largest Gd 5Si 4 NPs order ferromagnetically at 316 K. A second anomaly observed at 110 K can be ascribed to a Gd 5Si 3 impurity. Here as the particle sizes decrease, the volumemore » fraction of Gd 5Si 3 phase increases at the expense of the Gd 5Si 4 phase, and the ferromagnetic transition temperature of Gd 5Si 4 is reduced from 316 K to 310 K, while the ordering of the minor phase is independent of the particle size, remaining at 110 K.« less

Ca2+-induced phase separation in black lipid membranes and its effect on the transport of a hydrophobic ion.

PubMed

Miller, A; Schmidt, G; Eibl, H; Knoll, W

1985-03-14

Voltage jump-current relaxation studies have been performed with dipicrylamine-doped black membranes of binary lipid mixtures. As in the case of the carrier-mediated ion transport (Schmidt, G., Eibl, H. and Knoll, W. (1982) J. Membrane Biol. 70, 147-155) no evidence was found that the neutral lipid phosphatidylcholine (DPMPC) and the charged phosphatidic acid (DPMPA) are heterogeneously distributed in the membrane over the whole range of composition. However, besides a continuous dilution of the surface charges of DPMPA by the addition of DPMPC molecules, different structural properties of mixed membranes influence the kinetics of the dipicrylamine transport. The addition of Ca2+ to the electrolyte induces a lipid phase separation within the membrane into two fluid phases of distinctly different characteristics of the translocation of hydrophobic ions. Thus, it is possible to determine a preliminary composition phase diagram for the DPMPA/DPMPC mixtures as a function of the Ca2+ concentration.

Field induced ferromagnetic fraction enlargement in phase separated La_0.5Ca_0.5MnO_3

NASA Astrophysics Data System (ADS)

Ghivelder, Luis; Freitas, R. S.; Sacanel, J.; Parisi, F.; Levy, P.

2001-03-01

A systematic study of the magnetic and transport properties of a series of phase separated La_0.5Ca_0.5MnO3 compounds is reported. The investigated samples all have the same composition but different grain sizes, which modifies the volume fraction of the coexisting ferromagnetic (FM) and antiferromagnetic charge-ordered (AFM-CO) phases. Magnetoresistance and magnetization measurements were performed with two different experimental procedures: a standard field-cooled cooling (FC) mode, and a second method in which the field is turned on only while measuring each data point, and switched off while cooling the samples. Magnetization and magnetoresistance measurements display big differences when comparing the data obtained with the different procedures. The overall results are interpret in terms of a field induced FM fraction enlargement. In transport measurements this effect yield a percolative transition. Magnetization data shows evidence for the formation of AFM-CO regions within the FM phase. * e-mail: luisghiv@if.ufrj.br

Investigating phase transition temperatures of size separated gadolinium silicide magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Hunagund, Shivakumar G.; Harstad, Shane M.; El-Gendy, Ahmed A.; Gupta, Shalabh; Pecharsky, Vitalij K.; Hadimani, Ravi L.

2018-05-01

Gadolinium silicide (Gd5Si4) nanoparticles (NPs) exhibit different properties compared to their parent bulk materials due to finite size, shape, and surface effects. NPs were prepared by high energy ball-milling of the as-cast Gd5Si4 ingot and size separated into eight fractions using time sensitive sedimentation in an applied dc magnetic field with average particle sizes ranging from 700 nm to 82 nm. The largest Gd5Si4 NPs order ferromagnetically at 316 K. A second anomaly observed at 110 K can be ascribed to a Gd5Si3 impurity. As the particle sizes decrease, the volume fraction of Gd5Si3 phase increases at the expense of the Gd5Si4 phase, and the ferromagnetic transition temperature of Gd5Si4 is reduced from 316 K to 310 K, while the ordering of the minor phase is independent of the particle size, remaining at 110 K.

Investigating phase transition temperatures of size separated gadolinium silicide magnetic nanoparticles

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

Hunagund, Shivakumar G.; Harstad, Shane M.; El-Gendy, Ahmed A.

Gadolinium silicide (Gd 5Si 4) nanoparticles (NPs) exhibit different properties compared to their parent bulk materials due to finite size, shape, and surface effects. NPs were prepared by high energy ball-milling of the as-cast Gd 5Si 4 ingot and size separated into eight fractions using time sensitive sedimentation in an applied dc magnetic field with average particle sizes ranging from 700 nm to 82 nm. The largest Gd 5Si 4 NPs order ferromagnetically at 316 K. A second anomaly observed at 110 K can be ascribed to a Gd 5Si 3 impurity. Here as the particle sizes decrease, the volumemore » fraction of Gd 5Si 3 phase increases at the expense of the Gd 5Si 4 phase, and the ferromagnetic transition temperature of Gd 5Si 4 is reduced from 316 K to 310 K, while the ordering of the minor phase is independent of the particle size, remaining at 110 K.« less

Optical Properties of atmospheric dust from twilight observations

NASA Technical Reports Server (NTRS)

Divari, N. B.; Zaginayilo, Y. I.; Kovalchuk, L. V.

1973-01-01

Three methods of approximation are described and used to separate the primary twilight brightness from the observed brightness. Photoelectric observations obtained are combined with observations from a balloon and from the observatory to derive the atmospheric scattering phase functions of 0.37 micron and 0.58 micron as a function of height. Comparison of these data with data for a Rayleigh atmosphere provide information on the optical properties of dust in the upper atmosphere.

Evaluation and application of a mixed-mode chromatographic stationary phase in two-dimensional liquid chromatography for the separation of traditional Chinese medicine.

PubMed

Wei, Zhishen; Fu, Qing; Cai, Jianfeng; Huan, Liyun; Zhao, Jianchao; Shi, Hui; Jin, Yu; Liang, Xinmiao

2016-06-01

In this study, two mixed-mode chromatography stationary phases (C8SAX and C8SCX) were evaluated and used to establish a two-dimensional liquid chromatography system for the separation of traditional Chinese medicine. The chromatographic properties of the mixed-mode columns were systematically evaluated by comparing with other three columns of C8, strong anion exchanger, and strong cation exchanger. The result showed that C8SAX and C8SCX had a mixed-mode retention mechanism including electrostatic interaction and hydrophobic interaction. Especially, they were suitable for separating acidic and/or basic compounds and their separation selectivities could be easily adjusted by changing pH value. Then, several off-line 2D-LC systems based on the C8SAX in the first dimension and C8SAX, C8SCX, or C8 columns in the second dimension were developed to analyze a traditional Chinese medicine-Uncaria rhynchophylla. The two-dimensional liquid chromatography system of C8SAX (pH 3.0) × C8SAX (pH 6.0) exhibited the most effective peak distribution. Finally, fractions of U. rhynchophylla prepared from the first dimension were successfully separated on the C8SAX column with a gradient pH. Thus, the mixed-mode stationary phase could provide a platform to separate the traditional Chinese medicine in practical applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of Radiation Damage Reduction in Equiatomic Multicomponent Single Phase Alloys.

PubMed

Granberg, F; Nordlund, K; Ullah, Mohammad W; Jin, K; Lu, C; Bei, H; Wang, L M; Djurabekova, F; Weber, W J; Zhang, Y

2016-04-01

Recently a new class of metal alloys, of single-phase multicomponent composition at roughly equal atomic concentrations ("equiatomic"), have been shown to exhibit promising mechanical, magnetic, and corrosion resistance properties, in particular, at high temperatures. These features make them potential candidates for components of next-generation nuclear reactors and other high-radiation environments that will involve high temperatures combined with corrosive environments and extreme radiation exposure. In spite of a wide range of recent studies of many important properties of these alloys, their radiation tolerance at high doses remains unexplored. In this work, a combination of experimental and modeling efforts reveals a substantial reduction of damage accumulation under prolonged irradiation in single-phase NiFe and NiCoCr alloys compared to elemental Ni. This effect is explained by reduced dislocation mobility, which leads to slower growth of large dislocation structures. Moreover, there is no observable phase separation, ordering, or amorphization, pointing to a high phase stability of this class of alloys.

Mechanism of Radiation Damage Reduction in Equiatomic Multicomponent Single Phase Alloys

NASA Astrophysics Data System (ADS)

Granberg, F.; Nordlund, K.; Ullah, Mohammad W.; Jin, K.; Lu, C.; Bei, H.; Wang, L. M.; Djurabekova, F.; Weber, W. J.; Zhang, Y.

2016-04-01

Recently a new class of metal alloys, of single-phase multicomponent composition at roughly equal atomic concentrations ("equiatomic"), have been shown to exhibit promising mechanical, magnetic, and corrosion resistance properties, in particular, at high temperatures. These features make them potential candidates for components of next-generation nuclear reactors and other high-radiation environments that will involve high temperatures combined with corrosive environments and extreme radiation exposure. In spite of a wide range of recent studies of many important properties of these alloys, their radiation tolerance at high doses remains unexplored. In this work, a combination of experimental and modeling efforts reveals a substantial reduction of damage accumulation under prolonged irradiation in single-phase NiFe and NiCoCr alloys compared to elemental Ni. This effect is explained by reduced dislocation mobility, which leads to slower growth of large dislocation structures. Moreover, there is no observable phase separation, ordering, or amorphization, pointing to a high phase stability of this class of alloys.

Mechanism of Radiation Damage Reduction in Equiatomic Multicomponent Single Phase Alloys

DOE PAGES

Granberg, F.; Nordlund, K.; Ullah, Mohammad W.; ...

2016-04-01

Recently a new class of metal alloys, of single-phase multicomponent composition at roughly equal atomic concentrations (“equiatomic”), have been shown to exhibit promising mechanical, magnetic, and corrosion resistance properties, in particular, at high temperatures. These features make them potential candidates for components of next-generation nuclear reactors and other high-radiation environments that will involve high temperatures combined with corrosive environments and extreme radiation exposure. In spite of a wide range of recent studies of many important properties of these alloys, their radiation tolerance at high doses remains unexplored. In this work, a combination of experimental and modeling efforts reveals a substantialmore » reduction of damage accumulation under prolonged irradiation in single-phase NiFe and NiCoCr alloys compared to elemental Ni. This effect is explained by reduced dislocation mobility, which leads to slower growth of large dislocation structures. Finally and moreover, there is no observable phase separation, ordering, or amorphization, pointing to a high phase stability of this class of alloys.« less

Visualizing heavy fermion confinement and Pauli-limited superconductivity in layered CeCoIn 5

DOE PAGES

Gyenis, András; Feldman, Benjamin E.; Randeria, Mallika T.; ...

2018-02-07

Layered material structures play a key role in enhancing electron–electron interactions to create correlated metallic phases that can transform into unconventional superconducting states. The quasi-two-dimensional electronic properties of such compounds are often inferred indirectly through examination of bulk properties. Here we use scanning tunneling microscopy to directly probe in cross-section the quasi-two-dimensional electronic states of the heavy fermion superconductor CeCoIn 5. Our measurements reveal the strong confined nature of quasiparticles, anisotropy of tunneling characteristics, and layer-by-layer modulated behavior of the precursor pseudogap gap phase. In the interlayer coupled superconducting state, the orientation of line defects relative to the d-wave ordermore » parameter determines whether in-gap states form due to scattering. Spectroscopic imaging of the anisotropic magnetic vortex cores directly characterizes the short interlayer superconducting coherence length and shows an electronic phase separation near the upper critical in-plane magnetic field, consistent with a Pauli-limited first-order phase transition into a pseudogap phase.« less

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

Gyenis, András; Feldman, Benjamin E.; Randeria, Mallika T.

Layered material structures play a key role in enhancing electron–electron interactions to create correlated metallic phases that can transform into unconventional superconducting states. The quasi-two-dimensional electronic properties of such compounds are often inferred indirectly through examination of bulk properties. Here we use scanning tunneling microscopy to directly probe in cross-section the quasi-two-dimensional electronic states of the heavy fermion superconductor CeCoIn 5. Our measurements reveal the strong confined nature of quasiparticles, anisotropy of tunneling characteristics, and layer-by-layer modulated behavior of the precursor pseudogap gap phase. In the interlayer coupled superconducting state, the orientation of line defects relative to the d-wave ordermore » parameter determines whether in-gap states form due to scattering. Spectroscopic imaging of the anisotropic magnetic vortex cores directly characterizes the short interlayer superconducting coherence length and shows an electronic phase separation near the upper critical in-plane magnetic field, consistent with a Pauli-limited first-order phase transition into a pseudogap phase.« less

Order-disorder transition in a two-dimensional boron-carbon-nitride alloy

NASA Astrophysics Data System (ADS)

Lu, Jiong; Zhang, Kai; Feng Liu, Xin; Zhang, Han; Chien Sum, Tze; Castro Neto, Antonio H.; Loh, Kian Ping

2013-10-01

Two-dimensional boron-carbon-nitride materials exhibit a spectrum of electronic properties ranging from insulating to semimetallic, depending on their composition and geometry. Detailed experimental insights into the phase separation and ordering in such alloy are currently lacking. Here we report the mixing and demixing of boron-nitrogen and carbon phases on ruthenium (0001) and found that energetics for such processes are modified by the metal substrate. The brick-and-mortar patchwork observed of stoichiometrically percolated hexagonal boron-carbon-nitride domains surrounded by a network of segregated graphene nanoribbons can be described within the Blume-Emery-Griffiths model applied to a honeycomb lattice. The isostructural boron nitride and graphene assumes remarkable fluidity and can be exchanged entirely into one another by a catalytically assistant substitution. Visualizing the dynamics of phase separation at the atomic level provides the premise for enabling structural control in a two-dimensional network for broad nanotechnology applications.

Activation analysis of admixtures in certain semiconductive materials

NASA Technical Reports Server (NTRS)

Artyukhin, P. I.; Gilbert, E. P.; Pronin, V. A.

1978-01-01

The use of extractions and chromatographic operations to separate macrobases, and to divide elements into groups convenient for gamma-spectrometric analysis is discussed. Methods are described for the activation detection of some impurities in silicon, arsenic, thallium, and trichloromethylsilane, on the basis of the extraction properties of bis(2-chlorethyl ether) and dimethylbenzylalkylammonium chloride. A schematic diagram of the extraction separation of elements-admixture is presented showing the aqueous and organic phases. The content percentage of the various elements are given in tables.

Phase Contrast Microscopy Analysis of Breast Tissue

PubMed Central

Wells, Wendy A.; Wang, Xin; Daghlian, Charles P.; Paulsen, Keith D.; Pogue, Brian W.

2010-01-01

OBJECTIVE To assess how optical scatter properties in breast tissue, as measured by phase contrast microscopy and interpreted pathophysiologically, might be exploited as a diagnostic tool to differentiate cancer from benign tissue. STUDY DESIGN We evaluated frozen human breast tissue sections of adipose tissue, normal breast parenchyma, benign fibroadenoma tumors and noninvasive and invasive malignant cancers by phase contrast microscopy through quantification of grayscale values, using multiple regions of interest (ROI). Student’s t tests were performed on phase contrast measures across diagnostic categories testing data from individual cases; all ROI data were used as separate measures. RESULTS Stroma demonstrated significantly higher scatter intensity than did epithelium, with lower scattering in tumor-associated stroma as compared with normal or benign-associated stroma. Measures were comparable for invasive and noninvasive malignant tumors but were higher than those found in benign tumors and were lowest in adipose tissue. CONCLUSION Significant differences were found in scatter coefficient properties of epithelium and stroma across diagnostic categories of breast tissue, particularly between benign and malignant-associated stroma. Improved understanding of how scatter properties correlate with morphologic criteria used in routine pathologic diagnoses could have a significant clinical impact as developing optical technology allows macroscopic in situ phase contrast imaging. PMID:19736867

Separation of carbohydrates using hydrophilic interaction liquid chromatography.

PubMed

Fu, Qing; Liang, Tu; Li, Zhenyu; Xu, Xiaoyong; Ke, Yanxiong; Jin, Yu; Liang, Xinmiao

2013-09-20

A strategy was developed to rapidly evaluate chromatographic properties of hydrophilic interaction chromatography (HILIC) columns for separating carbohydrates. Seven HILIC columns (Silica, Diol, TSK Amide-80, XAmide, Click Maltose, Click β-CD, and Click TE-Cys columns) were evaluated by using three monosaccharide and seven disaccharides as probes. The influence of column temperature on the peak shape and tautomerization of carbohydrates, as well as column selectivity were investigated. The influence of surface charge property on the retention was also studied by using glucose, glucuronic acid, and glucosamine, which indicated that buffer salt concentration and pH value in mobile phase was necessary to control the ionic interactions between ionic carbohydrates and HILIC columns. According to evaluation results, the XAmide column was selected as an example to establish experimental schemes for separation of complex mixtures of oligosaccharide. Copyright © 2013 Elsevier Ltd. All rights reserved.

Preparation and evaluation of silica-UIO-66 composite as liquid chromatographic stationary phase for fast and efficient separation.

PubMed

Yan, Zhiming; Zheng, Jiangnan; Chen, Jinfeng; Tong, Ping; Lu, Minghua; Lin, Zian; Zhang, Lan

2014-10-31

A silica-UIO-66 composite was fabricated by a simple hydrothermal method and then applied as liquid chromatographic stationary phase for fast and efficient separation. X-ray diffraction patterns showed the presence of UIO-66 crystals in the silica-UIO-66 composites; while scanning electron microscope (SEM) images revealed that silica-UIO-66 composites were a homogeneous mixture of silica bead and UIO-66 crystals. A variety of substituted aromatics, chlorobenzene compounds and polycyclic aromatic hydrocarbons (PAHs) were used to evaluate the retention properties of the silica-UIO-66 composite packed column. Under the optimized conditions, baseline separation of ethylbenzene (EB) and styrene was obtained with high resolution and short retention time. In addition, the silica-UIO-66 composite packed column also showed some advantages in separation of positional isomers, with which baseline separation of EB and xylene, chlorotoluene and dichlorobenzene isomers was achieved. Moreover, the retention mechanisms of these compounds were also discussed in detail. The relative standard deviations (RSDs) for the separation of EB and xylene, chlorotoluene and dichlorobenzene isomers, as well as EB and styrene were 0.42-0.9%, 1.0-1.9%, 0.75-2.0%, and 0.9-2.1% for the retention time, peak area, peak height, and half peak width, respectively. The column efficiencies for EB, p-chlorotoluene, p-dichlorobenzene and styrene were 8780, 9060, 9990 and 5130 plates/m. The successful applications suggested high potentials of silica-MOFs composite as stationary phase for fast and efficient liquid chromatography separation. Copyright © 2014 Elsevier B.V. All rights reserved.

A Thermodynamically Consistent Approach to Phase-Separating Viscous Fluids

NASA Astrophysics Data System (ADS)

Anders, Denis; Weinberg, Kerstin

2018-04-01

The de-mixing properties of heterogeneous viscous fluids are determined by an interplay of diffusion, surface tension and a superposed velocity field. In this contribution a variational model of the decomposition, based on the Navier-Stokes equations for incompressible laminar flow and the extended Korteweg-Cahn-Hilliard equations, is formulated. An exemplary numerical simulation using C1-continuous finite elements demonstrates the capability of this model to compute phase decomposition and coarsening of the moving fluid.

A New Strategy to Prepare Polymer-based Shape Memory Elastomers.

PubMed

Song, Shijie; Feng, Jiachun; Wu, Peiyi

2011-10-04

A new strategy that utilizes the microphase separation of block copolymer and phase transition of small molecules for preparing polymer-based shape memory elastomer has been proposed. According to this strategy, a novel kind of shape memory elastomer comprising styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) and paraffin has been prepared. Because paraffins are midblock-selective molecules for SEBS, they will preferentially enter and swell EB blocks supporting paraffins as an excellent switch phase for shape memory effect. Microstructures of SEBS/paraffin composites have been characterized by transmission electron microscopy, polarized light microscopy, and differential scanning calorimetry. The composites demonstrate various phase morphologies with regard to different paraffin loading. It has been found that under low paraffin loading, all the paraffins precisely embed in and swell EB-rich domains. While under higher loading, part of the paraffins become free and a larger-scaled phase separation has been observed. However, within wide paraffin loadings, all composites show good shape fixing, shape recovery performances, and improved tensile properties. Compared to the reported methods for shape memory elastomers preparation, this method not only simplifies the fabrication procedure from raw materials to processing but also offers a controllable approach for the optimization of shape memory properties as well as balancing the rigidity and softness of the material. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fine-scale Horizontal Structure of Arctic Mixed-Phase Clouds.

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

Rambukkange,M.; Verlinde, J.; Elorante, E.

2006-07-10

Recent in situ observations in stratiform clouds suggest that mixed phase regimes, here defined as limited cloud volumes containing both liquid and solid water, are constrained to narrow layers (order 100 m) separating all-liquid and fully glaciated volumes (Hallett and Viddaurre, 2005). The Department of Energy Atmospheric Radiation Measurement Program's (DOE-ARM, Ackerman and Stokes, 2003) North Slope of Alaska (NSA) ARM Climate Research Facility (ACRF) recently started collecting routine measurement of radar Doppler velocity power spectra from the Millimeter Cloud Radar (MMCR). Shupe et al. (2004) showed that Doppler spectra has potential to separate the contributions to the total reflectivitymore » of the liquid and solid water in the radar volume, and thus to investigate further Hallett and Viddaurre's findings. The Mixed-Phase Arctic Cloud Experiment (MPACE) was conducted along the NSA to investigate the properties of Arctic mixed phase clouds (Verlinde et al., 2006). We present surface based remote sensing data from MPACE to discuss the fine-scale structure of the mixed-phase clouds observed during this experiment.« less

Transition from the diamagnetic insulator to ferromagnetic metal in La1-xSrxCoO3

NASA Astrophysics Data System (ADS)

Knížek, Karel; Jirák, Zdeněk; Hejtmánek, Jiří; Novák, Pavel

2010-05-01

We have analyzed, using the theoretical GGA+U calculations, different configurations of spin states (low-spin, LS; intermediate-spin, IS and high-spin, HS Co) and proposed a model that accounts for magnetic and electric transport properties of perovskite cobaltites upon doping by charge carriers. In particular, it appears that the compositional transition from the diamagnetic LS phase of LaCoO3 to the ferromagnetic metallic IS phase in La1-xSrxCoO3 ( x>0.2) involves the same mechanisms as the high-temperature transition in pure LaCoO3. The process occurs gradually via a phase-separated state, where metallic IS domains stabilized through a charge transfer between Co and Co neighbors coexist with the Co poor regions in the LS ground state (or at higher temperatures, in mixed LS/HS state). This phase separation vanishes when doping in La1-xSrxCoO3 reaches x˜0.2, and a uniform IS phase, analogous to that in pure LaCoO3 in the high-temperature limit, is established.

Gas and hydrocarbon vapor permeation in poly(1-trimethylsilyl-1-propyne)/poly(1-phenyl-1-propyne) blends

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

Morisato, A.; Shen, H.C.; Toy, L.G.

1996-12-31

Permeation properties of phase-separated blends prepared from glassy poly(1-trimethylsilyl-1-propyne) (PTMSP) and poly(1-phenyl-1-propyne) (PPP) were determined as a function of blend composition with pure hydrogen, nitrogen, oxygen, carbon dioxide, and butane. Blend permeabilities decrease significantly with increasing PPP concentration and suggest the occurrence of a phase inversion at low PPP content (5 to 20 wt%). Based on TEM analysis high-aspect-ratio (extended) PPP ellipsoidal dispersions are found in a PTMSP matrix, indicating that the phase inversion is closely related to dispersed-phase connectivity in the blends.

Synthesis of zirconia monoliths for chromatographic separations.

PubMed

Randon, Jérôme; Huguet, Samuel; Piram, Anne; Puy, Guillaume; Demesmay, Claire; Rocca, Jean-Louis

2006-03-17

The aim of this work is to join the advantages of two different kinds of stationary phases: monolithic columns and zirconia-based supports. On the one hand, silica monolithic columns allow a higher efficiency with a lower back-pressure than traditional packed columns. On the other hand, chromatographic stationary phases based on zirconia have a higher thermal and chemical stability and specific surface properties. Combining these advantages, a zirconia monolith with a macroporous framework could be a real improvement in separation sciences. Two main strategies can be used in order to obtain a zirconia surface on a monolithic skeleton: coating or direct synthesis. The coverage by a zirconia layer of the surface of a silica-based monolith can be performed using the chemical properties of the silanol surface groups. We realized this coverage using zirconium alkoxide and we further grafted n-dodecyl groups using phosphate derivatives. Any loss of efficiency was observed and fast separations have been achieved. The main advance reported in this paper is related to the preparation of zirconia monoliths by a sol-gel process starting from zirconium alkoxide. The synthesis parameters (hydrolysis ratio, porogen type, precursor concentration, drying step, etc.) were defined in order to produce a macroporous zirconia monoliths usable in separation techniques. We produced various homogeneous structures: zirconia rod 2 cm long with a diameter of 2.3 mm, and zirconia monolith inside fused silica capillaries with a 75 microm I.D. These monoliths have a skeleton size of 2 microm and have an average through pore size of 6 microm. Several separations have been reported.

Simple setup for gas-phase H/D exchange mass spectrometry coupled to electron transfer dissociation and ion mobility for analysis of polypeptide structure on a liquid chromatographic time scale.

PubMed

Mistarz, Ulrik H; Brown, Jeffery M; Haselmann, Kim F; Rand, Kasper D

2014-12-02

Gas-phase hydrogen/deuterium exchange (HDX) is a fast and sensitive, yet unharnessed analytical approach for providing information on the structural properties of biomolecules, in a complementary manner to mass analysis. Here, we describe a simple setup for ND3-mediated millisecond gas-phase HDX inside a mass spectrometer immediately after ESI (gas-phase HDX-MS) and show utility for studying the primary and higher-order structure of peptides and proteins. HDX was achieved by passing N2-gas through a container filled with aqueous deuterated ammonia reagent (ND3/D2O) and admitting the saturated gas immediately upstream or downstream of the primary skimmer cone. The approach was implemented on three commercially available mass spectrometers and required no or minor fully reversible reconfiguration of gas-inlets of the ion source. Results from gas-phase HDX-MS of peptides using the aqueous ND3/D2O as HDX reagent indicate that labeling is facilitated exclusively through gaseous ND3, yielding similar results to the infusion of purified ND3-gas, while circumventing the complications associated with the use of hazardous purified gases. Comparison of the solution-phase- and gas-phase deuterium uptake of Leu-Enkephalin and Glu-Fibrinopeptide B, confirmed that this gas-phase HDX-MS approach allows for labeling of sites (heteroatom-bound non-amide hydrogens located on side-chains, N-terminus and C-terminus) not accessed by classical solution-phase HDX-MS. The simple setup is compatible with liquid chromatography and a chip-based automated nanoESI interface, allowing for online gas-phase HDX-MS analysis of peptides and proteins separated on a liquid chromatographic time scale at increased throughput. Furthermore, online gas-phase HDX-MS could be performed in tandem with ion mobility separation or electron transfer dissociation, thus enabling multiple orthogonal analyses of the structural properties of peptides and proteins in a single automated LC-MS workflow.

The Effect of 4-Octyldecyloxybenzoic Acid on Liquid-Crystalline Polyurethane Composites with Triple-Shape Memory and Self-Healing Properties

PubMed Central

Ban, Jianfeng; Zhu, Linjiang; Chen, Shaojun; Wang, Yiping

2016-01-01

To better understand shape memory materials and self-healing materials, a new series of liquid-crystalline shape memory polyurethane (LC-SMPU) composites, named SMPU-OOBAm, were successfully prepared by incorporating 4-octyldecyloxybenzoic acid (OOBA) into the PEG-based SMPU. The effect of OOBA on the structure, morphology, and properties of the material has been carefully investigated. The results demonstrate that SMPU-OOBAm has liquid crystalline properties, triple-shape memory properties, and self-healing properties. The incorporated OOBA promotes the crystallizability of both soft and hard segments of SMPU, and the crystallization rate of the hard segment of SMPU decreases when the OOBA-content increases. Additionally, the SMPU-OOBAm forms a two-phase separated structure (SMPU phase and OOBA phase), and it shows two-step modulus changes upon heating. Therefore, the SMPU-OOBAm exhibits triple-shape memory behavior, and the shape recovery ratio decreases with an increase in the OOBA content. Finally, SMPU-OOBAm exhibits self-healing properties. The new mechanism can be ascribed to the heating-induced “bleeding” of OOBA in the liquid crystalline state and the subsequent re-crystallization upon cooling. This successful combination of liquid crystalline properties, triple-shape memory properties, and self-healing properties make the SMPU-OOBAm composites ideal for many promising applications in smart optical devices, smart electronic devices, and smart sensors. PMID:28773914

Emergence of superconductivity and magnetic ordering tuned by Fe-vacancy in alkali-metal Fe chalcogenides RbxFe2-ySe2

NASA Astrophysics Data System (ADS)

Kobayashi, Yoshiaki; Kototani, Shouhei; Itoh, Masayuki; Sato, Masatoshi

2014-12-01

Samples of RbxFe2-ySe2 exhibiting superconductivity [superconducting (SC) samples] undergo a phase-separation into two phases, a Fe-vacancy ordered phase with antiferromagnetic (AFM) transition at TN1~500 K (AFM1 phase) and a phase with little Fe- vacancy and SC transition at Tc~30 K (SC phase). The samples of RbxFe2-ySe2 exhibiting no SC behaviour (non-SC samples) are phase-separated into three phases, the AFM1 phase, another AFM phase with TN2 ~150 K (AFM2 phase), and a paramagnetic phase with no SC transitions (paramagnetic non-SC phase). In this paper, we present the experimental results of magnetic susceptibility, electrical resistivity, and NMR measurements on single crystals of RbxFe2-ySe2 to reveal physical properties of these co-existing phases in the SC and non-SC samples. The 87Rb and 77Se NMR spectra show that the Fe vacancy concentration is very small in the Fe planes of the SC phase, whereas the AFM2 and paramagnetic non-SC phases in non-SC samples have larger amount of Fe vacancies. The randomness induced by the Fe vacancy in the non-SC samples makes the AFM2 and paramagnetic non-SC phases insulating/semiconducting and magnetically active, resulting in the absence of the superconductivity in RbxFe2-ySe2.

Evaluation of the separation characteristics of application-specific (volatile organic compounds) open-tubular columns for gas chromatography.

PubMed

Poole, Colin F; Qian, Jing; Kiridena, Waruna; Dekay, Colleen; Koziol, Wladyslaw W

2006-11-17

The solvation parameter model is used to characterize the separation characteristics of two application-specific open-tubular columns (Rtx-Volatiles and Rtx-VGC) and a general purpose column for the separation of volatile organic compounds (DB-WAXetr) at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and retention factor correlation plots are then used to determine selectivity differences between the above columns and their closest neighbors in a large database of system constants and retention factors for forty-four open-tubular columns. The Rtx-Volatiles column is shown to have separation characteristics predicted for a poly(dimethyldiphenylsiloxane) stationary phase containing about 16% diphenylsiloxane monomer. The Rtx-VGC column has separation properties similar to the poly(cyanopropylphenyldimethylsiloxane) stationary phase containing 14% cyanopropylphenylsiloxane monomer DB-1701 for non-polar and dipolar/polarizable compounds but significantly different characteristics for the separation of hydrogen-bond acids. For all practical purposes the DB-WAXetr column is shown to be selectivity equivalent to poly(ethylene glycol) columns prepared using different chemistries for bonding and immobilizing the stationary phase. Principal component analysis and cluster analysis are then used to classify the system constants for the above columns and a sub-database of eleven open-tubular columns (DB-1, HP-5, DB-VRX, Rtx-20, DB-35, Rtx-50, Rtx-65, DB-1301, DB-1701, DB-200, and DB-624) commonly used for the separation of volatile organic compounds. A rationale basis for column selection based on differences in intermolecular interactions is presented as an aid to method development for the separation of volatile organic compounds.

Layer-by-layer self-assembled graphene oxide/silica microsphere composites as stationary phase for high performance liquid chromatography.

PubMed

Liang, Xiaojing; Liu, Shujuan; Song, Xinwang; Zhu, Yangwen; Jiang, Shengxiang

2012-11-21

Graphene oxide (GO) has been layer-by-layer assembled onto silica microspheres to form a GO/SiO(2) composite stationary phase. All the characterizations of GO/SiO(2) by elemental analysis, Raman spectroscopy and Fourier transformed infrared spectrometry confirmed that with the increase of the assembled layer, GO gradually increases on the silica surface. The chromatographic properties of bare SiO(2) and GO/SiO(2) with different GO assembled layers show that the amount of GO plays an important role in the separation of analytes. Only the appropriate amount of GO on SiO(2) can perform a good chromatographic separation. The comparison between chromatographic performances of bare SiO(2) column, GO/SiO(2)-2 column and C18 commercial column clearly show that GO/SiO(2)-2 and C18 columns obtained a better separation; GO/SiO(2)-2 exhibits a large π-electron system and C18 exhibits hydrophobicity. The eluting order, peak width and resolution of analyte on GO/SiO(2)-2 column was highly dependent on the size of its π-electron system, while on the C18 column the decisive factor is its hydrophobic property.

Potential role of gold nanoparticles for improved analytical methods: an introduction to characterizations and applications.

PubMed

Wu, Chung-Shu; Liu, Fu-Ken; Ko, Fu-Hsiang

2011-01-01

Nanoparticle-based material is a revolutionary scientific and engineering venture that will invariably impact the existing analytical separation and preconcentration for a variety of analytes. Nanoparticles can be regarded as a hybrid between small molecule and bulk material. A material on the nanoscale produces considerable changes on various properties, making them size- and shape-dependent. Gold nanoparticles (Au NPs), one of the wide variety of core materials available, coupled with tunable surface properties in the form of inorganic or inorganic-organic hybrid have been reported as an excellent platform for a broad range of analytical methods. This review aims to introduce the basic principles, examples, and descriptions of methods for the characterization of Au NPs by using chromatography, electrophoresis, and self-assembly strategies for separation science. Some of the latest important applications of using Au NPs as stationary phases toward open-tubular capillary electrochromatography, gas chromatography, and liquid chromatography as well as roles of run buffer additive to enhance separation and preconcentration in the field of chromatographic, electrophoretic and in chip-based systems are reviewed. Additionally, we review Au NPs-assisted state-of-the-art techniques involving the use of micellar electrokinetic chromatography, an online diode array detector, solid-phase extraction, and mass spectrometry for the preconcentration of some chemical compounds and biomolecules.

Superbase-derived protic ionic liquid extractants for metal ion separation

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

Bell, Jason R.; Dai, Sheng; Luo, Huimin

2014-04-19

Solvent extraction of La 3+ and Ba 2+ by an ionic liquid extractant in an imidazolium-based ionic liquid diluent was investigated. Seven protic ionic liquid extractants were examined and these protic ILs are based on five organic superbases and either 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione (Hfod) or 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) -diketones as anion. For fod-based extractants, the extraction efficiencies and separation factors were found to be concentration dependent. The effects of aqueous phase acidity, extractant structure, and extractant concentration on separation properties of La 3+ and Ba 2+ are discussed in this paper.

An investigation on microstructure and mechanical property of thermally aged stainless steel weld overlay cladding

NASA Astrophysics Data System (ADS)

Cao, X. Y.; Zhu, P.; Ding, X. F.; Lu, Y. H.; Shoji, T.

2017-04-01

Microstructural evolution and mechanical property change of E308L stainless steel weld overlay cladding aged at 400 °C for 400, 1000 and 5000 h were investigated by transmission electron microscope (TEM) and small punch test (SPT). The results indicated that thermal aging had no obvious effect on the volume fraction of ferrite, but can cause microstructural evolution by spinodal decomposotion and G-phase precipitation in the ferrite phase. Spinodal decomposition took place after aging up to 1000 h, while G-phase formed along dislocations, and growed up to 2-11 nm after aging for 5000 h. The total energy for inducing deformation and fracture by the small punch tests decreased with the increase of thermal aging time, and this decline was associated with spinodal decomposition and G-phase precipitation. Plastic deformation of the aged ferrite proceeded via formation of curvilinear slip bands. Nucleation of microcracks occurred at the δ/γ interface along the slip bands. The hardening of the ferrite and high stress concentration on δ/γ phase interface resulted in brittle fracture and phase boundary separation after thermal aging.

Imaging Nanometer Phase Coexistence at Defects During the Insulator-Metal Phase Transformation in VO2 Thin Films by Resonant Soft X-ray Holography.

PubMed

Vidas, Luciana; Günther, Christian M; Miller, Timothy A; Pfau, Bastian; Perez-Salinas, Daniel; Martínez, Elías; Schneider, Michael; Gührs, Erik; Gargiani, Pierluigi; Valvidares, Manuel; Marvel, Robert E; Hallman, Kent A; Haglund, Richard F; Eisebitt, Stefan; Wall, Simon

2018-05-18

We use resonant soft X-ray holography to image the insulator-metal phase transition in vanadium dioxide with element and polarization specificity and nanometer spatial resolution. We observe that nanoscale inhomogeneity in the film results in spatial-dependent transition pathways between the insulating and metallic states. Additional nanoscale phases form in the vicinity of defects which are not apparent in the initial or final states of the system, which would be missed in area-integrated X-ray absorption measurements. These intermediate phases are vital to understand the phase transition in VO 2 , and our results demonstrate how resonant imaging can be used to understand the electronic properties of phase-separated correlated materials obtained by X-ray absorption.

Water-Rock Differentiation of Icy Bodies by Darcy law, Stokes law, and Two-Phase Flow

NASA Astrophysics Data System (ADS)

Neumann, Wladimir; Breuer, Doris; Spohn, Tilman

2016-10-01

The early Solar system produced a variety of bodies with different properties. Among the small bodies, objects that contain notable amounts of water ice are of particular interest. Water-rock separation on such worlds is probable and has been confirmed in some cases. We couple accretion and water-rock separation in a numerical model. The model is applicable to Ceres, icy satellites, and Kuiper belt objects, and is suited to assess the thermal metamorphism of the interior and the present-day internal structures. The relative amount of ice determines the differentiation regime according to porous flow or Stokes flow. Porous flow considers differentiation in a rock matrix with a small degree of ice melting and is typically modelled either with the Darcy law or two-phase flow. We find that for small icy bodies two-phase flow differs from the Darcy law. Velocities derived from two-phase flow are at least one order of magnitude smaller than Darcy velocities. The latter do not account for the matrix resistance against the deformation and overestimate the separation velocity. In the Stokes regime that should be used for large ice fractions, differentiation is at least four orders of magnitude faster than porous flow with the parameters used here.

Facile preparation of a stable and functionalizable hybrid monolith via ring-opening polymerization for capillary liquid chromatography.

PubMed

Lin, Hui; Ou, Junjie; Tang, Shouwan; Zhang, Zhenbin; Dong, Jing; Liu, Zhongshan; Zou, Hanfa

2013-08-02

An organic-inorganic hybrid monolith was prepared by a single-step ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS) with poly(ethylenimine) (PEI). The obtained hybrid monoliths possessed high ordered 3D skeletal microstructure with dual retention mechanism that exhibits reversed-phase (RP) mechanism under polar mobile phase and hydrophilic-interaction liquid chromatography (HILIC) retention mechanism under less polar mobile phase. The high column efficiencies of 110,000N/m can be achieved for separation of alkylbenzenes in capillary reversed-phase liquid chromatography (cLC). Due to the robust property of hybrid monolith and the rich primary and secondary amino groups on its surface, the resulting hybrid monolith was easily modified with γ-gluconolactone and physically coated with cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC), respectively. The former was successfully applied for HILIC separation of neutral, basic and acidic polar compounds as well as small peptides, and the latter for enantioseparation of racemates in cLC. The high column efficiencies were achieved in all of those separations. These results demonstrated that the hybrid monolith (POSS-PEI) possessed high stability and good surface tailorbility, potentially being applied for other research fields. Copyright © 2013 Elsevier B.V. All rights reserved.

Properties of water as a novel stationary phase in capillary gas chromatography.

PubMed

Gallant, Jonathan A; Thurbide, Kevin B

2014-09-12

A novel method of separation that uses water as a stationary phase in capillary gas chromatography (GC) is presented. Through applying a water phase to the interior walls of a stainless steel capillary, good separations were obtained for a large variety of analytes in this format. It was found that carrier gas humidification and backpressure were key factors in promoting stable operation over time at various temperatures. For example, with these measures in place, the retention time of an acetone test analyte was found to reduce by only 44s after 100min of operation at a column temperature of 100°C. In terms of efficiency, under optimum conditions the method produced about 20,000 plates for an acetone test analyte on a 250μm i.d.×30m column. Overall, retention on the stationary phase generally increased with analyte water solubility and polarity, but was relatively little correlated with analyte volatility. Conversely, non-polar analytes were essentially unretained in the system. These features were applied to the direct analysis of different polar analytes in both aqueous and organic samples. Results suggest that this approach could provide an interesting alternative tool in capillary GC separations. Copyright © 2014 Elsevier B.V. All rights reserved.

Wall effects in continuous microfluidic magneto-affinity cell separation.

PubMed

Wu, Liqun; Zhang, Yong; Palaniapan, Moorthi; Roy, Partha

2010-05-01

Continuous microfluidic magneto-affinity cell separator combines unique microscale flow phenomenon with advantageous nanobead properties, to isolate cells with high specificity. Owing to the comparable size of the cell-bead complexes and the microchannels, the walls of the microchannel exert a strong influence on the separation of cells by this method. We present a theoretical and experimental study that provides a quantitative description of hydrodynamic wall interactions and wall rolling velocity of cells. A transient convection model describes the transport of cells in two-phase microfluidic flow under the influence of an external magnetic field. Transport of cells along the microchannel walls is also considered via an additional equation. Results show the variation of cell flux in the fluid phases and the wall as a function of a dimensionless parameter arising in the equations. Our results suggest that conditions may be optimized to maximize cell separation while minimizing contact with the wall surfaces. Experimentally measured cell rolling velocities on the wall indicate the presence of other near-wall forces in addition to fluid shear forces. Separation of a human colon carcinoma cell line from a mixture of red blood cells, with folic acid conjugated 1 microm and 200 nm beads, is reported.

Method and apparatus for physical separation of different sized nanostructures

DOEpatents

Roberts, Christopher B.; Saunders, Steven R.

2012-07-10

The present application provides apparatuses and methods for the size-selective fractionation of ligand-capped nanoparticles that utilizes the tunable thermophysical properties of gas-expanded liquids. The nanoparticle size separation processes are based on the controlled reduction of the solvent strength of an organic phase nanoparticle dispersion through increases in concentration of the antisolvent gas, such as CO.sub.2, via pressurization. The method of nanomaterial separation contains preparing a vessel having a solvent and dispersed nanoparticles, pressurizing the chamber with a gaseous antisolvent, and causing a first amount of the nanoparticles to precipitate, transporting the solution to a second vessel, pressurizing the second vessel with the gaseous antisolvent and causing further nanoparticles to separate from the solution.

Persistent mobility edges and anomalous quantum diffusion in order-disorder separated quantum films

NASA Astrophysics Data System (ADS)

Zhong, Jianxin; Stocks, G. Malcolm

2007-01-01

A concept of order-disorder separated quantum films is proposed for the design of ultrathin quantum films of a few atomic layers thick with unconventional transport properties. The concept is demonstrated through studying an atomic bilayer comprised of an ordered layer and a disordered layer. Without the disordered layer or the ordered layer, the system is a conducting two-dimensional (2D) crystal or an insulating disordered 2D electron system. Without the order-disorder phase separation, a disordered bilayer is insulating under large disorder. In an order-disorder separated atomic bilayer, however, we show that the system behaves remarkably different from conventional ordered or disordered electron systems, exhibiting metal-insulator transitions with persistent mobility edges and superdiffusive anomalous quantum diffusion.

Lamellar, micro-phase separated blends of methyl cellulose and dendritic polyethylene glycol, POSS-PEG.

PubMed

Chinnam, Parameswara Rao; Mantravadi, Ramya; Jimenez, Jayvic C; Dikin, Dmitriy A; Wunder, Stephanie L

2016-01-20

Blends of methyl cellulose (MC) and liquid pegylated polyoctahedralsilsesquioxane (POSS-PEG) were prepared from non-gelled, aqueous solutions at room temperature (RT), which was below their gel temperatures (Tm). Lamellar, fibrillated films (pure MC) and increasingly micro-porous morphologies with increasing POSS-PEG content were formed, which had RT moduli between 1 and 5GPa. Evidence of distinct micro-phase separated MC and POSS-PEG domains was indicated by the persistence of the MC and POSS-PEG (at 77K) crystal structures in the X-ray diffraction data, and scanning transmission electron images. Mixing of MC and POSS-PEG in the interface region was indicated by suppression of crystallinity in the POSS-PEG, and increases/decreases in the glass transition temperatures (Tg) of POSS-PEG/MC in the blends compared with the pure components. These interface interactions may serve as cross-link sites between the micro-phase separated domains that permit incorporation of high amounts of POSS-PEG in the blends, prevent macro-phase separation and result in rubbery material properties (at high POSS-PEG content). Above Tg/Tm of POSS-PEG, the moduli of the blends increase with MC content as expected. However, below Tg/Tm of POSS-PEG, the moduli are greater for blends with high POSS-PEG content, suggesting that it behaves like semi-crystalline polyethylene oxide reinforced with silica (SiO1.5). Copyright © 2015 Elsevier Ltd. All rights reserved.

Self-assembly of amorphous biophotonic nanostructures by phase separation

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

Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar

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 rolesmore » 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.« less

Cure kinetics, morphologies, and mechanical properties of thermoplastic/MWCNT modified multifunctional glassy epoxies prepared via continuous reaction methods

NASA Astrophysics Data System (ADS)

Cheng, Xiaole

The primary goal of this dissertation is to develop a novel continuous reactor method to prepare partially cured epoxy prepolymers for aerospace prepreg applications with the aim of replacing traditional batch reactors. Compared to batch reactors, the continuous reactor is capable of solubilizing and dispersing a broad range of additives including thermoplastic tougheners, stabilizers, nanoparticles and curatives and advancing epoxy molecular weights and viscosities while reducing energy consumption. In order to prove this concept, polyethersulfone (PES) modified 4, 4'-diaminodiphenylsulfone (44DDS)/tetraglycidyl-4, 4'-diaminodiphenylmethane (TGDDM) epoxy prepolymers were firstly prepared using both continuous reactor and batch reactor methods. Kinetic studies confirmed the chain extension reaction in the continuous reactor is similar to the batch reactor, and the molecular weights and viscosities of prepolymers were readily controlled through reaction kinetics. Atomic force microscopy (AFM) confirmed similar cured network morphologies for formulations prepared from batch and continuous reactors. Additionally tensile strength, tensile modulus and fracture toughness analyses concluded mechanical properties of cured epoxy matrices produced from both reactors were equivalent. Effects of multifunctional epoxy compositions on thermoplastics phase-separated morphologies were systematically studied using a combination of AFM with nanomechanical mapping, spectroscopic and calorimetric techniques to provide new insights to tailor cured reaction induced phase separation (CRIPS) in multifunctional epoxy blend networks. Furthermore, how resultant crosslinked glassy polymer network and phase-separated morphologies correlated with mechanical properties are discussed in detail. Multiwall carbon nanotube (MWCNT)/TGDDM epoxy prepolymers were further prepared by combining the successful strategies for advancing epoxy chemistries and dispersing nanotubes using the continuous reactor. Optical microscopy (OM) and scanning electron microscopy (SEM) were used to characterize the MWCNT dispersion states and stabilization in epoxy prepolymer matrix after continuous process and during curing cycles. Additionally, electrical conductivities and mechanical properties of final cured MWCNT/TGDDM composites were measured and discussed in view of their corresponding MWCNT dispersion states. Ternary blends of MWCNT reinforced thermoplastic/epoxy prepolymers were prepared by the continuous reactor. Influence of MWCNT on the CRIPS mechanism and the cured morphologies were systematically investigated using SEM and rheological analysis. Incorporation of MWCNT in thermoplastic/epoxy matrices can lead to a morphological transformation from phase inverted, to co-continuous, and to droplet dispersed morphology. In additional, dynamic mechanical analysis revealed the heterogeneity of MWCNT dispersion in thermoplastic/thermosets systems.

Lattice-patterned LC-polymer composites containing various nanoparticles as additives

PubMed Central

2012-01-01

In this study, we show the effect of various nanoparticle additives on phase separation behavior of a lattice-patterned liquid crystal [LC]-polymer composite system and on interfacial properties between the LC and polymer. Lattice-patterned LC-polymer composites were fabricated by exposing to UV light a mixture of a prepolymer, an LC, and SiO2 nanoparticles positioned under a patterned photomask. This resulted in the formation of an LC and prepolymer region through phase separation. We found that the incorporation of SiO2 nanoparticles significantly affected the electro-optical properties of the lattice-patterned LC-polymer composites. This effect is a fundamental characteristic of flexible displays. The electro-optical properties depend on the size and surface functional groups of the SiO2 nanoparticles. Compared with untreated pristine SiO2 nanoparticles, which adversely affect the performance of LC molecules surrounded by polymer walls, SiO2 nanoparticles with surface functional groups were found to improve the electro-optical properties of the lattice-patterned LC-polymer composites by increasing the quantity of SiO2 nanoparticles. The surface functional groups of the SiO2 nanoparticles were closely related to the distribution of SiO2 nanoparticles in the LC-polymer composites, and they influenced the electro-optical properties of the LC molecules. It is clear from our work that the introduction of nanoparticles into a lattice-patterned LC-polymer composite provides a method for controlling and improving the composite's electro-optical properties. This technique can be used to produce flexible substrates for various flexible electronic devices. PMID:22222011

Cesium vacancy ordering in phase-separated C s x F e 2 - y S e 2

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

Taddei, K. M.; Sturza, M.; Chung, D. Y.

2015-09-01

By simultaneously displaying magnetism and superconductivity in a single phase, the iron based superconductors provide a model system for the study of magnetism’s role in superconductivity. The class of intercalated iron selenide superconductors is unique amongst these in having the additional property of phase separation and coexistence of two distinct phases - one majority phase with iron vacancy ordering and strong antiferromagnetism and the other a poorly understood minority microscopic phase with a contested structure. Adding to the intrigue, the majority phase has never been found to show superconductivity on its own while the minority phase has never been successfullymore » synthesized separate from the majority phase. In order to better understand this minority phase, a series of high quality CsxFe2-ySe2 single crystals with (0.8 ≤ x ≤ 1; 0 ≤ y ≤ 0.3) were grown and studied. Neutron and x-ray powder diffraction performed on ground crystals show the average structure of the minority phase to be I4/mmm, however, the temperature evolution of its lattice parameters shows it to be distinct from the high temperature I4/mmm parent structure. Neutron and x-ray diffraction experiments performed on single crystal samples reveal the presence of previously unobserved discrete superlattice reflections that remove the degeneracy of the Cs sites in both the majority and minority phases and reduce their structural symmetries from body-centered to primitive. Group theoretical analysis in conjunction with structural modeling shows that the observed superlattice reflections originate from a three-dimensional Cs vacancy ordering in the minority phase. This model predicts a 25% vacancy of the Cs site which is consistent with the site’s refined occupancy. Magnetization measurements performed in tandem with neutron single crystal diffraction provide evidence that the minority phase is the host of superconductivity. Our results also reveal a superconducting dome in which the superconducting transition temperature varies as a function of the valence of iron.« less

Thick film magnetic nanoparticulate composites and method of manufacture thereof

NASA Technical Reports Server (NTRS)

Ge, Shihui (Inventor); Yan, Dajing (Inventor); Xiao, Danny T. (Inventor); Ma, Xinqing (Inventor); Zhang, Yide (Inventor); Zhang, Zongtao (Inventor)

2009-01-01

Thick film magnetic/insulating nanocomposite materials, with significantly reduced core loss, and their manufacture are described. The insulator coated magnetic nanocomposite comprises one or more magnetic components, and an insulating component. The magnetic component comprises nanometer scale particles (about 1 to about 100 nanometers) coated by a thin-layered insulating phase. While the intergrain interaction between the immediate neighboring magnetic nanoparticles separated by the insulating phase provides the desired soft magnetic properties, the insulating material provides high resistivity, which reduces eddy current loss.

Influence of physical properties and operating parameters on hydrodynamics in Centrifugal Partition Chromatography.

PubMed

Adelmann, S; Schembecker, G

2011-08-12

Besides the selection of a suitable biphasic solvent system the separation efficiency in Centrifugal Partition Chromatography (CPC) is mainly influenced by the hydrodynamics in the chambers. The flow pattern, the stationary phase retention and the interfacial area for mass transfer strongly depend on physical properties of the solvent system and operating parameters. In order to measure these parameters we visualized the hydrodynamics in a FCPC-chamber for five different solvent systems with an optical measurement system and calculated the stationary phase retention, interfacial area and the distribution of mobile phase thickness in the chamber. Although inclined chambers were used we found that the Coriolis force always deflected the mobile phase towards the chamber wall reducing the interfacial area. This effect increased for systems with low density difference. We also have shown that the stability of phase systems (stationary phase retention) and its tendency to disperse increased for smaller values of the ratio of interfacial tension and density difference. But also the viscosity ratio and the flow pattern itself had a significant effect on retention and dispersion of the mobile phase. As a result operating parameters should be chosen carefully with respect to physical properties for a CPC system. In order to reduce the effect of the Coriolis force CPC devices with greater rotor radius are desirable. Copyright © 2011 Elsevier B.V. All rights reserved.

Polarity-based fractionation in proteomics: hydrophilic interaction vs reversed-phase liquid chromatography.

PubMed

Jafari, M; Mirzaie, M; Khodabandeh, M; Rezadoost, H; Ghassempour, A; Aboul-Enein, H Y

2016-07-01

During recent decades, hydrophilic interaction liquid chromatography (HILIC) ahs been introduced to fractionate or purify especially polar solutes such as peptides and proteins while reversed-phase liquid chromatography (RPLC) is also a common strategy. RPLC is also a common dimension in multidimensional chromatography. In this study, the potential of HILIC vs RPLC chromatography was compared for proteome mapping of human peripheral blood mononuclear cell extract. In HILIC a silica-based stationary phase and for RPLC a C18 column were applied. Then separated proteins were eluted to an ion trap mass spectrometry system. Our results showed that the HILIC leads to more proteins being identified in comparison to RPLC. Among the total 181 identified proteins, 56 and 38 proteins were fractionated specifically by HILIC and RPLC, respectively. In order to demonstrate this, the physicochemical properties of identified proteins such as polarity and hydrophobicity were considered. This analysis indicated that polarity may play a major role in the HILIC separation of proteins vs RPLC. Using gene ontology enrichment analysis, it was also observed that differences in physicochemical properties conform to the cellular compartment and biological features. Finally, this study highlighted the potential of HILIC and the great orthogonality of RPLC in gel-free proteomic studies. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

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. Copyright © 2016 Elsevier B.V. All rights reserved.

Magnetic and transport signatures of Rashba spin-orbit coupling on the ferromagnetic Kondo lattice model in two dimensions

NASA Astrophysics Data System (ADS)

Meza, Giovany A.; Riera, José A.

2014-08-01

Motivated by emergent phenomena at oxide surfaces and interfaces, particularly those involving transition metal oxides with perovskite crystal structure such as LaTiO3/SrTiO3, we examine the ferromagnetic Kondo lattice model (FKLM) in the presence of a Rashba spin-orbit coupling (RSOC). Using numerical techniques, under the assumption that the electrons on localized orbitals may be treated as classical continuum spins, we compute various charge, spin, and transport properties on square clusters at zero temperature. We find that the main effect of the RSOC is the destruction of the ferromagnetic state present in the FKLM at low electron fillings, with the consequent suppression of conductivity. In addition, near half filling the RSOC leads to a departure of the antiferromagnetic state of the FKLM with a consequent reduction to the intrinsic tendency to electronic phase separation. The interplay between phase separation on one side, and magnetic and transport properties on the other, is carefully analyzed as a function of the RSOC/hopping ratio.

Lipid melting and cuticular permeability: new insights into an old problem.

PubMed

Gibbs, Allen G.

2002-04-01

The idea that the physical properties of cuticular lipids affect cuticular permeability goes back over 65 years. This proposal has achieved textbook status, despite controversy and the general lack of direct supporting evidence. Recent work supports the standard model, in which lipid melting results in increased cuticular permeability. Surprisingly, although all species studied to date can synthesize lipids that remain in a solid state at environmental temperatures, partial melting often occurs due to the deposition of lipids with low melting points. This will tend to increase water loss; the benefits may include better dispersal of lipids or other compounds across the cuticle or improved communication via cuticular pheromones. In addition, insects with high melting-point lipids are not necessarily less permeable at low temperatures. One likely reason is variation in lipid properties within the cuticle. Surface lipids differ from one region to another, and biophysical studies of model mixtures suggest the occurrence of phase separation between melted and solid lipid fractions. Lipid phase separation may have important implications for insect water balance and chemical communication.

[Separation of catechins and caffeine in tea polyphenol by isocratic elution high performance liquid chromatography].

PubMed

Tang, G Y; Wu, H J; Wu, L; Li, Z J; Yao, Y G

2001-05-01

The catechins, particularly in green tea, have been found to possess anti-mutagenic and anti-tumorigenic properties. As each catechin possesses distinct properties, a simple and rapid method that could be used for analysis of individual catechins in a complex mixture would be necessary. A relatively simple and rapid method for simultaneous separation of five catechins and caffeine in tea polyphenol by isocratic elution high performance liquid chromatography has been developed. The analysis could be finished within 30 min. They were measured using Resolve C18 column (at 43 degrees C) and UV detector (at 280 nm), water-85% phosphoric acid aqueous solution-acetonitrile-dimethyl formamide(DMF) (859:1:120:20, V/V) as mobile phase. There was a good linear relationship between the content of component and its peak area for catechins and caffeine, with the correlation coefficients of 0.9992-0.9999. The average recoveries (n = 5) were 83.33%-104.42%, and the relative standard deviations (n = 6) were 0.74%-1.43%. The effect of concentration of DMF in mobile phase was studied.

Cesium vacancy ordering in phase-separated C s x F e 2 - y S e 2

DOE PAGES

Taddei, Keith M.; Sturza, M.; Chung, Duck -Yung; ...

2015-09-14

By simultaneously displaying magnetism and superconductivity in a single phase, the iron-based superconductors provide a model system for the study of magnetism's role in superconductivity. The class of intercalated iron selenide superconductors is unique among these in having the additional property of phase separation and coexistence of two distinct phases—one majority phase with iron vacancy ordering and strong antiferromagnetism, and the other a poorly understood minority microscopic phase with a contested structure. Adding to the intrigue, the majority phase has never been found to show superconductivity on its own while the minority phase has never been successfully synthesized separate frommore » the majority phase. In order to better understand this minority phase, a series of high-quality Cs xFe 2–ySe 2 single crystals with (0.8 ≤ x ≤ 1;0 ≤ y ≤ 0.3) were grown and studied. Neutron and x-ray powder diffraction performed on ground crystals show that the average I4/mmm structure of the minority phase is distinctly different from the high-temperature I4/mmm parent structure. Moreover, single-crystal diffraction reveals the presence of discrete superlattice reflections that remove the degeneracy of the Cs sites in both the majority and minority phases and reduce their structural symmetries from body centered to primitive. Group theoretical analysis in conjunction with structural modeling shows that the observed superlattice reflections originate from three-dimensional Cs vacancy ordering. This model predicts a 25% vacancy of the Cs site in the minority phase which is consistent with the site's refined occupancy. Magnetization measurements performed in tandem with neutron single-crystal diffraction provide evidence that the minority phase is the host of superconductivity. Lastly, our results also reveal a superconducting dome in which the superconducting transition temperature varies as a function of the nominal valence of iron.« less

Nanoimprinting-induced nanomorphological transition in polymer solar cells: enhanced electrical and optical performance.

PubMed

Jeong, Seonju; Cho, Changsoon; Kang, Hyunbum; Kim, Ki-Hyun; Yuk, Youngji; Park, Jeong Young; Kim, Bumjoon J; Lee, Jung-Yong

2015-03-24

We have investigated the effects of a directly nanopatterned active layer on the electrical and optical properties of inverted polymer solar cells (i-PSCs). The capillary force in confined molds plays a critical role in polymer crystallization and phase separation of the film. The nanoimprinting process induced improved crystallization and multidimensional chain alignment of polymers for more effective charge transfer and a fine phase-separation between polymers and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) to favor exciton dissociation and increase the generation rate of charge transfer excitons. Consequently, the power conversion efficiency with a periodic nanostructure was enhanced from 7.40% to 8.50% and 7.17% to 9.15% in PTB7 and PTB7-Th based i-PSCs, respectively.

Phase Transition between Black and Blue Phosphorenes: A Quantum Monte Carlo Study

NASA Astrophysics Data System (ADS)

Li, Lesheng; Yao, Yi; Reeves, Kyle; Kanai, Yosuke

Phase transition of the more common black phosphorene to blue phosphorene is of great interest because they are predicted to exhibit unique electronic and optical properties. However, these two phases are predicted to be separated by a rather large energy barrier. In this work, we study the transition pathway between black and blue phosphorenes by using the variable cell nudge elastic band method combined with density functional theory calculation. We show how diffusion quantum Monte Carlo method can be used for determining the energetics of the phase transition and demonstrate the use of two approaches for removing finite-size errors. Finally, we predict how applied stress can be used to control the energetic balance between these two different phases of phosphorene.

Bacterial Tethering Analysis Reveals a “Run-Reverse-Turn” Mechanism for Pseudomonas Species Motility

PubMed Central

Qian, Chen; Wong, Chui Ching; Swarup, Sanjay

2013-01-01

We have developed a program that can accurately analyze the dynamic properties of tethered bacterial cells. The program works especially well with cells that tend to give rise to unstable rotations, such as polar-flagellated bacteria. The program has two novel components. The first dynamically adjusts the center of the cell's rotational trajectories. The second applies piecewise linear approximation to the accumulated rotation curve to reduce noise and separate the motion of bacteria into phases. Thus, it can separate counterclockwise (CCW) and clockwise (CW) rotations distinctly and measure rotational speed accurately. Using this program, we analyzed the properties of tethered Pseudomonas aeruginosa and Pseudomonas putida cells for the first time. We found that the Pseudomonas flagellar motor spends equal time in both CCW and CW phases and that it rotates with the same speed in both phases. In addition, we discovered that the cell body can remain stationary for short periods of time, leading to the existence of a third phase of the flagellar motor which we call “pause.” In addition, P. aeruginosa cells adopt longer run lengths, fewer pause frequencies, and shorter pause durations as part of their chemotactic response. We propose that one purpose of the pause phase is to allow the cells to turn at a large angle, where we show that pause durations in free-swimming cells positively correlate with turn angle sizes. Taken together, our results suggest a new “run-reverse-turn” paradigm for polar-flagellated Pseudomonas motility that is different from the “run-and-tumble” paradigm established for peritrichous Escherichia coli. PMID:23728820

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation

PubMed Central

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-01-01

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3, 5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. PMID:23891368

Forced Two-Phase Helium Cooling Scheme for the Mu2e Transport Solenoid

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

Tatkowski, G.; Cheban, S.; Dhanaraj, N.

2015-01-01

The Mu2e Transport Solenoid (TS) is an S-shaped magnet formed by two separate but similar magnets, TS-u and TS-d. Each magnet is quarter-toroid shaped with a centerline radius of approximately 3 m utilizing a helium cooling loop consisting of 25 to 27 horizontal-axis rings connected in series. This cooling loop configuration has been deemed adequate for cooling via forced single phase liquid helium; however it presents major challenges to forced two-phase flow such as “garden hose” pressure drop, concerns of flow separation from tube walls, difficulty of calculation, etc. Even with these disadvantages, forced two-phase flow has certain inherent advantagesmore » which make it a more attractive option than forced single phase flow. It is for this reason that the use of forced two-phase flow was studied for the TS magnets. This paper will describe the analysis using helium-specific pressure drop correlations, conservative engineering approach, helium properties calculated and updated at over fifty points, and how the results compared with those in literature. Based on the findings, the use of forced-two phase helium is determined to be feasible for steady-state cooling of the TS solenoids« less

H-T magnetic phase diagrams of electron-doped Sm1-xCaxMnO3: Evidence for phase separation and metamagnetic transitions

NASA Astrophysics Data System (ADS)

Respaud, M.; Broto, J. M.; Rakoto, H.; Vanacken, J.; Wagner, P.; Martin, C.; Maignan, A.; Raveau, B.

2001-04-01

The magnetic properties of the polycrystalline manganites Sm1-xCaxMnO3 have been studied for (1>=x>=2/3) under high magnetic fields up to 50 T. The phase diagrams in the H-T plane have been determined. The more representative systems have also been studied by means of neutron diffraction experiments. Increasing the electron concentration in CaMnO3 leads to an increasing minor ferromagnetic (FM) component superimposed on the antiferromagnetic (AFM) background. A cluster-glass regime is observed for x=0.9, where FM clusters are embedded in the G-type AFM matrix of the parent compound. For 0.8>=x, field-induced transitions from the AFM ground state to a FM one have been observed. They correspond to the melting of the C-type AFM orbital-ordered phase for x=0.8, and to the collapse of the charge-ordered phase for x=3/4. In between these two characteristic domains of concentration, x~0.85, the magnetization curves show a superposition of the two above behaviors, suggesting phase separation. This scenario is consistent with the neutron diffraction results showing that the crystalline and magnetic structures of each phase coexist.

Microphase Separation in Oil-Water Mixtures Containing Hydrophilic and Hydrophobic Ions

NASA Astrophysics Data System (ADS)

Tasios, Nikos; Samin, Sela; van Roij, René; Dijkstra, Marjolein

2017-11-01

We develop a lattice-based Monte Carlo simulation method for charged mixtures capable of treating dielectric heterogeneities. Using this method, we study oil-water mixtures containing an antagonistic salt, with hydrophilic cations and hydrophobic anions. Our simulations reveal several phases with a spatially modulated solvent composition, in which the ions partition between water-rich and water-poor regions according to their affinity. In addition to the recently observed lamellar phase, we find tubular and droplet phases, reminiscent of those found in block copolymers and surfactant systems. Interestingly, these structures stem from ion-mediated interactions, which allows for tuning of the phase behavior via the concentrations, the ionic properties, and the temperature.

Improved optimization of polycyclic aromatic hydrocarbons (PAHs) mixtures resolution in reversed-phase high-performance liquid chromatography by using factorial design and response surface methodology.

PubMed

Andrade-Eiroa, Auréa; Diévart, Pascal; Dagaut, Philippe

2010-04-15

A new procedure for optimizing PAHs separation in very complex mixtures by reverse phase high performance (RPLC) is proposed. It is based on changing gradually the experimental conditions all along the chromatographic procedure as a function of the physical properties of the compounds eluted. The temperature and speed flow gradients allowed obtaining the optimum resolution in large chromatographic determinations where PAHs with very different medium polarizability have to be separated. Whereas optimization procedures of RPLC methodologies had always been accomplished regardless of the physico-chemical properties of the target analytes, we found that resolution is highly dependent on the physico-chemical properties of the target analytes. Based on resolution criterion, optimization process for a 16 EPA PAHs mixture was performed on three sets of difficult-to-separate PAHs pairs: acenaphthene-fluorene (for the optimization procedure in the first part of the chromatogram where light PAHs elute), benzo[g,h,i]perylene-dibenzo[a,h]anthracene and benzo[g,h,i]perylene-indeno[1,2,3-cd]pyrene (for the optimization procedure of the second part of the chromatogram where the heavier PAHs elute). Two-level full factorial designs were applied to detect interactions among variables to be optimized: speed flow, temperature of column oven and mobile-phase gradient in the two parts of the studied chromatogram. Experimental data were fitted by multivariate nonlinear regression models and optimum values of speed flow and temperature were obtained through mathematical analysis of the constructed models. An HPLC system equipped with a reversed phase 5 microm C18, 250 mm x 4.6mm column (with acetonitrile/water mobile phase), a column oven, a binary pump, a photodiode array detector (PDA), and a fluorimetric detector were used in this work. Optimum resolution was achieved operating at 1.0 mL/min in the first part of the chromatogram (until 45 min) and 0.5 mL/min in the second one (from 45 min to the end) and by applying programmed temperature gradient (15 degrees C until 30 min and progressively increasing temperature until reaching 40 degrees C at 45 min). (c) 2009 Elsevier B.V. All rights reserved.

Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process.

PubMed

Zhang, Wenzhong; Hietala, Sami; Khriachtchev, Leonid; Hatanpää, Timo; Doshi, Bhairavi; Koivula, Risto

2018-06-21

The lanthanides (Ln) are an essential part of many advanced technologies. Our societal transformation toward renewable energy drives their ever-growing demand. The similar chemical properties of the Ln pose fundamental difficulties in separating them from each other, yet high purity elements are crucial for specific applications. Here, we propose an intralanthanide separation method utilizing a group of titanium(IV) butyl phosphate coordination polymers as solid-phase extractants. These materials are characterized, and they contain layered structures directed by the hydrophobic interaction of the alkyl chains. The selective Ln uptake results from the transmetalation reaction (framework metal cation exchange), where the titanium(IV) serves as sacrificial coordination centers. The "tetrad effect" is observed from a dilute Ln 3+ mixture. However, smaller Ln 3+ ions are preferentially extracted in competitive binary separation models between adjacent Ln pairs. The intralanthanide ion-exchange selectivity arises synergistically from the coordination and steric strain preferences, both of which follow the reversed Ln contraction order. A one-step aqueous separation of neodymium (Nd) and dysprosium (Dy) is quantitatively achievable by simply controlling the solution pH in a batch mode, translating into a separation factor of greater than 2000 and 99.1% molar purity of Dy in the solid phase. Coordination polymers provide a versatile platform for further exploring selective Ln separation processes via the transmetalation process.

Mixed-bed ion exchange chromatography employing a salt-free pH gradient for improved sensitivity and compatibility in MudPIT.

PubMed

Mommen, Geert P M; Meiring, Hugo D; Heck, Albert J R; de Jong, Ad P J M

2013-07-16

In proteomics, comprehensive analysis of peptides mixtures necessitates multiple dimensions of separation prior to mass spectrometry analysis to reduce sample complexity and increase the dynamic range of analysis. The main goal of this work was to improve the performance of (online) multidimensional protein identification technology (MudPIT) in terms of sensitivity, compatibility and recovery. The method employs weak anion and strong cation mixed-bed ion exchange chromatography (ACE) in the first separation dimension and reversed phase chromatography (RP) in the second separation dimension (Motoyama et.al. Anal. Chem 2007, 79, 3623-34.). We demonstrated that the chromatographic behavior of peptides in ACE chromatography depends on both the WAX/SCX mixing ratio as the ionic strength of the mobile phase system. This property allowed us to replace the conventional salt gradient by a (discontinuous) salt-free, pH gradient. First dimensional separation of peptides was accomplished with mixtures of aqueous formic acid and dimethylsulfoxide with increasing concentrations. The overall performance of this mobile phase system was found comparable to ammonium acetate buffers in application to ACE chromatography, but clearly outperformed strong cation exchange for use in first dimensional peptide separation. The dramatically improved compatibility between (salt-free) ion exchange chromatography and reversed phase chromatography-mass spectrometry allowed us to downscale the dimensions of the RP analytical column down to 25 μm i.d. for an additional 2- to 3-fold improvement in performance compared to current technology. The achieved levels of sensitivity, orthogonality, and compatibility demonstrates the potential of salt-free ACE MudPIT for the ultrasensitive, multidimensional analysis of very modest amounts of sample material.

A thermo-mechanical correlation with driving forces for hcp martensite and twin formations in the Fe-Mn-C system exhibiting multicomposition sets.

PubMed

Nakano, Jinichiro

2013-02-01

The thermodynamic properties of the Fe-Mn-C system were investigated by using an analytical model constructed by a CALPHAD approach. The stacking fault energy (SFE) of the fcc structure with respect to the hcp phase was always constant at T 0 , independent of the composition and temperature when other related parameters were assumed to be constant. Experimental limits for the thermal hcp formation and the mechanical (deformation-induced) hcp formation were separated by the SFE at T 0 . The driving force for the fcc to hcp transition, defined as a dimensionless value -d G m /( RT ), was determined in the presence of Fe-rich and Mn-rich composition sets in each phase. Carbon tended to partition to the Mn-rich phase rather than to the Fe-rich phase for the compositions studied. The results obtained revealed a thermo-mechanical correlation with empirical yield strength, maximum true stress and maximum true strain. The proportionality between thermodynamics and mechanical properties is discussed.

Determination of the thickness of the embedding phase in 0D nanocomposites

NASA Astrophysics Data System (ADS)

Martínez-Martínez, D.; Sánchez-López, J. C.

2017-11-01

0D nanocomposites formed by small nanoparticles embedded in a second phase are very interesting systems which may show properties that are beyond those observed in the original constituents alone. One of the main parameters to understand the behavior of such nanocomposites is the determination of the separation between two adjacent nanoparticles, in other words, the thickness of the embedding phase. However, its experimental measurement is extremely complicated. Therefore, its evaluation is performed by an indirect approach using geometrical models. The ones typically used represent the nanoparticles by cubes or spheres. In this paper the used geometrical models are revised, and additional geometrical models based in other parallelohedra (hexagonal prism, rhombic and elongated dodecahedron and truncated octahedron) are presented. Additionally, a hybrid model that shows a transition between the spherical and tessellated models is proposed. Finally, the different approaches are tested on a set of titanium carbide/amorphous carbon (TiC/a-C) nanocomposite films to estimate the thickness of the a-C phase and explain the observed hardness properties.

Static and dynamic dielectric properties of strongly polar liquids in the vicinity of first order and weakly first order phase transitions

NASA Astrophysics Data System (ADS)

Jadżyn, Jan; Czechowski, Grzegorz; Legrand, Christian; Douali, Redouane

2003-04-01

The paper presents the results of measurements of the linear dielectric properties of the compounds from the homologous series of alkylcyanobiphenyls (CnH2n+1PhPhCN, nCB) in the vicinity of the first order transition (from the isotropic liquid to the crystalline phase) of nonmesogenic nCB’s (n=2 4) and the weakly first order transition (from the isotropic liquid to the nematic phase) of 5CB. The experimental method for the separation of the critical part of the static permittivity derivative and the activation energy for rotation of the mesogenic molecules, in the vicinity of weakly first order phase transition, is proposed. It is shown that the critical temperature dependence of the permittivity and the activation energy can be described with a function of (T-T*)-α type, with the same values of the temperature of virtual transition of the second order (T*) and the critical exponent (α).

The effect of charged groups on hydrophilic monolithic stationary phases on their chromatographic properties.

PubMed

Li, Haibin; Liu, Chusheng; Wang, Qiqin; Zhou, Haibo; Jiang, Zhengjin

2016-10-21

In order to investigate the effect of charged groups present in hydrophilic monolithic stationary phases on their chromatographic properties, three charged hydrophilic monomers, i.e. N,N-dimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)ammonium betaine (SPDA), [2-(acryloyloxy)ethyl]trimethylammonium chloride (AETA), and 3-sulfopropyl acrylate potassium salt (SPA) were co-polymerized with the crosslinker N,N'-methylenebisacrylamide (MBA), respectively. The physicochemical properties of the three resulting charged hydrophilic monolithic columns were evaluated using scanning electron microscopy, ζ-potential analysis and micro-HPLC. High column efficiency was obtained on the three monolithic columns at a linear velocity of 1mm/s using thiourea as test compound. Comparative characterization of the three charged HILIC phases was then carried out using a set of model compounds, including nucleobases, nucleosides, benzoic acid derivatives, phenols, β-blockers and small peptides. Depending on the combination of stationary phase/mobile phase/solute, both hydrophilic interaction and other potential secondary interactions, including electrostatic interaction, hydrogen-bonding interaction, molecular shape selectivity, could contribute to the over-all retention of the analytes. Because of the strong electrostatic interaction provided by the quaternary ammonium groups in the poly (AETA-co-MBA) monolith, this cationic HILIC monolith exhibited the strongest retention for benzoic acid derivatives and small peptides with distorted peak shapes and the weakest retention for basic β-blockers. The sulfonyl groups on the poly (SPA-co-MBA) hydrophilic monolith could provide strong electrostatic attraction and hydrogen bonding for positively charged analytes and hydrogen-donor/acceptor containing analytes, respectively. Therefore, basic drugs, nucleobases and nucleotides exhibited the strongest retention on this anionic monolith. Because of the weak but distinct cation exchange properties of the zwitterionic poly (SPDA-co-MBA) hydrophilic monolith, it exhibited the best separation for most test analytes (including phenols, β-blockers and small peptides) in terms of selectivity, peak shape and analysis time. The poly (AETA-co-MBA) hydrophilic monolithic column provides the best separation of nucleobases and nucleosides. These results could guide the selection and application of these charged HILIC monoliths in the future. Copyright © 2016 Elsevier B.V. All rights reserved.

Crossover from Polaronic to Magnetically Phase-Separated Behavior in La1-xSrxCoO3

NASA Astrophysics Data System (ADS)

Phelan, D.; El Khatib, S.; Wang, S.; Barker, J.; Zhao, J.; Zheng, H.; Mitchell, J. F.; Leighton, C.

2013-03-01

Dilute hole-doping in La1-xSrxCoO3 leads to the formation of ``spin-state polarons'' where a non-zero spin-state is stabilized on the nearest Co3+ ions surrounding a hole. Here, we discuss the development of electronic/magnetic properties of this system from non-magnetic x=0, through the regime of spin-state polarons, and into the region where longer-range spin correlations and phase separation develop. We present magnetometry, transport, heat capacity, and small-angle neutron scattering (SANS) on single crystals. Magnetometry indicates a crossover with x from Langevin-like behavior (polaronic) to a state with a freezing temperature and finite coercivity. Fascinating correlations with this behavior are seen in transport measurements, the evolution from polaronic to clustered states being accompanied by a crossover from Mott variable range hopping to intercluster hopping. SANS data shows Lorentzian scattering from short-range ferromagnetic clusters first emerging around x = 0.03 with correlation lengths of order two unit cells. We argue that this system provides a unique opportunity to understand in detail the crossover from polaronic to truly phase-separated states.

Spinodal Decomposition in Functionally Graded Super Duplex Stainless Steel and Weld Metal

NASA Astrophysics Data System (ADS)

Hosseini, Vahid A.; Thuvander, Mattias; Wessman, Sten; Karlsson, Leif

2018-07-01

Low-temperature phase separations (T < 500 °C), resulting in changes in mechanical and corrosion properties, of super duplex stainless steel (SDSS) base and weld metals were investigated for short heat treatment times (0.5 to 600 minutes). A novel heat treatment technique, where a stationary arc produces a steady state temperature gradient for selected times, was employed to fabricate functionally graded materials. Three different initial material conditions including 2507 SDSS, remelted 2507 SDSS, and 2509 SDSS weld metal were investigated. Selective etching of ferrite significantly decreased in regions heat treated at 435 °C to 480 °C already after 3 minutes due to rapid phase separations. Atom probe tomography results revealed spinodal decomposition of ferrite and precipitation of Cu particles. Microhardness mapping showed that as-welded microstructure and/or higher Ni content accelerated decomposition. The arc heat treatment technique combined with microhardness mapping and electrolytical etching was found to be a successful approach to evaluate kinetics of low-temperature phase separations in SDSS, particularly at its earlier stages. A time-temperature transformation diagram was proposed showing the kinetics of 475 °C-embrittlement in 2507 SDSS.

Spinodal Decomposition in Functionally Graded Super Duplex Stainless Steel and Weld Metal

NASA Astrophysics Data System (ADS)

Hosseini, Vahid A.; Thuvander, Mattias; Wessman, Sten; Karlsson, Leif

2018-04-01

Low-temperature phase separations (T < 500 °C), resulting in changes in mechanical and corrosion properties, of super duplex stainless steel (SDSS) base and weld metals were investigated for short heat treatment times (0.5 to 600 minutes). A novel heat treatment technique, where a stationary arc produces a steady state temperature gradient for selected times, was employed to fabricate functionally graded materials. Three different initial material conditions including 2507 SDSS, remelted 2507 SDSS, and 2509 SDSS weld metal were investigated. Selective etching of ferrite significantly decreased in regions heat treated at 435 °C to 480 °C already after 3 minutes due to rapid phase separations. Atom probe tomography results revealed spinodal decomposition of ferrite and precipitation of Cu particles. Microhardness mapping showed that as-welded microstructure and/or higher Ni content accelerated decomposition. The arc heat treatment technique combined with microhardness mapping and electrolytical etching was found to be a successful approach to evaluate kinetics of low-temperature phase separations in SDSS, particularly at its earlier stages. A time-temperature transformation diagram was proposed showing the kinetics of 475 °C-embrittlement in 2507 SDSS.

PLUTONIUM COMPOUNDS AND PROCESS FOR THEIR PREPARATION

DOEpatents

Wolter, F.J.; Diehl, H.C. Jr.

1958-01-01

This patent relates to certain new compounds of plutonium, and to the utilization of these compounds to effect purification or separation of the plutonium. The compounds are organic chelate compounds consisting of tetravalent plutonium together with a di(salicylal) alkylenediimine. These chelates are soluble in various organic solvents, but not in water. Use is made of this property in extracting the plutonium by contacting an aqueous solution thereof with an organic solution of the diimine. The plutonium is chelated, extracted and effectively separated from any impurities accompaying it in the aqueous phase.

Effects of ZnO Nanoparticle on the Gas Separation Performance of Polyurethane Mixed Matrix Membrane

PubMed Central

Soltani, Banafsheh

2017-01-01

Polyurethane (PU)-ZnO mixed matrix membranes (MMM) were fabricated and characterized for gas separation. A thermogravimetric analysis (TGA), a scanning electron microscope (SEM) test and an atomic-force microscopy (AFM) revealed that the physical properties and thermal stability of the membranes were improved through filler loading. Hydrogen Bonding Index, obtained from the Fourier transform infrared spectroscopy (FTIR), demonstrate that the degree of phase separation in PU-ZnO 0.5 wt % MMM was more than the neat PU, while in PU-ZnO 1.0 wt % MMM, the phase mixing had increased. Compared to the neat membrane, the CO2 permeability of the MMMs increased by 31% for PU-ZnO 0.5 wt % MMM and decreased by 34% for 1.0 wt % ZnO MMM. The CO2/CH4 and CO2/N2 selectivities of PU-ZnO 0.5 wt % were 18.75 and 64.75, respectively. PMID:28800109

Mesoporous mixed-phase Ga{sub 2}O{sub 3}: Green synthesis and enhanced photocatalytic activity

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

Liu, Jin; The Key Laboratory of Rare Earth Functional Materials and Applications, Zhoukou Normal University, Zhoukou 466001; Zhang, Gaoke, E-mail: gkzhang@whut.edu.cn

2015-08-15

Highlights: • Mixed-phase Ga{sub 2}O{sub 3} was synthesized by a facile and green method. • Mixed-phase Ga{sub 2}O{sub 3} exhibited good photocatalytic activity and stability. • The reactive species in the photocatalytic process were investigated. - Abstract: Mesoporous mixed-phase Ga{sub 2}O{sub 3} was synthesized by calcining the GaOOH precursor. The composition, crystal phase and microstructures of Ga{sub 2}O{sub 3} were characterized in detail. The phase composition of the as-prepared Ga{sub 2}O{sub 3} depended on the calcination temperature and the mixed-phase Ga{sub 2}O{sub 3} was obtained at 600–700 °C. As compared to the pure-phase α-Ga{sub 2}O{sub 3} and β-Ga{sub 2}O{sub 3},more » the mixed-phase Ga{sub 2}O{sub 3} exhibited an enhanced photocatalytic property for the degradation of metronidazole solution. The heterojunction in the mixed-phase Ga{sub 2}O{sub 3} was beneficial to the separation of photogenerated electrons and holes. Moreover, the mixed-phase Ga{sub 2}O{sub 3} possessed mesopore structure, which increased more reaction sites and was in favor of the contact of metronidazole molecules with reaction sites. The recycling experiments show that the mixed-phase Ga{sub 2}O{sub 3} has good stability and can be separated easily from the reaction system.« less

Fast-responding bio-based shape memory thermoplastic polyurethanes

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

Petrovic, Zoran S.; Milic, Jelena; Zhang, Fan

Fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes was investigated by synchrotron ultra-small angle X-ray scattering, which revealed the inter-domain spacing between the hard and soft phases, the degree of phase separation, and the level of intermixing between the hard and soft phases. We also conducted thorough investigations of the thermal, mechanical, and dielectric properties of the polyurethanes, and found that high crystallization rate ofmore » the soft segment gives these polyurethanes unique properties suitable for shapememory applications, such as adjustable transition temperatures, high degree of elastic elongations, and good mechanical strength. In conclusion, these materials are also potentially biodegradable and biocompatible, therefore suitable for biomedical and environmental applications.« less

Fast-responding bio-based shape memory thermoplastic polyurethanes

DOE PAGES

Petrovic, Zoran S.; Milic, Jelena; Zhang, Fan; ...

2017-05-31

Fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes was investigated by synchrotron ultra-small angle X-ray scattering, which revealed the inter-domain spacing between the hard and soft phases, the degree of phase separation, and the level of intermixing between the hard and soft phases. We also conducted thorough investigations of the thermal, mechanical, and dielectric properties of the polyurethanes, and found that high crystallization rate ofmore » the soft segment gives these polyurethanes unique properties suitable for shapememory applications, such as adjustable transition temperatures, high degree of elastic elongations, and good mechanical strength. In conclusion, these materials are also potentially biodegradable and biocompatible, therefore suitable for biomedical and environmental applications.« less

Fast-Responding Bio-Based Shape Memory Thermoplastic Polyurethanes.

PubMed

Petrović, Zoran S; Milić, Jelena; Zhang, Fan; Ilavsky, Jan

2017-07-14

Novel fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol for the first time. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes was investigated by synchrotron ultra-small angle X-ray scattering, which revealed the inter-domain spacing between the hard and soft phases, the degree of phase separation, and the level of intermixing between the hard and soft phases. We also conducted thorough investigations of the thermal, mechanical, and dielectric properties of the polyurethanes, and found that high crystallization rate of the soft segment gives these polyurethanes unique properties suitable for shape-memory applications, such as adjustable transition temperatures, high degree of elastic elongations, and good mechanical strength. These materials are also potentially biodegradable and biocompatible, therefore suitable for biomedical and environmental applications.

Measurement of acoustic properties of the composite materials constituting the main rotor hub of the Agusta-Westland helicopter EH-101 (civil version)

NASA Astrophysics Data System (ADS)

Tenti, L.; Denis, R.; Lakestani, F.

1991-10-01

The acoustic properties of the EH-101 helicopter rotor hub are tested by characterizing the ultrasonic propagation phenomena in the main directions of the composite materials. The carbon fiber and epoxy resin that make up the rotor hub are measured to determine the attenuation coefficient, phase propagation at normal incidence, and phase propagation as a function of angle of incidence. The speeds are measured for external box and filler samples, and strap samples are discussed separately because of their anisotropic nature and structural importance. Deviations angles of 5 deg cause refraction angles of 10 deg in the deviation of the phase propagation; therefore planar defects with an angle of 10 deg relative to the fiber direction can be easily detected. The method presented is useful in characterizing and locating defects in the composite materials that make up the main rotor hub of helicopters.

Thermodynamic model effects on the design and optimization of natural gas plants

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

Diaz, S.; Zabaloy, M.; Brignole, E.A.

1999-07-01

The design and optimization of natural gas plants is carried out on the basis of process simulators. The physical property package is generally based on cubic equations of state. By rigorous thermodynamics phase equilibrium conditions, thermodynamic functions, equilibrium phase separations, work and heat are computed. The aim of this work is to analyze the NGL turboexpansion process and identify possible process computations that are more sensitive to model predictions accuracy. Three equations of state, PR, SRK and Peneloux modification, are used to study the effect of property predictions on process calculations and plant optimization. It is shown that turboexpander plantsmore » have moderate sensitivity with respect to phase equilibrium computations, but higher accuracy is required for the prediction of enthalpy and turboexpansion work. The effect of modeling CO{sub 2} solubility is also critical in mixtures with high CO{sub 2} content in the feed.« less

Crystallization features of normal alkanes in confined geometry.

PubMed

Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin

2014-01-21

How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.

Industrially relevant epoxy-acrylate hybrid resin photopolymerizations

NASA Astrophysics Data System (ADS)

Ajiboye, Gbenga I.

Photopolymerization of epoxy-acrylate hybrid resins takes advantages of inherent properties present in the free-radical and cationic reactions to reduce oxygen inhibition problems that plague free-radical reactions. Similarly, the combined reaction mechanisms reduce moisture sensitivity of the cationic reactions. Despite the advantages of epoxy-acrylate hybrid resins, problems persist that need to be addressed. For example, low conversion and polymerization rate of the epoxides are a problem, because the fast acrylate conversion prevents the epoxide from reaching high conversion. Controlling phase separation is challenging, since two moieties with different properties are reacting. The physical properties of the polymer will be impacted by the availability of different moieties. High shrinkage stress results from the acrylate moiety, causing buckling and cracking in film and coating applications. The overall goal of this study is to use the fundamental knowledge of epoxy-acrylate hybrid resins to formulate industrially viable polymers. In order to achieve this goal, the study focuses on the following objectives: (I) determine the apparent activation energy of the hybrid monomer METHB, (II) increase epoxide conversion and polymerization rate of hybrid formulations, and (III) control physical properties in epoxy-acrylate hybrid resins. In order to increase the epoxide conversion and rate of polymerization, the sensitivity of epoxides to alcohol is used to facilitate the activated monomer (AM) mechanism and induce a covalent bond between the epoxide and acrylate polymers through the hydroxyl group. It is hypothesized that if the AM mechanism is facilitated, epoxide conversion will increase. As a result, the resins can be tailored to control phase separation and physical properties, and shrinkage stress can be reduced. In pursuit of these objectives, the hybrid monomer METHB was polymerized at temperatures ranging from 30°C to 70°C to obtain apparent activation energy of 23.49 kJ/mol for acrylate and 57 kJ/mol for epoxide moeities. Then, hybrid systems pairing hydroxyl-containing acrylates with epoxides were formulated to promote the faster AM mechanism. Monomer composition was changed in the presence of hydroxyl-containing acrylate, and initiators were carefully selected in order to control phase separation. The conversion of acrylate and epoxide was monitored in real time by Raman spectroscopy. The physical and mechanical properties were monitored using dynamic mechanical analysis. Epoxide conversion and rate of polymerization in epoxide-acrylate hybrid monomer systems were shown to increase through the introduction of a hydroxyl group on the meth/acrylate monomer, taking advantage of the faster AM mechanism. In addition, this covalent bond linking the epoxide network to the meth/acrylate polymer chains resulted in little or no phase separation and a reduction of the Tg for the hybrid polymer compared to the neat epoxide. Fundamental knowledge gained from this research will enable the use of epoxy-acrylate hybrid resins in variety of applications. For instance, shrinkage may be reduced in dental fillings, noise and vibration problems in aircraft and other machinery may be controlled, and photopolymerization cost could be reduced in thin film applications.

Understanding and Controlling Nanoscale Morphology in Self-Assembled Semiconducting Materials

NASA Astrophysics Data System (ADS)

Kang, Hyeyeon

Self-assembled semiconducting materials have been rapidly developed for a range of applications. This work aims to control the morphology of nanostructured semiconductors to understand how their functions arise from the structural properties. The first part of this dissertation focuses on the formation of a bulk-heterojunction (BHJ) in the active layer of organic photovoltaics (OPV). A BHJ is a bicontinuous interpenetrating network of organic components. The phase separation of the electron donor and the acceptor is required to achieve a BHJ structure in the nanostructured morphology, which promotes an efficient charge transportation. The use of solvent additive is one of the strategies to control the spontaneous phase separation during the film formation. Low vapor pressure solvent additives are introduced to a polymer casting solution in a sequentially processed OPV system, to study the swelling effect on the phase separation. In particular, the change in crystallinity and vertical mixing will be intensively studied upon polymer swelling. As another strategy, we introduce a molecular structure change to fullerene derivatives. A small structural variation leads to a large enough contrast of their surface energy, which is attributed to different vertical phase separation in the active layer. It eventually allows us to examine photovoltaic performance and device physics. In the second part, mesoporous inorganic films are investigated by preparation from a nanocrystal solution or sol-gel precursors for solar energy applications. Mesoporous nanocrystal-based titania is synthesized for inorganic/organic hybrid solar cells. The effect of surface modification is examined by anchoring a fullerene derivative on to titania surface. 3D interconnected mesoporous tantalum nitride films are prepared via sol-gel method as photoanodes in solar water splitting. The simple synthetic method using polymer template enables us to successfully prepare nitride films with excellent pore periodicity. The porous tantalum nitride film is examined with photoelectrochemical measurement to investigate the correlation between nanostructuring and photocatalytic activity. For the final part of this dissertation, porous cobalt ferrite and cadmium sulfide films are studied using ellipsometric porosimetry. Understanding the nature of their pores allows us to tune the intrinsic properties of the materials or prove the newly designed synthetic method.

Chemistry Division. Quarterly progress report for period ending June 30, 1949

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

Not Available

1949-09-14

Progress reports are presented for the following tasks: (1) nuclear and chemical properties of heavy elements (solution chemistry, phase rule studies); (2) nuclear and chemical properties of elements in the fission product region; (3) general nuclear chemistry; (4) radio-organic chemistry; (5) chemistry of separations processes; (6) physical chemistry and chemical physics; (7) radiation chemistry; (8) physical measurements and instrumentation; and (9) analytical chemistry. The program of the chemistry division is divided into two efforts of approximately equal weight with respect to number of personnel, chemical research, and analytical service for the Laboratory. The various research problems fall into the followingmore » classifications: (1) chemical separation processes for isolation and recovery of fissionable material, production of radioisotopes, and military applications; (2) reactor development; and (3) fundamental research.« less

The growth and structure of dark matter haloes

NASA Astrophysics Data System (ADS)

Zhao, D. H.; Mo, H. J.; Jing, Y. P.; Börner, G.

2003-02-01

In this paper, we analyse in detail the mass-accretion histories and structural properties of dark haloes in high-resolution N-body simulations. We model the density distribution in individual haloes using the Navarro-Frenk-White (NFW) profile. For a given halo, there is a tight correlation between its inner-scale radius rs and the mass within it, Ms, for all its main progenitors. Using this correlation, one can predict quite well the structural properties of a dark halo at any time in its history from its mass-accretion history, implying that the structure properties and the mass-accretion history are closely correlated. The predicted growing rate of concentration c with time tends to increase with decreasing mass-accretion rate. The build-up of dark haloes in cold dark matter (CDM) models generally consists of an early phase of fast accretion (where the halo mass Mh increases with time much faster than the expansion rate of the Universe) and a late phase of slow accretion (where Mh increases with time approximately as the expansion rate). These two phases are separated at a time when c~ 4 and the typical binding energy of the halo is approximately equal to that of a singular isothermal sphere with the same circular velocity. Haloes in the two accretion phases show systematically different properties, for example, the circular velocity vh increases rapidly with time in the fast accretion phase but remains almost constant in the slow accretion phase, the inner properties of a halo, such as rs and Ms increase rapidly with time in the fast accretion phase but change only slowly in the slow accretion phase, the inner circular velocity vs is approximately equal to vh in the fast accretion phase but is larger in the slow accretion phase. The potential well associated with a halo is built up mainly in the fast accretion phase, while a large amount of mass can be accreted in the slow accretion phase without changing the potential well significantly. We discuss our results in connection with the formation of dark haloes and galaxies in hierarchical models.

Group Contribution Methods for Phase Equilibrium Calculations.

PubMed

Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

2015-01-01

The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

Phase-Array Approach to Optical Whispering Gallery Modulators

NASA Technical Reports Server (NTRS)

Strekalov, Dmitry

2010-01-01

This technology leverages the well-defined orbital number of a whispering gallery modulator (WGM) to expand the range of applications for such resonators. This property rigidly connects the phase variation of the field in this mode with the azimuthal angle between the coupling locations. A WGM with orbital momentum L has exactly L instant nodes around the circumference of the WGM resonator supporting such a mode. Therefore, in two locations separated by the arc alpha, the phase difference of such a field will be equal to phi= alpha L. Coupling the field out of such locations, and into a balanced interferometer, once can observe a complete constructive or distractive interference (or have any situation in between) depending on the angle alpha. Similarly, a mode L + delta L will pick up the phase phi + alpha delta L. In all applications of a WGM resonator as a modulator, the orbital numbers for the carrier and sidebands are different, and their differences delta L are known (usually, but not necessarily, delta L = 1). Therefore, the choice of the angle alpha, and of the interferometer arms difference, allows one to control the relative phase between different modes and to perform the conversion, separation, and filtering tasks necessary.

An automated cirrus classification

NASA Astrophysics Data System (ADS)

Gryspeerdt, Edward; Quaas, Johannes; Sourdeval, Odran; Goren, Tom

2017-04-01

Cirrus clouds play an important role in determining the radiation budget of the earth, but our understanding of the lifecycle and controls on cirrus clouds remains incomplete. Cirrus clouds can have very different properties and development depending on their environment, particularly during their formation. However, the relevant factors often cannot be distinguished using commonly retrieved satellite data products (such as cloud optical depth). In particular, the initial cloud phase has been identified as an important factor in cloud development, but although back-trajectory based methods can provide information on the initial cloud phase, they are computationally expensive and depend on the cloud parametrisations used in re-analysis products. In this work, a classification system (Identification and Classification of Cirrus, IC-CIR) is introduced. Using re-analysis and satellite data, cirrus clouds are separated in four main types: frontal, convective, orographic and in-situ. The properties of these classes show that this classification is able to provide useful information on the properties and initial phase of cirrus clouds, information that could not be provided by instantaneous satellite retrieved cloud properties alone. This classification is designed to be easily implemented in global climate models, helping to improve future comparisons between observations and models and reducing the uncertainty in cirrus clouds properties, leading to improved cloud parametrisations.

Preparative isolation and purification of four flavonoids from the petals of Nelumbo nucifera by high-speed counter-current chromatography.

PubMed

Xingfeng, Guo; Daijie, Wang; Wenjuan, Duan; Jinhua, Du; Xiao, Wang

2010-01-01

Flavonoids, the primary constituents of the petals of Nelumbo nucifera, are known to have antioxidant properties and antibacterial bioactivities. However, efficient methods for the preparative isolation and purification of flavonoids from this plant are not currently available. To develop an efficient method for the preparative isolation and purification of flavonoids from the petals of N. nucifera by high-speed counter-current chromatography (HSCCC). Following an initial clean-up step on a polyamide column, HSCCC was utilised to separate and purify flavonoids. Purities and identities of the isolated compounds were established by HPLC-PAD, ESI-MS, (1)H-NMR and (13)C-NMR. The separation was performed using a two-phase solvent system composed of ethyl acetate-methanol-water-acetic acid (4 : 1 : 5 : 0.1, by volume), in which the upper phase was used as the stationary phase and the lower phase was used as the mobile phase at a flow-rate of 1.0 mL/min in the head-to-tail elution mode. Ultimately, 5.0 mg syringetin-3-O-beta-d-glucoside, 6.5 mg quercetin-3-O-beta-d-glucoside, 12.8 mg isorhamnetin-3-O-beta-d-glucoside and 32.5 mg kaempferol-3-O-beta-d-glucoside were obtained from 125 mg crude sample. The combination of HSCCC with a polyamide column is an efficient method for the preparative separation and purification of flavonoids from the petals of N. nucifera. (c) 2009 John Wiley & Sons, Ltd.

Silica aerogel coated on metallic wire by phase separation of polystyrene for in-tube solid phase microextraction.

PubMed

Baktash, Mohammad Yahya; Bagheri, Habib

2017-06-02

In this research, an attempt was made toward synthesizing a sol-gel-based silica aerogel and its subsequent coating on a copper wire by phase separation of polystyrene. Adaption of this new approach enabled us to coat the metallic wire with powder materials. The use of this method for coating, led to the formation of a porous and thick structure of silica aerogel. The coated wire was placed in a needle and used as the sorbent for in-tube solid phase microextraction of chlorobenzenes (CBs). The superhydrophobicity of sorbent on extraction efficiency was investigated by using different ratios of tetraethylorthosilicate/methyltrimethoxysilane. The surface coated with the prepared silica aerogel by the phase separation of polystyrene showed high contact angle, approving the desired superhydrophobic properties. Effects of major parameters influencing the extraction efficiency including the extraction temperature, extraction time, ionic strength, desorption time were investigated and optimized. The limits of detection and quantification of the method under the optimized condition were 0.1-1.2 and 0.4-4.1ngL -1 , respectively. The relative standard deviations (RSD%) at a concentration level of 10ngL -1 were between 4 and 10% (n=3). The calibration curves of CBs showed linearity from 1 to100ngL -1 . Eventually, the method was successfully applied to the extraction of model compounds from real water samples and relative recoveries varied from 88 to 115%. Copyright © 2017 Elsevier B.V. All rights reserved.

Ultrafast Dynamics in Vanadium Dioxide: Separating Spatially Segregated Mixed Phase Dynamics in the Time-domain

NASA Astrophysics Data System (ADS)

Hilton, David

2011-10-01

In correlated electronic systems, observed electronic and structural behavior results from the complex interplay between multiple, sometimes competing degrees-of- freedom. One such material used to study insulator-to-metal transitions is vanadium dioxide, which undergoes a phase transition from a monoclinic-insulating phase to a rutile-metallic phase when the sample is heated to 340 K. The major open question with this material is the relative influence of this structural phase transition (Peirels transition) and the effects of electronic correlations (Mott transition) on the observed insulator-to-metal transition. Answers to these major questions are complicated by vanadium dioxide's sensitivity to perturbations in the chemical structure in VO2. For example, related VxOy oxides with nearly a 2:1 ratio do not demonstrate the insulator-to- metal transition, while recent work has demonstrated that W:VO2 has demonstrated a tunable transition temperature controllable with tungsten doping. All of these preexisting results suggest that the observed electronic properties are exquisitely sensitive to the sample disorder. Using ultrafast spectroscopic techniques, it is now possible to impulsively excite this transition and investigate the photoinduced counterpart to this thermal phase transition in a strongly nonequilibrium regime. I will discuss our recent results studying the terahertz-frequency conductivity dynamics of this photoinduced phase transition in the poorly understood near threshold temperature range. We find a dramatic softening of the transition near the critical temperature, which results primarily from the mixed phase coexistence near the transition temperature. To directly study this mixed phase behavior, we directly study the nucleation and growth rates of the metallic phase in the parent insulator using non-degenerate optical pump-probe spectroscopy. These experiments measure, in the time- domain, the coexistent phase separation in VO2 (spatially separated insulator and metal islands) and, more importantly, their dynamic evolution in response to optical excitation.

Ionic liquid stationary phases for gas chromatography.

PubMed

Poole, Colin F; Poole, Salwa K

2011-04-01

This article provides a summary of the development of ionic liquids as stationary phases for gas chromatography beginning with early work on packed columns that established details of the retention mechanism and established working methods to characterize selectivity differences compared with molecular stationary phases through the modern development of multi-centered cation and cross-linked ionic liquids for high-temperature applications in capillary gas chromatography. Since there are many reviews on ionic liquids dealing with all aspects of their chemical and physical properties, the emphasis in this article is placed on the role of gas chromatography played in the design of ionic liquids of low melting point, high thermal stability, high viscosity, and variable selectivity for separations. Ionic liquids provide unprecedented opportunities for extending the selectivity range and temperature-operating range of columns for gas chromatography, an area of separation science that has otherwise been almost stagnant for over a decade. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

EBSD as a tool to identify and quantify bainite and ferrite in low-alloyed Al-TRIP steels.

PubMed

Zaefferer, S; Romano, P; Friedel, F

2008-06-01

Bainite is thought to play an important role for the chemical and mechanical stabilization of metastable austenite in low-alloyed TRIP steels. Therefore, in order to understand and improve the material properties, it is important to locate and quantify the bainitic phase. To this aim, electron backscatter diffraction-based orientation microscopy has been employed. The main difficulty herewith is to distinguish bainitic ferrite from ferrite because both have bcc crystal structure. The most important difference between them is the occurrence of transformation induced geometrically necessary dislocations in the bainitic phase. To determine the areas with larger geometrically necessary dislocation density, the following orientation microscopy maps were explored: pattern quality maps, grain reference orientation deviation maps and kernel average misorientation maps. We show that only the latter allow a reliable separation of the bainitic and ferritic phase. The kernel average misorientation threshold value that separates both constituents is determined by an algorithm that searches for the smoothness of the boundaries between them.

Thermoelectric Properties of Self Assembled TiO2/SnO2 Nanocomposites

NASA Technical Reports Server (NTRS)

Dynys, Fred; Sayir, Ali; Sehirlioglu, Alp

2008-01-01

Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 W/mK2 at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.

Thermoelectric Properties of Self Assemble TiO2/SnO2 Nanocomposites

NASA Technical Reports Server (NTRS)

Dynys, Fred; Sayir, Ali; Sehirlioglu, Alp

2008-01-01

Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 (mu)W/m sq K at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.

Reversed Phase HPLC-DAD Profiling of Carotenoids, Chlorophylls and Phenolic Compounds in Adiantum capillus-veneris Leaves

NASA Astrophysics Data System (ADS)

Zeb, Alam; Ullah, Fareed

2017-04-01

Adiantum capillus-veneris is important endangered fern species with several medicinal properties. In this study, the leaves samples were extracted and separated using reversed phase HPLC with DAD for carotenoids, chlorophylls and phenolic compounds. Separation of carotenoids and chlorophylls were carried out using a tertiary gradient system of water, MTBE and methanol-water, while a binary gradient system of methanol-water-acetic acid was used for phenolic profiling. Results revealed eight carotenoids, four pheophytins and two chlorophylls. Lutein (806.0 µg/g), chlorophyll b' (410.0 µg/g), chlorophyll a (162.4 µg/g), 9'-Z-neoxanthin (142.8 µg/g) and all-E-violaxanthin (82.2 µg/g)) were present in higher amounts. The relatively high amounts of lutein may be one of the key indicator of beneficial antioxidant properties. The phenolic profile revealed a total of thirteen compounds, namely p-hydroxybenzoic acid, chlorogenic acid, caftaric acid, kaempferol glycosides, p-coumaric acid, rosmarinic acid, 5-caffeoylquinic acid, and quercetin glycosides. Kaempferol-3-sophorotrioside (58.7 mg/g), chlorogenic acid (28.5 mg/g), 5-O-caffeoylquinic acid (18.7 mg/g), coumaric acid (11.2 mg/g) and its derivative (33.1 mg/g) were present in high amounts. These results suggest that the reversed phase HPLC profiling of adiantum leaves provides a better understanding in to the actual composition of bioactive compounds, which may be responsible for possible medicinal properties. Adiantum leaves rich in important bioactive phytochemicals can be used as a potential source of nutraceuticals or as a functional food ingredient.

Reversed Phase HPLC-DAD Profiling of Carotenoids, Chlorophylls and Phenolic Compounds in Adiantum capillus-veneris Leaves

PubMed Central

Zeb, Alam; Ullah, Fareed

2017-01-01

Adiantum capillus-veneris is important endangered fern species with several medicinal properties. In this study, the leaves samples were extracted and separated using reversed phase HPLC with DAD for carotenoids, chlorophylls and phenolic compounds. Separation of carotenoids and chlorophylls were carried out using a tertiary gradient system of water, MTBE and methanol-water, while a binary gradient system of methanol-water-acetic acid was used for phenolic profiling. Results revealed eight carotenoids, four pheophytins, and two chlorophylls. Lutein (806.0 μg/g), chlorophyll b′ (410.0 μg/g), chlorophyll a (162.4 μg/g), 9′-Z-neoxanthin (142.8 μg/g) and all-E-violaxanthin (82.2 μg/g) were present in higher amounts. The relatively high amounts of lutein may be one of the key indicator of beneficial antioxidant properties. The phenolic profile revealed a total of 13 compounds, namely 4-hydroxybenzoic acid, chlorogenic acid, caftaric acid, kaempferol glycosides, p-coumaric acid, rosmarinic acid, 5-caffeoylquinic acid, and quercetin glycosides. Kaempferol-3-sophorotrioside (58.7 mg/g), chlorogenic acid (28.5 mg/g), 5-O-caffeoylquinic acid (18.7 mg/g), coumaric acid (11.2 mg/g), and its derivative (33.1 mg/g) were present in high amounts. These results suggest that the reversed phase HPLC profiling of Adiantum leaves provides a better understanding in to the actual composition of bioactive compounds, which may be responsible for the potential medicinal properties. Adiantum leaves rich in important bioactive phytochemicals can be used as a possible source of nutraceuticals or as a functional food ingredient. PMID:28497036

Reversed Phase HPLC-DAD Profiling of Carotenoids, Chlorophylls and Phenolic Compounds in Adiantum capillus-veneris Leaves.

PubMed

Zeb, Alam; Ullah, Fareed

2017-01-01

Adiantum capillus-veneris is important endangered fern species with several medicinal properties. In this study, the leaves samples were extracted and separated using reversed phase HPLC with DAD for carotenoids, chlorophylls and phenolic compounds. Separation of carotenoids and chlorophylls were carried out using a tertiary gradient system of water, MTBE and methanol-water, while a binary gradient system of methanol-water-acetic acid was used for phenolic profiling. Results revealed eight carotenoids, four pheophytins, and two chlorophylls. Lutein (806.0 μg/g), chlorophyll b ' (410.0 μg/g), chlorophyll a (162.4 μg/g), 9'- Z -neoxanthin (142.8 μg/g) and all- E -violaxanthin (82.2 μg/g) were present in higher amounts. The relatively high amounts of lutein may be one of the key indicator of beneficial antioxidant properties. The phenolic profile revealed a total of 13 compounds, namely 4-hydroxybenzoic acid, chlorogenic acid, caftaric acid, kaempferol glycosides, p-coumaric acid, rosmarinic acid, 5-caffeoylquinic acid, and quercetin glycosides. Kaempferol-3-sophorotrioside (58.7 mg/g), chlorogenic acid (28.5 mg/g), 5- O -caffeoylquinic acid (18.7 mg/g), coumaric acid (11.2 mg/g), and its derivative (33.1 mg/g) were present in high amounts. These results suggest that the reversed phase HPLC profiling of Adiantum leaves provides a better understanding in to the actual composition of bioactive compounds, which may be responsible for the potential medicinal properties. Adiantum leaves rich in important bioactive phytochemicals can be used as a possible source of nutraceuticals or as a functional food ingredient.

Polymer blends based on epoxy resin and polyphenylene ether as a matrix material for high-performance composites

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

Venderbosch, R.W.; Nelissen, J.G.L.; Peijs, A.A.J.M.

1993-12-31

The application of poly(2,6-dimethyl-1,4-phenylene ether), PPE, as a matrix material for continuous carbon fiber reinforced composites was studied. PPE is an amorphous thermoplastic exhibiting a high glass transition temperature (220 C) and outstanding mechanical properties with respect to e.g. toughness. However, due to the limited thermal stability at temperatures above T{sub g}, PPE can be regarded as an intractable polymer. Consequently, the introduction of PPE in a composite structure via a melt impregnation route is not feasible. In this investigation a solution impregnation route, using epoxy resin as a reactive solvent, was developed. During impregnation epoxy resin acts as amore » solvent which results in enhanced flow and a reduced processing temperature enabling the preparation of high quality composites, avoiding any degradation. Upon curing of the neat system, phase separation and phase inversion occurs resulting in a continuous PPE matrix filled with glassy epoxy spheres. As a result of this morphology the mechanical and thermal properties of the final material are mainly dominated by the PPE component. In composite applications, a strong influence of the polarity of the carbon fiber surface on the resulting matrix morphology was found. Upon curing, phase separation is initiated at the fiber surface resulting in an epoxy `interlayer` at the fiber surface. This phenomenon can provide a high level of interfacial adhesion. A preliminary investigation of the resulting composite materials revealed outstanding mechanical properties with respect to e.g. interlaminar toughness and strength.« less

77 FR 33733 - Regulation of Fuel and Fuel Additives: Modification to Octamix Waiver (TXCeed)

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-07

... must meet ASTM volatility specifications contained in ASTM D439-85a, as well as phase separation conditions specified in ASTM D-2 Proposal P-176 and Texas Methanol alcohol purity specifications. \\4\\ 53 FR..., TXCeed, met ASTM \\11\\ and NACE \\12\\ corrosion test results, as well as physical property information. \\11...

Bivalent metal-based MIL-53 analogues: Synthesis, properties and application

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

Liu, Yongxin; University of the Chinese Academy of Science, Beijing 100049; Liu, Dan, E-mail: liudan2007@ciac.ac.cn

Trivalent metal-based MIL-53 (Al{sup 3+}, Cr{sup 3+}, Fe{sup 3+}, In{sup 3+}) compounds are interesting metal–organic frameworks (MOFs) with breathing effect and are promising gas sorption materials. Replacing bridging μ{sub 2}-OH group by neutral ligands such as pyridine N-oxide and its derivatives (PNOs), the trivalent metal-based MIL-53 analogous structures could be extended to bivalent metal systems. The introduction of PNOs and bivalent metal elements endows the frameworks with new structural features and physical and chemical properties. This minireview summarizes the recent development of bivalent metal-based MIL-53 analogues (Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}), typically, focusing on the synthetic strategies and potentialmore » applications based on our own works and literatures. We present the synthetic strategy to achieve structures evolution from single-ligand-walled to double-ligand-walled channel. Properties and application of these new materials in a wide range of potential areas are discussed including thermal stability, gas adsorption, magnetism and liquid-phase separation. Promising directions of this research field are also highlighted. - Graphical abstract: The recent development of bivalent metal-based MIL-53 analogues (Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}) on their synthetic strategies, properties and potential applications was reviewed. - Highlights: • Structure features of bivalent metal-based MIL-53 analogues are illustrated. • Important properties and application are presented. • Host–guest interactions are main impetus for liquid-phase separation. • Promising directions of bivalent metal-based MIL-53 analogues are highlighted.« less

Separation of very hydrophobic analytes by micellar electrokinetic chromatography IV. Modeling of the effective electrophoretic mobility from carbon number equivalents and octanol-water partition coefficients.

PubMed

Huhn, Carolin; Pyell, Ute

2008-07-11

It is investigated whether those relationships derived within an optimization scheme developed previously to optimize separations in micellar electrokinetic chromatography can be used to model effective electrophoretic mobilities of analytes strongly differing in their properties (polarity and type of interaction with the pseudostationary phase). The modeling is based on two parameter sets: (i) carbon number equivalents or octanol-water partition coefficients as analyte descriptors and (ii) four coefficients describing properties of the separation electrolyte (based on retention data for a homologous series of alkyl phenyl ketones used as reference analytes). The applicability of the proposed model is validated comparing experimental and calculated effective electrophoretic mobilities. The results demonstrate that the model can effectively be used to predict effective electrophoretic mobilities of neutral analytes from the determined carbon number equivalents or from octanol-water partition coefficients provided that the solvation parameters of the analytes of interest are similar to those of the reference analytes.

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.

Microstructure and High Temperature Mechanical Property of Fe-Cr-B Based Metal/Ceramic Composite Manufactured by Metal Injection Molding Process

NASA Astrophysics Data System (ADS)

Lee, Kee-Ahn; Gwon, Jin-Han; Yoon, Tae-Sik

2018-03-01

This study investigated the microstructure and the room and high temperature mechanical properties of Fe-Cr-B alloy manufactured by metal injection molding. In addition, hot isostatic pressing was performed to increase the density of the material, and a comparison of properties was made. Microstructural observation confirmed a bi-continuous structure composed of a three-dimensional network of α-Fe phase and (Cr,Fe)2B phase. The HIPed specimen featured a well-formed adhesion between the α-Fe phase and boride, and the number of fine pores was significantly reduced. The tensile results confirmed that the HIPed specimen (RT to 900 °C) had higher strengths compared to the as-sintered specimen, and the change of elongation starting from 700 °C was significantly greater in the HIPed specimen. Fractography suggested that cracks propagated mostly along the interface between the α-Fe matrix and boride in the as-sintered specimen, while direct fracture of boride was observed in addition to interface separation in the HIPed specimen.

Separation of betacyanins from purple flowers of Gomphrena globosa L. by ion-pair high-speed counter-current chromatography.

PubMed

Spórna-Kucab, Aneta; Jagodzińska, Joanna; Wybraniec, Sławomir

2017-03-17

Betacyanins, known as antioxidants and chemopreventive natural compounds with colourful properties, were extracted from purple flowers of Gomphrena globosa L. belonging to the Amaranthaceae family and separated for the first time by ion-pair high-speed counter-current chromatography (HSCCC). The pigments were detected by LC-DAD-ESI-MS/MS technique. Separation of betacyanins (300mg) by HSCCC was accomplished in four solvent systems: tert-butyl methyl ether - butanol - acetonitrile - water (0.7% and 1.0% HFBA - heptafluorobutyric acid - system I and III) and tert-butyl methyl ether - butanol - methanol - water (0.7% and 1.0% HFBA - system II and IV) (2:2:1:5, v/v/v/v) in the head-to-tail mode. The mobile phase (aqueous phase) was run at 2.0ml/min and the column rotation speed was 860rpm. The applied systems enabled to study the influence of HFBA concentration as well as systems polarity on betacyanins separation. Comparison of the systems containing 0.7% HFBA (systems I-II) demonstrates that the replacement of acetonitrile by methanol increases the resolution (R s ) between all betacyanins and does not influence the retention of the stationary phase (S f =76%). Higher concentration of the acid in systems III-IV slightly decreases S f to 71% in the systems with 1.0% HFBA. Comparison of the resolution values for betacyanins in the systems with 0.7% and 1.0% HFBA demonstrates that higher concentration of the acid improves the separation effectiveness for all betacyanins as a result of increasing of the chemical affinity of the pigments to the organic stationary phase in HSCCC. The systems III-IV with 1% HFBA are the most effective for the separation of all the studied betacyanins. Copyright © 2017 Elsevier B.V. All rights reserved.

On-Chip Microfluidic Components for In Situ Analysis, Separation, and Detection of Amino Acids

NASA Technical Reports Server (NTRS)

Zheng, Yun; Getty, Stephanie; Dworkin, Jason; Balvin, Manuel; Kotecki, Carl

2013-01-01

The Astrobiology Analytical Laboratory at GSFC has identified amino acids in meteorites and returned cometary samples by using liquid chromatography-electrospray ionization time-of-flight mass spectrometry (LCMS). These organic species are key markers for life, having the property of chirality that can be used to distinguish biological from non-biological amino acids. One of the critical components in the benchtop instrument is liquid chromatography (LC) analytical column. The commercial LC analytical column is an over- 250-mm-long and 4.6-mm-diameter stainless steel tube filled with functionized microbeads as stationary phase to separate the molecular species based on their chemistry. Miniaturization of this technique for spaceflight is compelling for future payloads for landed missions targeting astrobiology objectives. A commercial liquid chromatography analytical column consists of an inert cylindrical tube filled with a stationary phase, i.e., microbeads, that has been functionalized with a targeted chemistry. When analyte is sent through the column by a pressurized carrier fluid (typically a methanol/ water mixture), compounds are separated in time due to differences in chemical interactions with the stationary phase. Different species of analyte molecules will interact more strongly with the column chemistry, and will therefore take longer to traverse the column. In this way, the column will separate molecular species based on their chemistry. A lab-on-chip liquid analysis tool was developed. The microfluidic analytical column is capable of chromatographically separating biologically relevant classes of molecules based on their chemistry. For this analytical column, fabrication, low leak rate, and stationary phase incorporation of a serpentine microchannel were demonstrated that mimic the dimensions of a commercial LC column within a 5 10 1 mm chip. The microchannel in the chip has a 75- micrometer-diameter oval-shaped cross section. The serpentine microchannel has four different lengths: 40, 60, 80, and 100 mm. Functionized microbeads were filled inside the microchannel to separate molecular species based on their chemistry.

Achievement of high coercivity in sintered R-Fe-B magnets based on misch-metal by dual alloy method

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

Niu, E, E-mail: niue@aphy.iphy.ac.cn; Wang, Zhen-Xi; Beijing Zhong Ke San Huan Research, No.10 Chuangxin Road, Changping District, Beijing 102200

2014-03-21

The R-Fe-B (R, rare earth) sintered magnets prepared with different ratio of alloys of MM-Fe-B (MM, misch-metal) and Nd-Fe-B by dual alloy method were investigated. As expected, the high ratio of MM-Fe-B alloy degrades the hard magnetic properties heavily with intrinsic coercivity lower than 5 kOe. When the atomic ratio MM/R ≤ 21.5% the magnetic properties can reach a practical level of B{sub r} ≥ 12.1 kGs, H{sub cj} ≥ 10.7 kOe, and (BH){sub max} ≥ 34.0 MGOe. And the effect of H{sub cj} enhancement by the grain boundary diffusion process is obvious when MM/R ≤ 21.5%. It is revealed that the decrement of intrinsic magnetic properties of R{sub 2}Fe{submore » 14}B matrix phase is not the main reason of the degradation of the magnets with high MM ratio. The change of deteriorated microstructure together with phase component plays fundamental roles in low H{sub cj}. In high MM ratio magnets, (a) after annealing, Ce atoms inside main phase are inclined to be segregated in the outer layer of the main phase grains; (b) there is no thin layer of Ce-rich phase as an analogue of Nd-rich phase to separate main phase grains; (c) excessive Ce tends to form CeFe{sub 2} grains.« less

Rare earth separations by selective borate crystallization

PubMed Central

Yin, Xuemiao; Wang, Yaxing; Bai, Xiaojing; Wang, Yumin; Chen, Lanhua; Xiao, Chengliang; Diwu, Juan; Du, Shiyu; Chai, Zhifang; Albrecht-Schmitt, Thomas E.; Wang, Shuao

2017-01-01

Lanthanides possess similar chemical properties rendering their separation from one another a challenge of fundamental chemical and global importance given their incorporation into many advanced technologies. New separation strategies combining green chemistry with low cost and high efficiency remain highly desirable. We demonstrate that the subtle bonding differences among trivalent lanthanides can be amplified during the crystallization of borates, providing chemical recognition of specific lanthanides that originates from Ln3+ coordination alterations, borate polymerization diversity and soft ligand coordination selectivity. Six distinct phases are obtained under identical reaction conditions across lanthanide series, further leading to an efficient and cost-effective separation strategy via selective crystallization. As proof of concept, Nd/Sm and Nd/Dy are used as binary models to demonstrate solid/aqueous and solid/solid separation processes. Controlling the reaction kinetics gives rise to enhanced separation efficiency of Nd/Sm system and a one-step quantitative separation of Nd/Dy with the aid of selective density-based flotation. PMID:28290448

Fluids Density Functional Theory of Salt-Doped Block Copolymers

NASA Astrophysics Data System (ADS)

Brown, Jonathan R.; Hall, Lisa M.

Block copolymers have attracted a great deal of recent interest as potential non-flammable, solid-state, electrolyte materials for batteries or other charge carrying applications. The microphase separation in block copolymers combines the properties of a conductive (though mechanically soft) polymer with a mechanically robust (though non-conductive) polymer. We use fluids density functional theory (fDFT) to study the phase behavior of salt-doped block copolymers. Because the salt prefers to preferentially solvate into the conductive phase, salt doping effectively enhances the segregation strength between the two polymer types. We consider the effects of this preferential solvation and of charge correlations by separately modeling the ion-rich phase, without bonding, using the Ornstein-Zernike equation and the hypernetted-chain closure. We use the correlations from this subsystem in the inhomogeneous fDFT calculations. Initial addition of salt increases the domain spacing and sharpens the interfacial region, but for high salt loadings the interface can broaden. Addition of salt can also drive a system with a low copolymer segregation strength to order by first passing through a two phase regime with a salt-rich ordered phase and a salt-poor disordered phase. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0014209.

Aqueous two-phase partition applied to the isolation of plasma membranes and Golgi apparatus from cultured mammalian cells.

PubMed

Morré, D M; Morre, D J

2000-06-23

Partitioning in dextran-poly(ethylene)glycol (PEG) aqueous-aqueous phase systems represents a mature technology with many applications to separations of cells and to the preparation of membranes from mammalian cells. Most applications to membrane isolation and purification have focused on plasma membranes, plasma membrane domains and separation of right side-out and inside-out plasma membrane vesicles. The method exploits a combination of membrane properties, including charge and hydrophobicity. Purification is based upon differential distributions of the constituents in a sample between the two principal compartments of the two phases (upper and lower) and at the interface. The order of affinity of animal cell membranes for the upper phase is: endoplasmic reticulum

Effects of Frequency Separation and Diotic/Dichotic Presentations on the Alternation Frequency Limits in Audition Derived from a Temporal Phase Discrimination Task.

PubMed

Kanaya, Shoko; Fujisaki, Waka; Nishida, Shin'ya; Furukawa, Shigeto; Yokosawa, Kazuhiko

2015-02-01

Temporal phase discrimination is a useful psychophysical task to evaluate how sensory signals, synchronously detected in parallel, are perceptually bound by human observers. In this task two stimulus sequences synchronously alternate between two states (say, A-B-A-B and X-Y-X-Y) in either of two temporal phases (ie A and B are respectively paired with X and Y, or vice versa). The critical alternation frequency beyond which participants cannot discriminate the temporal phase is measured as an index characterizing the temporal property of the underlying binding process. This task has been used to reveal the mechanisms underlying visual and cross-modal bindings. To directly compare these binding mechanisms with those in another modality, this study used the temporal phase discrimination task to reveal the processes underlying auditory bindings. The two sequences were alternations between two pitches. We manipulated the distance between the two sequences by changing intersequence frequency separation, or presentation ears (diotic vs dichotic). Results showed that the alternation frequency limit ranged from 7 to 30 Hz, becoming higher as the intersequence distance decreased, as is the case with vision. However, unlike vision, auditory phase discrimination limits were higher and more variable across participants. © 2015 SAGE Publications.

Aqueous two-phase partition applied to the isolation of plasma membranes and Golgi apparatus from cultured mammalian cells

NASA Technical Reports Server (NTRS)

Morre, D. M.; Morre, D. J.

2000-01-01

Partitioning in dextran-poly(ethylene)glycol (PEG) aqueous-aqueous phase systems represents a mature technology with many applications to separations of cells and to the preparation of membranes from mammalian cells. Most applications to membrane isolation and purification have focused on plasma membranes, plasma membrane domains and separation of right side-out and inside-out plasma membrane vesicles. The method exploits a combination of membrane properties, including charge and hydrophobicity. Purification is based upon differential distributions of the constituents in a sample between the two principal compartments of the two phases (upper and lower) and at the interface. The order of affinity of animal cell membranes for the upper phase is: endoplasmic reticulum

A novel mechanical model for phase-separation in debris flows

NASA Astrophysics Data System (ADS)

Pudasaini, Shiva P.

2015-04-01

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

Lattice Supersymmetry and Order-Disorder Coexistence in the Tricritical Ising Model

NASA Astrophysics Data System (ADS)

O'Brien, Edward; Fendley, Paul

2018-05-01

We introduce and analyze a quantum spin or Majorana chain with a tricritical Ising point separating a critical phase from a gapped phase with order-disorder coexistence. We show that supersymmetry is not only an emergent property of the scaling limit but also manifests itself on the lattice. Namely, we find explicit lattice expressions for the supersymmetry generators and currents. Writing the Hamiltonian in terms of these generators allows us to find the ground states exactly at a frustration-free coupling. These confirm the coexistence between two (topologically) ordered ground states and a disordered one in the gapped phase. Deforming the model by including explicit chiral symmetry breaking, we find the phases persist up to an unusual chiral phase transition where the supersymmetry becomes exact even on the lattice.

Managing Zirconium Chemistry and Phase Compatibility in Combined Process Separations for Minor Actinide Partitioning

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

Wall, Nathalie; Nash, Ken; Martin, Leigh

In response to the NEUP Program Supporting Fuel Cycle R&D Separations and Waste Forms call DEFOA- 0000799, this report describes the results of an R&D project focusing on streamlining separation processes for advanced fuel cycles. An example of such a process relevant to the U.S. DOE FCR&D program would be one combining the functions of the TRUEX process for partitioning of lanthanides and minor actinides from PUREX(UREX) raffinates with that of the TALSPEAK process for separating transplutonium actinides from fission product lanthanides. A fully-developed PUREX(UREX)/TRUEX/TALSPEAK suite would generate actinides as product(s) for reuse (or transmutation) and fission products as waste.more » As standalone, consecutive unit-operations, TRUEX and TALSPEAK employ different extractant solutions (solvating (CMPO, octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide) vs. cation exchanging (HDEHP, di-2(ethyl)hexylphosphoric acid) extractants), and distinct aqueous phases (2-4 M HNO 3 vs. concentrated pH 3.5 carboxylic acid buffers containing actinide selective chelating agents). The separate processes may also operate with different phase transfer kinetic constraints. Experience teaches (and it has been demonstrated at the lab scale) that, with proper control, multiple process separation systems can operate successfully. However, it is also recognized that considerable economies of scale could be achieved if multiple operations could be merged into a single process based on a combined extractant solvent. The task of accountability of nuclear materials through the process(es) also becomes more robust with fewer steps, providing that the processes can be accurately modeled. Work is underway in the U.S. and Europe on developing several new options for combined processes (TRUSPEAK, ALSEP, SANEX, GANEX, ExAm are examples). There are unique challenges associated with the operation of such processes, some relating to organic phase chemistry, others arising from the variable composition of the aqueous medium. This project targets in particular two problematic issues in designing combined process systems: managing the chemistry of challenging aqueous species (like Zr 4+) and optimizing the composition and properties of combined extractant organic phases.« less

Spatial mapping of electronic states in κ-(BEDT-TTF)2X using infrared reflectivity

PubMed Central

Sasaki, Takahiko; Yoneyama, Naoki

2009-01-01

We review our recent work on spatial inhomogeneity of the electronic states in the strongly correlated molecular conductors κ-(BEDT-TTF)2X. Spatial mapping of infrared spectra (SMIS) is used for imaging the distribution of the local electronic states. In molecular materials, the infrared response of the specific molecular vibration mode with a strong electron–molecular vibration coupling can reflect the electronic states via the change in the vibration frequency. By spatially mapping the frequency shift of the molecular vibration mode, an electronic phase separation has been visualized near the first-order Mott transition in the bandwidth-controlled organic conductor κ-(BEDT-TTF)2Cu[N(CN)2]Br. In addition to reviewing SMIS of the phase separation, we briefly mention the electronic and optical properties of κ-(BEDT-TTF)2X. PMID:27877279

Multiple fuel supply system for an internal combustion engine

DOEpatents

Crothers, William T.

1977-01-01

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

Numerical studies of the topological Chern numbers in two dimensional electron system

NASA Astrophysics Data System (ADS)

Sheng, Donna

2004-03-01

I will report on the numerical results of the exact calculation of the topological Chern numbers in fractional and bilayer quantum Hall systems[1]. I will show that following the evolution of the Chern numbers as a function of the disorder strength and/or layer separations, various quantum phase transitions as well as the characteristic transport properties of the phases, can be determined. The hidden topological ordering in other two dimensional electron systems will also be discussed. 1. D. N. Sheng et. al., Phys. Rev. Lett. 90, 256802 (2003).

Preparation and characterization of PVDF separators for lithium ion cells using hydroxyl-terminated polybutadiene grafted methoxyl polyethylene glycol (HTPB-g-MPEG) as additive

NASA Astrophysics Data System (ADS)

Li, Hao; Niu, Dong-Hui; Zhou, Hui; Chao, Chun-Ying; Wu, Li-Jun; Han, Pei-Lin

2018-05-01

Hydroxyl-terminated polybutadiene grafted methoxyl polyethylene glycol (HTPB-g-MPEG) with different arm length were synthesized by grafting methoxyl poly(ethylene glycol)s (MPEGs, Mn = 350, 750, 1900 and 5000, respectively) to the hydroxyl-terminated polybutadiene (HTPB) molecule using isophorone diisocyanate (IPDI) as the coupling agent, and blended with PVDF to fabricate porous separators via phase inversion process. By measuring the composition, morphology and ion conductivity etc., the influence of HTPB-g-MPEG on structure and property of blend separators were discussed. Compared with pure PVDF separator with comparable porous structure, the adoption of HTPB-g-MPEG could not only decrease the crystallinity, but also enhance the stability of entrapped liquid electrolyte and corresponding ion conductivity. The cells assembled with such separators showed good initial discharge capacity and cyclic stability.

Effects of organoclay to miscibility, mechanical and thermal properties of poly(lactic acid) and propylene-ethylene copolymer blends

NASA Astrophysics Data System (ADS)

Wacharawichanant, S.; Ounyai, C.; Rassamee, P.

2017-07-01

The effects of propylene-ethylene copolymer (PEC or PEC3300) and clay surface modified with 25-30 wt% of trimethylstearyl ammonium (Clay-TSA) on morphology, thermal and mechanical properties of poly(lactic acid) (PLA) were investigated. The morphology analysis showed PLA/PEC3300 blends clearly demonstrated a two-phase separation of dispersed phase and the matrix phase and the addition of Clay-TSA could improve the miscibility of PLA and PEC3300 blends due to the decreased of the domain sizes of dispersed PEC3300 phase in the polymer matrix. From X-ray diffraction analysis showed the intercalation of PLA chains inside the Clay-TSA and this result implied that Clay-TSA platelets acted as an effective compatibilizer. The tensile properties showed the strain at break of PLA was improved after adding PEC3300 while Young’s modulus, tensile strength and storage modulus decreased. The addition of Clay-TSA could improve Young’s modulus of PLA/PEC3300 blends. The addition of Clay-TSA 7 phr showed the maximum of Young’s modulus of PLA/PEC3300/Clay-TSA composites. The thermal properties found that the addition of PEC3300 and Clay-TSA did not change significantly on the glass transition temperature and melting point temperature of PLA. The percent of crystallinity of PLA decreased with increasing PEC content. The thermal stability of PLA improved after adding PEC3300.

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

DOEpatents

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

2012-07-17

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

Critical behavior of a quantum chain with four-spin interactions in the presence of longitudinal and transverse magnetic fields.

PubMed

Boechat, B; Florencio, J; Saguia, A; de Alcantara Bonfim, O F

2014-03-01

We study the ground-state properties of a spin-1/2 model on a chain containing four-spin Ising-like interactions in the presence of both transverse and longitudinal magnetic fields. We use entanglement entropy and finite-size scaling methods to obtain the phase diagrams of the model. Our numerical calculations reveal a rich variety of phases and the existence of multicritical points in the system. We identify phases with both ferromagnetic and antiferromagnetic orderings. We also find periodically modulated orderings formed by a cluster of like spins followed by another cluster of opposite like spins. The quantum phases in the model are found to be separated by either first- or second-order transition lines.

Structural metatransition of energetically tangled crystalline phases.

PubMed

Zhou, Dan; Li, Quan; Zheng, Weitao; Ma, Yanming; Chen, Changfeng

2017-02-08

We solve the longstanding puzzle of pressure induced structural evolution of SnSe using a swarm structure search method combined with first-principles phonon and kinetic barrier calculations. Our results identify a dynamic set of nearly degenerate crystalline SnSe phases that are separated by low kinetic barriers and undergo an unusual type of structural transitions characterized by a dynamically changing mix of the constituent phases. We introduce a new concept of structural metatransition to highlight the transitional nature of such phase transitions. Our theoretical prediction is corroborated by X-ray diffraction measurements, and this intriguing phenomenon offers insights into the enigmatic property variations of SnSe under pressure. This work raises prospects of considerably improving characterization and understanding of intrinsic multiphase crystals and their dynamic evolution.

Chiral HPLC for a study of the optical purity of new liquid crystalline materials derived from lactic acid

NASA Astrophysics Data System (ADS)

Vojtylová, T.; Kašpar, M.; Hamplová, V.; Novotná, V.; Sýkora, D.

2014-08-01

New liquid crystalline (LC) materials were prepared by derivatization of lactic acid. First compound possesses the lactic acid unit as the only chiral center and the second group of LC materials contains two chiral centers. Mesomorphic properties of both the newly synthesized LC materials were studied and the presence of the SmA*-SmC* or exhibit the twist grain boundary (TGB) phases, namely TGBA and TGBC, in a wide range of temperatures down to the room temperature was established. The potential of high-performance liquid chromatography (HPLC) applying chiral stationary phases to separate enantiomers or diastereoisomers of the synthesized LC compounds was evaluated. Two different brands of commercial chiral sorbents, Lux Amylose-2 and Chiralpak AD-3, both based on modified silica with derivatized polysaccharide, were employed in the development of separation procedures. The optimized chiral HPLC method provided a baseline separation of the individual enantiomers for the LC material containing one chiral center. In the case of the more complex compound with two asymmetric carbon atoms, where four isomers exist, partial separation was reached only using the current chiral HPLC.

[Characteristics of electroosmotic flow in open-tubular capillary electrochromatography with magnetic nanoparticle coating as mixed-mode stationary phase].

PubMed

Qin, Sasa; Zhou, Chaoran; Zhu, Yaxian; Ren, Zhiyu; Zhang, Lingyi; Fu, Honggang; Zhang, Weibing

2011-09-01

A novel open-tubular capillary electrochromatography (OT-CEC) column with magnetic nanoparticle coating as mixed-mode stationary phase was prepared. The mixed-mode stationary phases were obtained by mixing C18 and amino modified magnetic nanoparticles with different ratios. The mixed modified magnetic nanoparticles as stationary phase were introduced into the capillary by using external magnetic force. The magnetic nanoparticle coating can be easily regenerated by removing the external magnetic field, and applied to other separation modes. The characteristics of electroosmotic flow (EOF) were theoretically investigated through the effect of physicochemical properties of different stationary phases on EOF. The experiment was conducted under different ratios of mixed-mode stationary phases and coating lengths, and it was verified that the theoretical conclusions accorded with the experimental results. It was shown that the EOF can be easily adjusted by changing the ratio of stationary phases or the number of permanent magnets.

Microfluidic and nanofluidic phase behaviour characterization for industrial CO2, oil and gas.

PubMed

Bao, Bo; Riordon, Jason; Mostowfi, Farshid; Sinton, David

2017-08-08

Microfluidic systems that leverage unique micro-scale phenomena have been developed to provide rapid, accurate and robust analysis, predominantly for biomedical applications. These attributes, in addition to the ability to access high temperatures and pressures, have motivated recent expanded applications in phase measurements relevant to industrial CO 2 , oil and gas applications. We here present a comprehensive review of this exciting new field, separating microfluidic and nanofluidic approaches. Microfluidics is practical, and provides similar phase properties analysis to established bulk methods with advantages in speed, control and sample size. Nanofluidic phase behaviour can deviate from bulk measurements, which is of particular relevance to emerging unconventional oil and gas production from nanoporous shale. In short, microfluidics offers a practical, compelling replacement of current bulk phase measurement systems, whereas nanofluidics is not practical, but uniquely provides insight into phase change phenomena at nanoscales. Challenges, trends and opportunities for phase measurements at both scales are highlighted.

Method for separating disparate components in a fluid stream

DOEpatents

Meikrantz, David H.

1990-01-01

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

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.

Preparation of a silica stationary phase co-functionalized with Wulff-type phenylboronate and C12 for mixed-mode liquid chromatography.

PubMed

Li, Hengye; Zhang, Xuemeng; Zhang, Lin; Wang, Xiaojin; Kong, Fenying; Fan, Dahe; Li, Lei; Wang, Wei

2017-04-15

A silica stationary phase was designed and synthesized through the co-functionalization of silica with Wulff-type phenylboronate and C12 for mixed-mode liquid chromatography applications. The as-synthesized stationary phase was characterized by elemental analysis and Fourier Transform-InfraRed Spectroscopy (FT-IR). Retention mechanisms, including boronate affinity (BA), reversed-phase (RP) and anion-exchange (AE), were involved. Retention mechanism switching was easily realized by adjustment of the mobile phase constitution. Cis-diol compounds could be selectively captured under neutral conditions in BA mode and off-line separated in RP mode. Neutral, basic, acidic and amphiprotic compounds were chromatographed on the column in RP chromatography, while inorganic anions were chromatographed in AE chromatography to characterize the mixed-mode nature of the prepared stationary phase. In addition, the RP performance was compared with an octadecyl silica column in terms of column efficiency (N/m), asymmetry factor (A f ), retention factor (k) and resolution (Rs). The prepared stationary phase offered multiple interactions with analytes in addition to hydrophobic interactions under RP elution conditions. Based on the mixed-mode properties, off-line 2D-LC, for selective capture and separation of urinary nucleosides, was successfully realized on a single column, demonstrating its powerful application potential for complex samples. Copyright © 2017 Elsevier B.V. All rights reserved.

THE ROLE OF METASTABLE STATES IN POLYMER PHASE TRANSITIONS: Concepts, Principles, and Experimental Observations

NASA Astrophysics Data System (ADS)

Cheng, Stephen Z. D.; Keller, Andrew

1998-08-01

Polymer phases can be described in the same way as phases in other condensed matter using a number density operator and its correlation functions. This description requires the understanding of symmetry operations and order at different atomic and molecular levels. Statistical mechanics provides a link between the microscopic description of the structure and motion and the macroscopic thermodynamic properties. Within the limits of the laws of thermodynamics, polymers exhibit a rich variety of phase transition behaviors. By definition, a first-order phase transition describes a transformation that involves a sudden change of thermodynamic properties at its transition temperature, whereas higher-order phase transitions are classified as critical phenomena. Of special interest is the role of metastability in phase and phase transition behaviors. Although a metastable state possesses a local free energy minimum, it is not at the global equilibrium. Furthermore, metastable states can also be associated with phase sizes. Metastable behavior is also observed in phase transformations that are impeded by kinetic limitations along the pathway to thermodynamic equilibrium. This is illustrated in structural and morphological investigations of crystallization and mesophase transitions, liquid-liquid phase separation, vitrification, and gel formation, as well as combinations of transformation processes. In these cases, the metastable state often becomes the dominant state for the entire system and is observed over a range of time and size scales. This review describes the general principles of metastability in polymer phases and phase transitions and provides illustrations from current experimental works in selected areas.

Simultaneous Control of Multispecies Particle Transport and Segregation in Driven Lattices

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Aritra K.; Liebchen, Benno; Schmelcher, Peter

2018-05-01

We provide a generic scheme to separate the particles of a mixture by their physical properties like mass, friction, or size. The scheme employs a periodically shaken two-dimensional dissipative lattice and hinges on a simultaneous transport of particles in species-specific directions. This selective transport is achieved by controlling the late-time nonlinear particle dynamics, via the attractors embedded in the phase space and their bifurcations. To illustrate the spectrum of possible applications of the scheme, we exemplarily demonstrate the separation of polydisperse colloids and mixtures of cold thermal alkali atoms in optical lattices.

Glass science tutorial: Lecture No. 7, Waste glass technology for Hanford

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

Kruger, A.A.

1995-07-01

This paper presents the details of the waste glass tutorial session that was held to promote knowledge of waste glass technology and how this can be used at the Hanford Reservation. Topics discussed include: glass properties; statistical approach to glass development; processing properties of nuclear waste glass; glass composition and the effects of composition on durability; model comparisons of free energy of hydration; LLW glass structure; glass crystallization; amorphous phase separation; corrosion of refractories and electrodes in waste glass melters; and glass formulation for maximum waste loading.

On S-mixing entropy of quantum channels

NASA Astrophysics Data System (ADS)

Mukhamedov, Farrukh; Watanabe, Noboru

2018-06-01

In this paper, an S-mixing entropy of quantum channels is introduced as a generalization of Ohya's S-mixing entropy. We investigate several properties of the introduced entropy. Moreover, certain relations between the S-mixing entropy and the existing map and output entropies of quantum channels are investigated as well. These relations allowed us to find certain connections between separable states and the introduced entropy. Hence, there is a sufficient condition to detect entangled states. Moreover, several properties of the introduced entropy are investigated. Besides, entropies of qubit and phase-damping channels are calculated.

Nanoparticle Analysis by Online Comprehensive Two-Dimensional Liquid Chromatography combining Hydrodynamic Chromatography and Size-Exclusion Chromatography with Intermediate Sample Transformation

PubMed Central

2017-01-01

Polymeric nanoparticles have become indispensable in modern society with a wide array of applications ranging from waterborne coatings to drug-carrier-delivery systems. While a large range of techniques exist to determine a multitude of properties of these particles, relating physicochemical properties of the particle to the chemical structure of the intrinsic polymers is still challenging. A novel, highly orthogonal separation system based on comprehensive two-dimensional liquid chromatography (LC × LC) has been developed. The system combines hydrodynamic chromatography (HDC) in the first-dimension to separate the particles based on their size, with ultrahigh-performance size-exclusion chromatography (SEC) in the second dimension to separate the constituting polymer molecules according to their hydrodynamic radius for each of 80 to 100 separated fractions. A chip-based mixer is incorporated to transform the sample by dissolving the separated nanoparticles from the first-dimension online in tetrahydrofuran. The polymer bands are then focused using stationary-phase-assisted modulation to enhance sensitivity, and the water from the first-dimension eluent is largely eliminated to allow interaction-free SEC. Using the developed system, the combined two-dimensional distribution of the particle-size and the molecular-size of a mixture of various polystyrene (PS) and polyacrylate (PACR) nanoparticles has been obtained within 60 min. PMID:28745485

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation.

PubMed

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-08-30

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3,5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. Copyright © 2013 Elsevier B.V. All rights reserved.

Surface and Bulk Phase Separations in Block Copolymers and Their Blends.

DTIC Science & Technology

1984-03-01

research effort in _. the biomedical area to study polymeric surfaces which may be applied where biocompatibility (particularly, blood compatibilty) is...elasticity(thermoplastic) and good biocompatibility . Two such commercially available polyurethanes-, Avcothane and Biomer, have been used in this...the biocompatible properties depended considerably on the rate of evaporation of solvent during the film preparation. ATR-IR spectroscopy showed that

Solubilization of lipids and lipid phases by the styrene-maleic acid copolymer.

PubMed

Dominguez Pardo, Juan J; Dörr, Jonas M; Iyer, Aditya; Cox, Ruud C; Scheidelaar, Stefan; Koorengevel, Martijn C; Subramaniam, Vinod; Killian, J Antoinette

2017-01-01

A promising tool in membrane research is the use of the styrene-maleic acid (SMA) copolymer to solubilize membranes in the form of nanodiscs. Since membranes are heterogeneous in composition, it is important to know whether SMA thereby has a preference for solubilization of either specific types of lipids or specific bilayer phases. Here, we investigated this by performing partial solubilization of model membranes and analyzing the lipid composition of the solubilized fraction. We found that SMA displays no significant lipid preference in homogeneous binary lipid mixtures in the fluid phase, even when using lipids that by themselves show very different solubilization kinetics. By contrast, in heterogeneous phase-separated bilayers, SMA was found to have a strong preference for solubilization of lipids in the fluid phase as compared to those in either a gel phase or a liquid-ordered phase. Together the results suggest that (1) SMA is a reliable tool to characterize native interactions between membrane constituents, (2) any solubilization preference of SMA is not due to properties of individual lipids but rather due to properties of the membrane or membrane domains in which these lipids reside and (3) exploiting SMA resistance rather than detergent resistance may be an attractive approach for the isolation of ordered domains from biological membranes.

Physical stability of R-(+)-Limonene emulsions stabilized by Ulva fasciata algae polysaccharide.

PubMed

Shao, Ping; Ma, Huiling; Qiu, Qiang; Jing, Weiping

2016-11-01

The physical stability of R-(+)-Limonene emulsions stabilized by Ulva fasciata polysaccharide (UFP) was investigated in this study. Emulsion physical stability was evaluated under different polysaccharide concentrations (1%-5%, wt/wt) and pH values (3.0-11.0). The stability of R-(+)-Limonene emulsions was demonstrated by droplet size distribution, rheological properties, zeta potential and visual phase separation. R-(+)-Limonene emulsions displayed monomodal droplet size distributions, high absolute values of zeta potential and good storage stability when 3% (wt/wt) UFP was used. The rheological properties and stability of R-(+)-Limonene emulsions appeared to be dependent on polysaccharide concentration. The emulsion stability was impacted by pH. Higher zeta potential (-52.6mV) and smaller mean droplet diameter (2.45μm) were achieved in neutral liquid environment (pH 7.0). Extreme acidity caused the flocculation of emulsions, which was manifested as phase separation, while emulsions were quite stable in an alkaline environment. Through comparing the stabilities of emulsions stabilized by different emulsifiers (i.e. UFP, GA and Gelatin), the result suggested that UFP was the best emulsifying agent among them. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface Nanostructures Formed by Phase Separation of Metal Salt-Polymer Nanocomposite Film for Anti-reflection and Super-hydrophobic Applications

NASA Astrophysics Data System (ADS)

Con, Celal; Cui, Bo

2017-12-01

This paper describes a simple and low-cost fabrication method for multi-functional nanostructures with outstanding anti-reflective and super-hydrophobic properties. Our method employed phase separation of a metal salt-polymer nanocomposite film that leads to nanoisland formation after etching away the polymer matrix, and the metal salt island can then be utilized as a hard mask for dry etching the substrate or sublayer. Compared to many other methods for patterning metallic hard mask structures, such as the popular lift-off method, our approach involves only spin coating and thermal annealing, thus is more cost-efficient. Metal salts including aluminum nitrate nonahydrate (ANN) and chromium nitrate nonahydrate (CNN) can both be used, and high aspect ratio (1:30) and high-resolution (sub-50 nm) pillars etched into silicon can be achieved readily. With further control of the etching profile by adjusting the dry etching parameters, cone-like silicon structure with reflectivity in the visible region down to a remarkably low value of 2% was achieved. Lastly, by coating a hydrophobic surfactant layer, the pillar array demonstrated a super-hydrophobic property with an exceptionally high water contact angle of up to 165.7°.

Surface Nanostructures Formed by Phase Separation of Metal Salt-Polymer Nanocomposite Film for Anti-reflection and Super-hydrophobic Applications.

PubMed

Con, Celal; Cui, Bo

2017-12-16

This paper describes a simple and low-cost fabrication method for multi-functional nanostructures with outstanding anti-reflective and super-hydrophobic properties. Our method employed phase separation of a metal salt-polymer nanocomposite film that leads to nanoisland formation after etching away the polymer matrix, and the metal salt island can then be utilized as a hard mask for dry etching the substrate or sublayer. Compared to many other methods for patterning metallic hard mask structures, such as the popular lift-off method, our approach involves only spin coating and thermal annealing, thus is more cost-efficient. Metal salts including aluminum nitrate nonahydrate (ANN) and chromium nitrate nonahydrate (CNN) can both be used, and high aspect ratio (1:30) and high-resolution (sub-50 nm) pillars etched into silicon can be achieved readily. With further control of the etching profile by adjusting the dry etching parameters, cone-like silicon structure with reflectivity in the visible region down to a remarkably low value of 2% was achieved. Lastly, by coating a hydrophobic surfactant layer, the pillar array demonstrated a super-hydrophobic property with an exceptionally high water contact angle of up to 165.7°.

Theoretical prediction and atomic kinetic Monte Carlo simulations of void superlattice self-organization under irradiation.

PubMed

Gao, Yipeng; Zhang, Yongfeng; Schwen, Daniel; Jiang, Chao; Sun, Cheng; Gan, Jian; Bai, Xian-Ming

2018-04-26

Nano-structured superlattices may have novel physical properties and irradiation is a powerful mean to drive their self-organization. However, the formation mechanism of superlattice under irradiation is still open for debate. Here we use atomic kinetic Monte Carlo simulations in conjunction with a theoretical analysis to understand and predict the self-organization of nano-void superlattices under irradiation, which have been observed in various types of materials for more than 40 years but yet to be well understood. The superlattice is found to be a result of spontaneous precipitation of voids from the matrix, a process similar to phase separation in regular solid solution, with the symmetry dictated by anisotropic materials properties such as one-dimensional interstitial atom diffusion. This discovery challenges the widely accepted empirical rule of the coherency between the superlattice and host matrix crystal lattice. The atomic scale perspective has enabled a new theoretical analysis to successfully predict the superlattice parameters, which are in good agreement with independent experiments. The theory developed in this work can provide guidelines for designing target experiments to tailor desired microstructure under irradiation. It may also be generalized for situations beyond irradiation, such as spontaneous phase separation with reaction.

Simultaneous liquid chromatography/mass spectrometry determination of both polar and "multiresidue" pesticides in food using parallel hydrophilic interaction/reversed-phase liquid chromatography and a hybrid sample preparation approach.

PubMed

Robles-Molina, José; Gilbert-López, Bienvenida; García-Reyes, Juan F; Molina-Díaz, Antonio

2017-09-29

Pesticide testing of foodstuffs is usually accomplished with generic wide-scope multi-residue methods based on liquid chromatography tandem mass spectrometry (LC-MS/MS). However, this approach does not cover some special pesticides, the so called "single-residue method" compounds, that are hardly compatible with standard reversed-phase (RP) separations due to their specific properties. In this article, we propose a comprehensive strategy for the integration of single residue method compounds and standard multiresidue pesticides within a single run. It is based on the use of a parallel LC column assembly with two different LC gradients performing orthogonal hydrophilic interaction chromatography (HILIC) and reversed-phase (RPLC) chromatography within one analytical run. Two sample aliquots were simultaneously injected on each column, using different gradients, being the eluents merged post-column prior to mass spectrometry detection. The approach was tested with 41 multiclass pesticides covering a wide range of physicochemical properties across several orders of log K ow (from -4 to +5.5). With this assembly, distinct separation from the void was attained for all the pesticides studied, keeping similar performance in terms of sensitivity, peak area reproducibility (<6 RSD% in most cases) and retention time stability of standard single column approaches (better than±0.1min). The application of the proposed approach using parallel HILIC/RPLC and RPLC/aqueous normal phase (Obelisc) were assessed in leek using LC-MS/MS. For this purpose, a hybrid QuEChERS (Quick, easy, cheap, effective, rugged and safe)/QuPPe (quick method for polar pesticides) method was evaluated based on solvent extraction with MeOH and acetonitrile followed by dispersive solid-phase extraction, delivering appropriate recoveries for most of the pesticides included in the study within the log K ow in the range from -4 to +5.5. The proposed strategy may be extended to other fields such as sport drug testing or environmental analysis, where the same type of variety of analytes featuring poor retention within a single chromatographic separation occurs. Copyright © 2017 Elsevier B.V. All rights reserved.

Ferritin nanocontainers that self-direct in synthetic polymer systems

NASA Astrophysics Data System (ADS)

Sengonul, Merih C.

Currently, there are many approaches to introduce functionality into synthetic polymers. Among these, for example, are copolymerization, grafting, and blending methods. However, modifications made by such methods also change the thermodynamics and rheological properties of the polymer system of interest, and each new modification often requires a costly reoptimization of polymer processing. Such a reoptimalization would not be necessary if new functionality could be introduced via a container whose external surface is chemically and physically tuned to interact with the parent polymer. The contents of the container could then be changed without changing other important properties of the parent polymer. In this context this thesis project explores an innovative nanocontainer platform which can be introduced into phase-separating homopolymer blends. Ferritin is a naturally existing nanocontainer that can be used synthetically to package and selectively transport functional moieties to a particular phase that is either in the bulk or on the surface of a homopolymer blend system. The principal focus of this work centers on modifying the surface of wild ferritin to: (1) render modified ferritin soluble in a non-aqueous solvent; and (2) impart it with self-directing properties when exposed to a homopolymer blend surface or incorporated into the bulk of a homopolymer blend. Wild ferritin is water soluble, and this research project successfully modified wild ferritin by grafting either amine-functional poly(ethylene glycol) (PEG) or short-chain alkanes to carbodiimide activated carboxylate groups on ferritin's surface. Such modified ferritin is soluble in dichloromethane (DCM). Modification was confirmed by ion-exchange chromatography, zeta-potential measurements, and electrospray mass spectroscopy. FT-IR was used to quantify the extent of PEGylation of the reaction products through area ratios of the -C-O-C asymmetric stretching vibration of the grafted PEG chains to the carbonyl stretching vibration (amide I band) of the protein. The dimensionless grafting density after PEGylation was found to be 0.13 with 120 average grafted PEG chains per ferritin nanocontainer. Modified ferritin was used for bulk modification of a phase-separated polymer blend of poly(desaminotyrosyl tyrosine dodecyl ester carbonate) [PDTD] and PEG. TEM micrographs showed remarkable selectivity of PEGylated ferritin to PEG domains, while alkylated ferritin self-directs to the PDTD matrix. We explain this strong selectivity by the favourable interaction energies between the grafted and free matrix chains. In addition, both modified and wild ferritin were used for surface modification of the phase-separated homopolymer blend of PDTD and poly(ε-caprolactone) (PCL). At physiological pH wild ferritin selectively adsorbed onto the PDTD phase, while alkylated ferritin showed a striking selectivity to PCL phase. We attribute this behavior to the increase in protein's pI point above physiological pH after modification, which changes the electrostatic interactions between the ferritin and the polymer surface. Collectively, these results demonstrate the versatile use of ferritin as a model nanocontainer for the selective modification of surface and bulk properties of polymers.

Separation of aqueous two-phase polymer systems in microgravity

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Single-Phase Concentrated Solid-Solution Alloys: Bridging Intrinsic Transport Properties and Irradiation Resistance

DOE PAGES

Jin, Ke; Bei, Hongbin

2018-04-30

Single-phase concentrated solid-solution alloys (SP-CSAs), including high entropy alloys (HEAs), are compositionally complex but structurally simple, and provide a playground of tailoring material properties through modifying their compositional complexity. The recent progress in understanding the compositional effects on the energy and mass transport properties in a series of face-centered-cubic SP-CSAs is the focus of this review. Relatively low electrical and thermal conductivities, as well as small separations between the interstitial and vacancy migration barriers have been generally observed, but largely depend on the alloying constituents. We further discuss the impact of such intrinsic transport properties on their irradiation response; themore » linkage to the delayed damage accumulation, slow defect aggregation, and suppressed irradiation induced swelling and segregation has been presented. We emphasize that the number of alloying elements may not be a critical factor on both transport properties and the defect behaviors under ion irradiations. Furthermore, the recent findings have stimulated novel concepts in the design of new radiation-tolerant materials, but further studies are demanded to enable predictive models that can quantitatively bridge the transport properties to the radiation damage.« less

Single-Phase Concentrated Solid-Solution Alloys: Bridging Intrinsic Transport Properties and Irradiation Resistance

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

Jin, Ke; Bei, Hongbin

Single-phase concentrated solid-solution alloys (SP-CSAs), including high entropy alloys (HEAs), are compositionally complex but structurally simple, and provide a playground of tailoring material properties through modifying their compositional complexity. The recent progress in understanding the compositional effects on the energy and mass transport properties in a series of face-centered-cubic SP-CSAs is the focus of this review. Relatively low electrical and thermal conductivities, as well as small separations between the interstitial and vacancy migration barriers have been generally observed, but largely depend on the alloying constituents. We further discuss the impact of such intrinsic transport properties on their irradiation response; themore » linkage to the delayed damage accumulation, slow defect aggregation, and suppressed irradiation induced swelling and segregation has been presented. We emphasize that the number of alloying elements may not be a critical factor on both transport properties and the defect behaviors under ion irradiations. Furthermore, the recent findings have stimulated novel concepts in the design of new radiation-tolerant materials, but further studies are demanded to enable predictive models that can quantitatively bridge the transport properties to the radiation damage.« less

Superficially Porous Particles with 1000 Å Pores for Large Biomolecule High Performance Liquid Chromatography and Polymer Size Exclusion Chromatography

PubMed Central

Wagner, Brian M.; Schuster, Stephanie A.; Boyes, Barry E.; Shields, Taylor J.; Miles, William L.; Haynes, Mark J.; Moran, Robert E.; Kirkland, Joseph J.; Schure, Mark R.

2017-01-01

To facilitate mass transport and column efficiency, solutes must have free access to particle pores to facilitate interactions with the stationary phase. To ensure this feature, particles should be used for HPLC separations which have pores sufficiently large to accommodate the solute without restricted diffusion. This paper describes the design and properties of superficially porous (also called Fused-Core®, core shell or porous shell) particles with very large (1000 Å) pores specifically developed for separating very large biomolecules and polymers. Separations of DNA fragments, monoclonal antibodies, large proteins and large polystyrene standards are used to illustrate the utility of these particles for efficient, high-resolution applications. PMID:28213987

Superficially porous particles with 1000Å pores for large biomolecule high performance liquid chromatography and polymer size exclusion chromatography.

PubMed

Wagner, Brian M; Schuster, Stephanie A; Boyes, Barry E; Shields, Taylor J; Miles, William L; Haynes, Mark J; Moran, Robert E; Kirkland, Joseph J; Schure, Mark R

2017-03-17

To facilitate mass transport and column efficiency, solutes must have free access to particle pores to facilitate interactions with the stationary phase. To ensure this feature, particles should be used for HPLC separations which have pores sufficiently large to accommodate the solute without restricted diffusion. This paper describes the design and properties of superficially porous (also called Fused-Core ® , core shell or porous shell) particles with very large (1000Å) pores specifically developed for separating very large biomolecules and polymers. Separations of DNA fragments, monoclonal antibodies, large proteins and large polystyrene standards are used to illustrate the utility of these particles for efficient, high-resolution applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Methods for determining infrasound phase velocity direction with an array of line sensors.

PubMed

Walker, Kristoffer T; Zumberge, Mark A; Hedlin, Michael A H; Shearer, Peter M

2008-10-01

Infrasound arrays typically consist of several microbarometers separated by distances that provide predictable signal time separations, forming the basis for processing techniques that estimate the phase velocity direction. The directional resolution depends on the noise level and is proportional to the number of these point sensors; additional sensors help attenuate noise and improve direction resolution. An alternative approach is to form an array of directional line sensors, each of which emulates a line of many microphones that instantaneously integrate pressure change. The instrument response is a function of the orientation of the line with respect to the signal wavefront. Real data recorded at the Piñon Flat Observatory in southern California and synthetic data show that this spectral property can be exploited with multiple line sensors to determine the phase velocity direction with a precision comparable to a larger aperture array of microbarometers. Three types of instrument-response-dependent beamforming and an array deconvolution technique are evaluated. The results imply that an array of five radial line sensors, with equal azimuthal separation and an aperture that depends on the frequency band of interest, provides directional resolution while requiring less space compared to an equally effective array of five microbarometers with rosette wind filters.

On the Role of High Amounts of Mn Element in CdS Structure

NASA Astrophysics Data System (ADS)

Gonullu, Meryem Polat; Kose, Salih

2017-03-01

CdS and MnS are technologically important semiconducting materials. In this work, due to the limited ability of these materials separately, a detailed characterization of the new samples formed by the combined use of them has been reported. CdS films, with the incorporation of Mn in a wide range of concentrations, have been produced by a low-cost Ultrasonic Spray Pyrolysis set-up. Spectroscopic Ellipsometry (SE) has been used to determine the thicknesses and optical constants ( n, k) of the samples. It has been determined that samples with high amounts of Mn have lower refractive index values. Absorbance spectra have shown additional band edges along with the one belonging to CdS, for samples with Mn concentrations higher than 50 pct. This has been attributed to a phase separation above this limit. Raman spectroscopy analysis which shows additional Raman peaks belonging to MnS phase also supports these findings. Depending on this phase separation, crystalline structure has been deteriorated. Surface properties of the samples have been investigated by SEM and AFM. Elemental analysis has been performed by EDS. Resistivity measurements performed by a four-probe set-up have shown that samples containing high amount of Mn have lower electrical resistivity values.

Pre-biotic stage of life origin under non-photosynthetic conditions

NASA Technical Reports Server (NTRS)

Bartsev, S. I.; Mezhevikin, V. V.

2005-01-01

Spontaneous assembling of a simplest bacterial cell even if all necessary molecules are present in a solution seems to be extremely rare event and from the scientific standpoint has to be considered as impossible. Therefore, a predecessor of a living cell has to be very simple for providing its self-assembling and at the same time it should be able of progressive increase in complexity. Now phase-separated particles, first of all micelles, are put forward as possible predecessors of living cell. According to the offered working concept only phase-separated particles possessing autocatalytic properties can be considered as predecessors of living cells. The first stage of evolution of these phase-separated autocatalytic systems is the appearance of pre-biotic metabolism providing synthesis of amphiphiles for formation of capsules of these systems. This synthesis is maintained by the energy of a base reaction being a component of a planet-chemical cycle. Catalytic system providing functioning of pre-biotic metabolism is based on multivariate oligomeric autocatalyst, which reproduces itself from monomers, penetrating the particles from the outside. Since the autocatalyst realizes random polymerization then a collection of other oligomers possessing different catalytic functions is produced. In the paper the functioning of multivariate oligomeric autocatalyst in flow reactor is analyzed. c2005 Published by Elsevier Ltd on behalf of COSPAR.

Melt Extrusion of High-Dose Co-Amorphous Drug-Drug Combinations : Theme: Formulation and Manufacturing of Solid Dosage Forms Guest Editors: Tony Zhou and Tonglei Li.

PubMed

Arnfast, Lærke; Kamruzzaman, Md; Löbmann, Korbinian; Aho, Johanna; Baldursdottir, Stefania; Rades, Thomas; Rantanen, Jukka

2017-12-01

Many future drug products will be based on innovative manufacturing solutions, which will increase the need for a thorough understanding of the interplay between drug material properties and processability. In this study, hot melt extrusion of a drug-drug mixture with minimal amount of polymeric excipient was investigated. Using indomethacin-cimetidine as a model drug-drug system, processability of physical mixtures with and without 5% (w/w) of polyethylene oxide (PEO) were studied using Differential Scanning Calorimetry (DSC) and Small Amplitude Oscillatory Shear (SAOS) rheometry. Extrudates containing a co-amorphous glass solution were produced and the solid-state composition of these was studied with DSC. Rheological analysis indicated that the studied systems display viscosities higher than expected for small molecule melts and addition of PEO decreased the viscosity of the melt. Extrudates of indomethacin-cimetidine alone displayed amorphous-amorphous phase separation after 4 weeks of storage, whereas no phase separation was observed during the 16 week storage of the indomethacin-cimetidine extrudates containing 5% (w/w) PEO. Melt extrusion of co-amorphous extrudates with low amounts of polymer was found to be a feasible manufacturing technique. Addition of 5% (w/w) polymer reduced melt viscosity and prevented phase separation.

Chromatographic test methods for characterizing alkylsiloxane-bonded silica columns for reversed-phase liquid chromatography.

PubMed

Poole, Colin F

2018-06-07

Major obstacles to formulating a simple retention mechanism for reversed-phase liquid chromatography have a direct impact on the development of experimental methods for column characterization as they limit our capability to understand observed differences in retention at a system level. These problems arise from the heterogeneous composition of the stationary phase, the difficulty of providing a working definition for the phase ratio, and uncertainty as to whether the distribution mechanism for varied compounds is a partition, adsorption or mixed (combination) of these models. Retention factor and separation factor measurements offer little guidance as they represent an average of various and variable contributing factors that can only be interpreted by assuming a specific model. Column characterization methods have tended to ignore these difficulties by inventing a series of terms to describe column properties, such as hydrophobicity, hydrophilicity, silanol activity, steric resistance, etc., without proper definition. This has allowed multiple scales to be proposed for the same property which generally are only weakly correlated. Against this background we review the major approaches for the characterization of alkylsiloxane-bonded silica stationary phases employing prototypical compounds, the hydrophobic-subtraction model and the solvation parameter model. Those methods using prototypical compounds are limited by the lack of compounds with a singular dominant interaction. The multivariate approaches that extract column characteristic properties from the retention of varied compounds are more hopeful but it is important to be more precise in defining the characteristic column properties and cognizant that general interpretation of these properties for varied columns cannot escape the problem of a poor understanding of the distribution mechanism. Copyright © 2018 Elsevier B.V. All rights reserved.

Ceramic composite separators coated with moisturized ZrO(2) nanoparticles for improving the electrochemical performance and thermal stability of lithium ion batteries.

PubMed

Kim, Ki Jae; Kwon, Hyuk Kwon; Park, Min-Sik; Yim, Taeeun; Yu, Ji-Sang; Kim, Young-Jun

2014-05-28

We introduce a ceramic composite separator prepared by coating moisturized ZrO2 nanoparticles with a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-12wt%HFP) copolymer on a polyethylene separator. The effect of moisturized ZrO2 nanoparticles on the morphology and the microstructure of the polymeric coating layer is investigated. A large number of micropores formed around the embedded ZrO2 nanoparticles in the coating layer as a result of the phase inversion caused by the adsorbed moisture. The formation of micropores highly affects the ionic conductivity and electrolyte uptake of the ceramic composite separator and, by extension, the rate discharge properties of lithium ion batteries. In particular, thermal stability of the ceramic composite separators coated with the highly moisturized ZrO2 nanoparticles (a moisture content of 16 000 ppm) is dramatically improved without any degradation in electrochemical performance compared to the performance of pristine polyethylene separators.

Development of a process for separation of mogroside V from Siraitia grosvenorii by macroporous resins.

PubMed

Zhang, Min; Yang, Huihua; Zhang, Hongyang; Wang, Yuerong; Hu, Ping

2011-08-25

A separation method was developed for the preparative separation and enrichment of the non-caloric sweetener mogroside V from Siraitia grosvenorii. The adsorption properties of six macroporous resins were evaluated. Results showed that HZ 806 resin offered the best adsorption and desorption capacities. Based on the adsorption experiments on HZ 806, the adsorption data were found to fit the Freundlich model well. The pseudo-second-order kinetic model showed the highest correlation with the experimental results. Separation was performed with deionized water and 40% aqueous ethanol solution as mobile phases. In a typical run, 100 g of herb was processed and 3.38 g of mogroside V with a purity of 10.7% was harvested. This separation method provided a 15.1-fold increase in the purification factor from 0.5% to 10.7%. The present study showed that HZ 806 resins were effective for the separation and enrichment of mogroside V from S. grosvenorii.

Tuning Phase Composition of TiO2 by Sn(4+) Doping for Efficient Photocatalytic Hydrogen Generation.

PubMed

Wang, Fenglong; Ho, Jie Hui; Jiang, Yijiao; Amal, Rose

2015-11-04

The anatase-rutile mixed-phase photocatalysts have attracted extensive research interest because of the superior activity compared to their single phase counterparts. In this study, doping of Sn(4+) ions into the lattice of TiO2 facilitates the phase transformation from anatase to rutile at a lower temperature while maintaining the same crystal sizes compared to the conventional annealling approach. The mass ratios between anatase and rutile phases can be easily manipulated by varying the Sn-dopant content. Characterization results reveal that the Sn(4+) ions entered into the lattice of TiO2 by substituting some of the Ti(4+) ions and distributed evenly in the matrix of TiO2. The substitution induced the distortion of the lattice structure, which realized the phase transformation from anatase to rutile at a lower temperature and the close-contact phase junctions were consequently formed between anatase and rutile, accounting for the efficient charge separations. The mixed-phase catalysts prepared by doping Sn(4+) ions into the TiO2 exhibit superior activity for photocatalytic hydrogen generation in the presence of Au nanoparticles, relatively to their counterparts prepared by the conventional annealling at higher temperatures. The band allignment between anatase and rutile phases is established based on the valence band X-ray photoelectron spectra and diffuse reflectance spectra to understand the spatial charge separation process at the heterojunction between the two phases. The study provides a new route for the synthesis of mixed-phase TiO2 catalysts for photocatalytic applications and advances the understanding on the enhanced photocatalytic properties of anatase-rutile mixtures.

Traditional Portland cement and MgO-based cement: a promising combination?

NASA Astrophysics Data System (ADS)

Tonelli, Monica; Martini, Francesca; Calucci, Lucia; Geppi, Marco; Borsacchi, Silvia; Ridi, Francesca

2017-06-01

MgO/SiO2 cements are materials potentially very useful for radioactive waste disposal, but knowledge about their physico-chemical properties is still lacking. In this paper we investigated the hydration kinetics of cementitious formulations prepared by mixing MgO/SiO2 and Portland cement in different proportions and the structural properties of the hydrated phases formed in the first month of hydration. In particular, the hydration kinetics was investigated by measuring the free water index on pastes by means of differential scanning calorimetry, while the structural characterization was carried out by combining thermal (DTA), diffractometric (XRD), and spectroscopic (FTIR, 29Si solid state NMR) techniques. It was found that calcium silicate hydrate (C-S-H) and magnesium silicate hydrate (M-S-H) gels mainly form as separate phases, their relative amount and structural characteristics depending on the composition of the hydrated mixture. Moreover, the composition of the mixtures strongly affects the kinetics of hydration and the pH of the aqueous phase in contact with the cementitious materials. The results here reported show that suitable mixtures of Portland cement and MgO/SiO2 could be used to modify the properties of hydrated phases with potential application in the storage of nuclear waste in clayey disposal.

Quenched bond randomness: Superfluidity in porous media and the strong violation of universality

NASA Astrophysics Data System (ADS)

Falicov, Alexis; Berker, A. Nihat

1997-04-01

The effects of quenched bond randomness are most readily studied with superfluidity immersed in a porous medium. A lattice model for3He-4He mixtures and incomplete4He fillings in aerogel yields the signature effect of bond randomness, namely the conversion of symmetry-breaking first-order phase transitions into second-order phase transitions, the λ-line reaching zero temperature, and the elimination of non-symmetry-breaking first-order phase transitions. The model recognizes the importance of the connected nature of aerogel randomness and thereby yields superfluidity at very low4He concentrations, a phase separation entirely within the superfluid phase, and the order-parameter contrast between mixtures and incomplete fillings, all in agreement with experiments. The special properties of the helium mixture/aerogel system are distinctly linked to the aerogel properties of connectivity, randomness, and tenuousness, via the additional study of a regularized “jungle-gym” aerogel. Renormalization-group calculations indicate that a strong violation of the empirical universality principle of critical phenomena occurs under quenched bond randomness. It is argued that helium/aerogel critical properties reflect this violation and further experiments are suggested. Renormalization-group analysis also shows that, adjoiningly to the strong universality violation (which hinges on the occurrence or non-occurrence of asymptotic strong coupling—strong randomness under rescaling), there is a new “hyperuniversality” at phase transitions with asymptotic strong coupling—strong randomness behavior, for example assigning the same critical exponents to random- bond tricriticality and random- field criticality.

Metal-organic frameworks for analytical chemistry: from sample collection to chromatographic separation.

PubMed

Gu, Zhi-Yuan; Yang, Cheng-Xiong; Chang, Na; Yan, Xiu-Ping

2012-05-15

In modern analytical chemistry researchers pursue novel materials to meet analytical challenges such as improvements in sensitivity, selectivity, and detection limit. Metal-organic frameworks (MOFs) are an emerging class of microporous materials, and their unusual properties such as high surface area, good thermal stability, uniform structured nanoscale cavities, and the availability of in-pore functionality and outer-surface modification are attractive for diverse analytical applications. This Account summarizes our research on the analytical applications of MOFs ranging from sampling to chromatographic separation. MOFs have been either directly used or engineered to meet the demands of various analytical applications. Bulk MOFs with microsized crystals are convenient sorbents for direct application to in-field sampling and solid-phase extraction. Quartz tubes packed with MOF-5 have shown excellent stability, adsorption efficiency, and reproducibility for in-field sampling and trapping of atmospheric formaldehyde. The 2D copper(II) isonicotinate packed microcolumn has demonstrated large enhancement factors and good shape- and size-selectivity when applied to on-line solid-phase extraction of polycyclic aromatic hydrocarbons in water samples. We have explored the molecular sieving effect of MOFs for the efficient enrichment of peptides with simultaneous exclusion of proteins from biological fluids. These results show promise for the future of MOFs in peptidomics research. Moreover, nanosized MOFs and engineered thin films of MOFs are promising materials as novel coatings for solid-phase microextraction. We have developed an in situ hydrothermal growth approach to fabricate thin films of MOF-199 on etched stainless steel wire for solid-phase microextraction of volatile benzene homologues with large enhancement factors and wide linearity. Their high thermal stability and easy-to-engineer nanocrystals make MOFs attractive as new stationary phases to fabricate MOF-coated capillaries for high-resolution gas chromatography (GC). We have explored a dynamic coating approach to fabricate a MOF-coated capillary for the GC separation of important raw chemicals and persistent organic pollutants with high resolution and excellent selectivity. We have combined a MOF-coated fiber for solid-phase microextraction with a MOF-coated capillary for GC separation, which provides an effective MOF-based tandem molecular sieve platform for selective microextraction and high-resolution GC separation of target analytes in complex samples. Microsized MOFs with good solvent stability are attractive stationary phases for high-performance liquid chromatography (HPLC). These materials have shown high resolution and good selectivity and reproducibility in both the normal-phase HPLC separation of fullerenes and substituted aromatics on MIL-101 packed columns and position isomers on a MIL-53(Al) packed column and the reversed-phase HPLC separation of a wide range of analytes from nonpolar to polar and acidic to basic solutes. Despite the above achievements, further exploration of MOFs in analytical chemistry is needed. Especially, analytical application-oriented engineering of MOFs is imperative for specific applications.

Metal-Organic Frameworks for Separation.

PubMed

Zhao, Xiang; Wang, Yanxiang; Li, Dong-Sheng; Bu, Xianhui; Feng, Pingyun

2018-03-27

Separation is an important industrial step with critical roles in the chemical, petrochemical, pharmaceutical, and nuclear industries, as well as in many other fields. Although much progress has been made, the development of better separation technologies, especially through the discovery of high-performance separation materials, continues to attract increasing interest due to concerns over factors such as efficiency, health and environmental impacts, and the cost of existing methods. Metal-organic frameworks (MOFs), a rapidly expanding family of crystalline porous materials, have shown great promise to address various separation challenges due to their well-defined pore size and unprecedented tunability in both composition and pore geometry. In the past decade, extensive research is performed on applications of MOF materials, including separation and capture of many gases and vapors, and liquid-phase separation involving both liquid mixtures and solutions. MOFs also bring new opportunities in enantioselective separation and are amenable to morphological control such as fabrication of membranes for enhanced separation outcomes. Here, some of the latest progress in the applications of MOFs for several key separation issues, with emphasis on newly synthesized MOF materials and the impact of their compositional and structural features on separation properties, are reviewed and highlighted. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A thermo-mechanical correlation with driving forces for hcp martensite and twin formations in the Fe–Mn–C system exhibiting multicomposition sets

PubMed Central

Nakano, Jinichiro

2013-01-01

The thermodynamic properties of the Fe–Mn–C system were investigated by using an analytical model constructed by a CALPHAD approach. The stacking fault energy (SFE) of the fcc structure with respect to the hcp phase was always constant at T0, independent of the composition and temperature when other related parameters were assumed to be constant. Experimental limits for the thermal hcp formation and the mechanical (deformation-induced) hcp formation were separated by the SFE at T0. The driving force for the fcc to hcp transition, defined as a dimensionless value –dGm/(RT), was determined in the presence of Fe-rich and Mn-rich composition sets in each phase. Carbon tended to partition to the Mn-rich phase rather than to the Fe-rich phase for the compositions studied. The results obtained revealed a thermo-mechanical correlation with empirical yield strength, maximum true stress and maximum true strain. The proportionality between thermodynamics and mechanical properties is discussed. PMID:27877555

A thermo-mechanical correlation with driving forces for hcp martensite and twin formations in the Fe–Mn–C system exhibiting multicomposition sets

DOE PAGES

Nakano, Jinichiro

2013-03-15

Thermodynamic properties of the Fe-Mn-C system were investigated by using an analytical model constructed by a CALPHAD approach. Stacking fault energy (SFE) of the fcc structure with respect to the hcp phase was always constant at T 0, independent of composition and temperature when the other related parameters were assumed to be constant. Experimental limits for the thermal hcp formation and the mechanical (deformation-induced) hcp formation were separated by the SFE at T 0. The driving force for the fcc to hcp transition, defined as a dimensionless value –dG m/(RT), was determined in the presence of Fe-rich and Mn-rich compositionmore » sets in each phase. Carbon tended to partition to the Mn-rich phase rather than to the Fe-rich phase for the studied compositions. The obtained results revealed a thermo-mechanical correlation with empirical yield strength, maximum true stress and maximum true strain. The proportionality between thermodynamics and mechanical properties is discussed.« less

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-05-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, C*j, by including water and other inorganics in the absorbing phase. Such a C*j definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.

Parameter estimation of qubit states with unknown phase parameter

NASA Astrophysics Data System (ADS)

Suzuki, Jun

2015-02-01

We discuss a problem of parameter estimation for quantum two-level system, qubit system, in presence of unknown phase parameter. We analyze trade-off relations for mean square errors (MSEs) when estimating relevant parameters with separable measurements based on known precision bounds; the symmetric logarithmic derivative (SLD) Cramér-Rao (CR) bound and Hayashi-Gill-Massar (HGM) bound. We investigate the optimal measurement which attains the HGM bound and discuss its properties. We show that the HGM bound for relevant parameters can be attained asymptotically by using some fraction of given n quantum states to estimate the phase parameter. We also discuss the Holevo bound which can be attained asymptotically by a collective measurement.

Changes in the zero-point energy of the protons as the source of the binding energy of water to A-phase DNA.

PubMed

Reiter, G F; Senesi, R; Mayers, J

2010-10-01

The measured changes in the zero-point kinetic energy of the protons are entirely responsible for the binding energy of water molecules to A phase DNA at the concentration of 6  water molecules/base pair. The changes in kinetic energy can be expected to be a significant contribution to the energy balance in intracellular biological processes and the properties of nano-confined water. The shape of the momentum distribution in the dehydrated A phase is consistent with coherent delocalization of some of the protons in a double well potential, with a separation of the wells of 0.2 Å.

Anomalous critical behavior in the polymer collapse transition of three-dimensional lattice trails.

PubMed

Bedini, Andrea; Owczarek, Aleksander L; Prellberg, Thomas

2012-07-01

Trails (bond-avoiding walks) provide an alternative lattice model of polymers to self-avoiding walks, and adding self-interaction at multiply visited sites gives a model of polymer collapse. Recently a two-dimensional model (triangular lattice) where doubly and triply visited sites are given different weights was shown to display a rich phase diagram with first- and second-order collapse separated by a multicritical point. A kinetic growth process of trails (KGTs) was conjectured to map precisely to this multicritical point. Two types of low-temperature phases, a globule phase and a maximally dense phase, were encountered. Here we investigate the collapse properties of a similar extended model of interacting lattice trails on the simple cubic lattice with separate weights for doubly and triply visited sites. Again we find first- and second-order collapse transitions dependent on the relative sizes of the doubly and triply visited energies. However, we find no evidence of a low-temperature maximally dense phase with only the globular phase in existence. Intriguingly, when the ratio of the energies is precisely that which separates the first-order from the second-order regions anomalous finite-size scaling appears. At the finite-size location of the rounded transition clear evidence exists for a first-order transition that persists in the thermodynamic limit. This location moves as the length increases, with its limit apparently at the point that maps to a KGT. However, if one fixes the temperature to sit at exactly this KGT point, then only a critical point can be deduced from the data. The resolution of this apparent contradiction lies in the breaking of crossover scaling and the difference in the shift and transition width (crossover) exponents.

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

PubMed

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

2010-09-21

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

Extension of the carotenoid test to superficially porous C18 bonded phases, aromatic ligand types and new classical C18 bonded phases.

PubMed

Lesellier, E

2012-11-30

The recent introduction of new stationary phases for liquid chromatography based on superficially porous particles, called core-shell or fused-core, dramatically improved the separation performances through very high efficiency, due mainly to reduced eddy diffusion. However, few studies have evaluated the retention and selectivity of C18 phases based on such particles, despite some retention order change reported in literature between some of these phases. The carotenoid test has been developed a few years ago in the goal to compare the chromatographic properties of C18 bonded phases. Based on the analysis of carotenoid pigments by using Supercritical Fluid Chromatography (SFC), it allows, with a single analysis, to measure three main properties of reversed phase chromatography stationary phases: hydrophobicity, polar surface activity and shape selectivity. Previous studies showed the effect of the endcapping treatment, the bonding density, the pore size, and the type of bonding (monomeric vs. polymeric) on these studied properties, and described the classification map used for a direct column comparison. It was applied to ten ODS superficially porous stationary phases, showing varied chromatographic behaviors amongst these phases. As expected, due to the lower specific surface area, these superficially porous phases are less hydrophobic than the fully porous one. In regards of the polar surface activity (residual silanols) and to the shape selectivity, some of these superficially porous phases display close chromatographic properties (Poroshell 120, Halo C18, Ascentis Express, Accucore C18, Nucleoshell C18 on one side and Aeris Wide pore, Aeris peptide and Kinetex XDB on the other side), whereas others, Kinetex C18 and Halo peptide ES C18 display more specific ones. Besides, they can be compared to classical fully porous phases, in the goal to improve method transfer from fully to superficially porous particles. By the way, the paper also report the extension of the test to other ligands such as naphtyl, cholester, phenyl-hexyl, or to the new ODS bonded phases, such as charge surface hybrid phases, High Strength Silica, and Hybrid ones, and also presents results for identical brands using different particle size, such as Luna and Synergi phases. Phenyl-hexyl and napthyl ligands show rather close properties, low hydrophobicity, high polar surface activity and specific shape selectivity, whereas, at the opposite, the cholester phase display a polymeric behavior and a high hydrophobicity. Finally, additional classical (fully porous particles) C18 bonded phases are also reported to complete the data set presented in previous papers. Copyright © 2012 Elsevier B.V. All rights reserved.

Apker Award Recipient: Renormalization-Group Study of Helium Mixtures Immersed in a Porous Medium

NASA Astrophysics Data System (ADS)

Lopatnikova, Anna

1998-03-01

Superfluidity and phase separation in ^3He-^4He mixtures immersed in aerogel are studied by renormalization-group theory. Firstly, the theory is applied to jungle-gym (non-random) aerogel.(A. Lopatnikova and A.N. Berker, Phys. Rev. B 55, 3798 (1997).) This calculation is conducted via the coupled renormalization-group mappings of interactions near and away from aerogel. Superfluidity at very low ^4He concentrations and a depressed tricritical temperature are found at the onset of superfludity. A superfluid-superfluid phase separation, terminating at an isolated critical point, is found entirely within the superfluid phase. Secondly, the theory is applied to true aerogel, which has quenched disorder at both atomic and geometric levels.(A. Lopatnikova and A.N. Berker, Phys. Rev. B 56, 11865 (1997).) This calculation is conducted via the coupled renormalization-group mappings, near and away from aerogel, of quenched probability distributions of random interactions. Random-bond effects on superfluidity onset and random-field effects on superfluid phase separation are seen. The quenched randomness causes the λ line of second-order phase transitions of superfluidity onset to reach zero temperature, in agreement with general prediction and experiments. Based on these studies, the experimentally observed(S.B. Kim, J. Ma, and M.H.W. Chan, Phys. Rev. Lett. 71, 2268 (1993); N. Mulders and M.H.W. Chan, Phys. Rev. Lett. 75, 3705 (1995).) distinctive characteristics of ^3He-^4He mixtures in aerogel are related to the aerogel properties of connectivity, tenuousness, and atomic and geometric randomness.

Time-of-flight expansion of binary Bose–Einstein condensates at finite temperature

NASA Astrophysics Data System (ADS)

Lee, K. L.; Jørgensen, N. B.; Wacker, L. J.; Skou, M. G.; Skalmstang, K. T.; Arlt, J. J.; Proukakis, N. P.

2018-05-01

Ultracold quantum gases provide a unique setting for studying and understanding the properties of interacting quantum systems. Here, we investigate a multi-component system of 87Rb–39K Bose–Einstein condensates (BECs) with tunable interactions both theoretically and experimentally. Such multi-component systems can be characterized by their miscibility, where miscible components lead to a mixed ground state and immiscible components form a phase-separated state. Here we perform the first full simulation of the dynamical expansion of this system including both BECs and thermal clouds, which allows for a detailed comparison with experimental results. In particular we show that striking features emerge in time-of-flight (TOF) for BECs with strong interspecies repulsion, even for systems which were separated in situ by a large gravitational sag. An analysis of the centre of mass positions of the BECs after expansion yields qualitative agreement with the homogeneous criterion for phase-separation, but reveals no clear transition point between the mixed and the separated phases. Instead one can identify a transition region, for which the presence of a gravitational sag is found to be advantageous. Moreover, we analyse the situation where only one component is condensed and show that the density distribution of the thermal component also shows some distinct features. Our work sheds new light on the analysis of multi-component systems after TOF and will guide future experiments on the detection of miscibility in these systems.

Antifouling Cellulose Hybrid Biomembrane for Effective Oil/Water Separation.

PubMed

Kollarigowda, Ravichandran H; Abraham, Sinoj; Montemagno, Carlo D

2017-09-06

Oil/water separation has been of great interest worldwide because of the increasingly serious environmental pollution caused by the abundant discharge of industrial wastewater, oil spill accidents, and odors. Here, we describe simple and economical superhydrophobic hybrid membranes for effective oil/water separation. Eco-friendly, antifouling membranes were fabricated for oil/water separation, waste particle filtration, the blocking of thiol-based odor materials, etc., by using a cellulose membrane (CM) filter. The CM was modified from its original superhydrophilic nature into a superhydrophobic surface via a reversible addition-fragmentation chain transfer technique. The block copolymer poly{[3-(trimethoxysilyl)propyl acrylate]-block-myrcene} was synthesized using a "grafting-from" approach on the CM. The surface contact angle that we obtained was >160°, and absorption tests of several organic contaminants (oils and solvents) exhibited superior levels of extractive activity and excellent reusability. These properties rendered this membrane a promising surface for oil/water separation. Interestingly, myrcene blocks thiol (through "-ene-" chemistry) contaminants, thereby bestowing a pleasant odor to polluted water by acting as an antifouling material. We exploited the structural properties of cellulose networks and simple chemical manipulations to fabricate an original material that proved to be effective in separating water from organic and nano/microparticulate contaminants. These characteristics allowed our material to effectively separate water from oily/particulate phases as well as embed antifouling materials for water purification, thus making it an appropriate absorber for chemical processes and environmental protection.

Impact of molecular solvophobicity vs. solvophilicity on device performances of dimeric perylene diimide based solution-processed non-fullerene organic solar cells.

PubMed

Lu, Zhenhuan; Zhang, Xin; Zhan, Chuanlang; Jiang, Bo; Zhang, Xinliang; Chen, Lili; Yao, Jiannian

2013-07-21

Because of their outstanding molecular optoelectronic properties, perylene diimides (PDIs) are promising alternatives to the commonly used PCBM. However, the overly strong aggregation ability, poor solution-processability and compatibility of PDIs severely limit their photovoltaic applications. We turned to borrowing the amphiphile concept to improve these supramolecular properties. Practically, we fine-tuned the molecular solvophobicity with respect to the molecular solvophilicity, e.g. F(solvophob/solvophil), by changing the number of the weakly solvophobic 2-methoxyethoxyl (EG) groups in the bay-region of the thienyl-bridged dimeric PDI backbone, forming three PDI dimers of Bis-PDI-T (0 EG), Bis-PDI-T-EG (2 EG) and Bis-PDI-T-di-EG (4 EG) (Scheme 1). The photovoltaic properties using these dimers as the solution-processed non-fullerene electron-acceptor and P3HT as the electron-donor were investigated via the device configuration of ITO/PEDOT:PSS/P3HT:PDI dimer/Ca/Al. Bis-PDI-T exhibited overly strong aggregation ability and very poor solution-processability, which severely limited compatibility, giving a very poor power conversion efficiency (PCE) of 0.007%. When two EG groups were attached at the 1,1'-positions, the resulted Bis-PDI-T-EG showed dramatically reduced aggregation ability, improved solution-processability, compatibility and proper phase separation. Small sized phases (∼20 nm) dominated in the active layer and the best PCE was increased to 0.39%. When four solvophobic EG functions were introduced, affording Bis-PDI-T-di-EG with excellent supramolecular properties, particularly, the improvement of the phase separation with an increased phase size of 24 nm and the enhanced electron and hole mobilities, by 2-4 times, with respect to that of Bis-PDI-T-EG. The best PCE was further enhanced to 0.88%. After using 1-chloronaphthalene as the co-solvent of 1,2-dichlorobenzene to further improve the compatibility, the PCE was improved further up to 0.41% for Bis-PDI-T, 0.76% for Bis-PDI-T-EG and 1.54% for Bis-PDI-T-di-EG.

Planetary period oscillations in Saturn's magnetosphere: Further comments on the relationship between post-equinox properties deduced from magnetic field and Saturn kilometric radiation measurements

NASA Astrophysics Data System (ADS)

Cowley, S. W. H.; Provan, G.

2016-07-01

We discuss the planetary period oscillations (PPOs) observed by the Cassini spacecraft in Saturn's magnetosphere, in particular the relationship between the properties of the PPOs in the post-equinox interval as observed in magnetic field data by Andrews et al. (2012) and Provan et al. (2013, 2014) and in Saturn kilometric radiation (SKR) emissions by Fischer et al. (2014, 2015), whose results are somewhat discrepant. We show that differences in the reported PPO periods, a fundamental property which should be essentially identical in the two data sets, can largely be accounted for by the phenomenon of dual modulation of the SKR emissions in polarization-separated data, in which the modulation associated with one hemisphere is also present in the other. Misidentification of the modulations results in a reported reversal in the SKR periods in the initial post-equinox interval, south for north and vice versa, relative to the magnetic oscillations whose hemispheric origin is more securely identified through the field component phase relations. Dual modulation also results in the apparent occurrence of phase-locked common periods in the northern and southern SKR data during later intervals during which two separate periods are clearly discerned in the magnetic data through beat modulations in both phase and amplitude. We further show that the argument of Fischer et al. (2015) concerning the phase relation between the magnetic field oscillations and the SKR modulations is erroneous, the phase difference between them revealing the local time (LT) of the upward field-aligned current of the PPO current system at times of SKR modulation maxima. Furthermore, this LT is found to vary significantly over the Cassini mission from dawn, to dusk, and to noon, depending on the LT of apoapsis where the spacecraft spends most time. These variations are consistent with the view that the SKR modulation is fundamentally a rotating system like the magnetic perturbations, though complicated by the strong LT asymmetry in the strength of the sources, and rule out a mainly clock-like (strobe) modulation as argued by Fischer et al. (2015), for which no physical mechanism is suggested. We also elucidate the nature of the magnetic periods, criticized by Fischer et al. (2015), which have previously been derived in ∼100-200 day post-equinox intervals between abrupt changes in PPO properties, and further show that their argument that the magnetic phase data provide evidence for the occurrence of common phase-locked magnetic oscillations in some intervals is fallacious. The most important consequence of our results, however, is that they demonstrate the essential compatibility of the post-equinox magnetic field and SKR data, despite the contrary results published to date. They also show that due to the dual modulation effect in polarization-separated SKR data, analysis and interpretation may contain more subtleties than previously realized. Joint examination of the combined magnetic and SKR data clearly provides greater insight and enhanced confidence compared with analyses of these data sets individually.

Phase separation in SiGe nanocrystals embedded in SiO{sub 2} matrix during high temperature annealing

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

Mogaddam, N. A. P.; Turan, R.; Alagoz, A. S.

2008-12-15

SiGe nanocrystals have been formed in SiO{sub 2} matrix by cosputtering Si, Ge, and SiO{sub 2} independently on Si substrate. Effects of the annealing time and temperature on structural and compositional properties are studied by transmission electron microscopy, x-ray diffraction (XRD), and Raman spectroscopy measurements. It is observed that Ge-rich Si{sub (1-x)}Ge{sub x} nanocrystals do not hold their compositional uniformity when annealed at high temperatures for enough long time. A segregation process leading to separation of Ge and Si atoms from each other takes place. This process has been evidenced by a double peak formation in the XRD and Ramanmore » spectra. We attributed this phase separation to the differences in atomic size, surface energy, and surface diffusion disparity between Si and Ge atoms leading to the formation of nonhomogenous structure consist of a Si-rich SiGe core covered by a Ge-rich SiGe shell. This experimental observation is consistent with the result of reported theoretical and simulation methods.« less

Entanglement entropy for the long-range Ising chain in a transverse field.

PubMed

Koffel, Thomas; Lewenstein, M; Tagliacozzo, Luca

2012-12-28

We consider the Ising model in a transverse field with long-range antiferromagnetic interactions that decay as a power law with their distance. We study both the phase diagram and the entanglement properties as a function of the exponent of the interaction. The phase diagram can be used as a guide for future experiments with trapped ions. We find two gapped phases, one dominated by the transverse field, exhibiting quasi-long-range order, and one dominated by the long-range interaction, with long-range Néel ordered ground states. We determine the location of the quantum critical points separating those two phases. We determine their critical exponents and central charges. In the phase with quasi-long-range order the ground states exhibit exotic corrections to the area law for the entanglement entropy coexisting with gapped entanglement spectra.

Determination of solute descriptors by chromatographic methods.

PubMed

Poole, Colin F; Atapattu, Sanka N; Poole, Salwa K; Bell, Andrea K

2009-10-12

The solvation parameter model is now well established as a useful tool for obtaining quantitative structure-property relationships for chemical, biomedical and environmental processes. The model correlates a free-energy related property of a system to six free-energy derived descriptors describing molecular properties. These molecular descriptors are defined as L (gas-liquid partition coefficient on hexadecane at 298K), V (McGowan's characteristic volume), E (excess molar refraction), S (dipolarity/polarizability), A (hydrogen-bond acidity), and B (hydrogen-bond basicity). McGowan's characteristic volume is trivially calculated from structure and the excess molar refraction can be calculated for liquids from their refractive index and easily estimated for solids. The remaining four descriptors are derived by experiment using (largely) two-phase partitioning, chromatography, and solubility measurements. In this article, the use of gas chromatography, reversed-phase liquid chromatography, micellar electrokinetic chromatography, and two-phase partitioning for determining solute descriptors is described. A large database of experimental retention factors and partition coefficients is constructed after first applying selection tools to remove unreliable experimental values and an optimized collection of varied compounds with descriptor values suitable for calibrating chromatographic systems is presented. These optimized descriptors are demonstrated to be robust and more suitable than other groups of descriptors characterizing the separation properties of chromatographic systems.

Chromatographic performance of synthetic polycrystalline diamond as a stationary phase in normal phase high performance liquid chromatography.

PubMed

Peristyy, Anton; Paull, Brett; Nesterenko, Pavel N

2015-04-24

The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated in normal phase mode of high performance liquid chromatography. Purified nonporous irregular shape particles of average particles size 1.2 μm and specific surface area 5.1 m(2) g(-1) were used for packing 100×4.6 mm ID or 50×4.6 mm ID stainless steel columns. The retention behaviour of several classes of compounds including alkyl benzenes, polyaromatic hydrocarbons (PAH), alkylphenylketones, phenols, aromatic acids and bases were studied using n-hexane-2-propanol mixtures as mobile phase. The results are compared with those observed for microdispersed sintered detonation nanodiamond (MSDN) and porous graphitic carbon (PGC). HPHT diamond revealed distinctive separation selectivity, which is orthogonal to that observed for porous graphitic carbon; while selectivities of HPHT diamond and microdispersed sintered detonation nanodiamonds are similar. Owing to non-porous particle nature, columns packed with high pressure high temperature diamond exhibited excellent mass transfer and produce separations with maximum column efficiency of 128,200 theoretical plates per meter. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of solid dispersions of itraconazole and hydroxypropylmethylcellulose prepared by melt extrusion, Part II.

PubMed

Six, Karel; Berghmans, Hugo; Leuner, Christian; Dressman, Jennifer; Van Werde, Kristof; Mullens, Jules; Benoist, Luc; Thimon, Mireille; Meublat, Laurent; Verreck, Geert; Peeters, Jef; Brewster, Marcus; Van den Mooter, Guy

2003-07-01

This study was done to elucidate the physical and pharmaceutical properties of itraconazole-HPMC dispersions and the influence of water on the phase separation. Extrudates were prepared using a corotating twin-screw hot-stage extruder with fixed process parameters. Modulated-temperature differential scanning calorimetry (MTDSC) and DSC 111 were used to examine the mixing behavior of itraconazole and the carrier by evaluation of the glass transition region. High temperature diffuse reflectance infrared transform spectroscopy (HT-DRIFT) was performed to reveal interactions between itraconazole and HPMC. Dissolution was performed to investigate the pharmaceutical performance of the dispersions. Although the dissolution rate of itraconazole significantly increased, we found that the solid dispersions do not form a homogeneous system. A different picture was obtained depending on the way MTDSC analysis was performed, i.e., using open or closed sample pans. Water can evaporate in open pans, which allows itraconazole to interact with HPMC and leads to a partially mixed phase. Analysis in hermetically closed pans revealed a further phase separation as water remains on the sample and impedes the interaction between drug and polymer. Solid dispersions of itraconazole and HPMC do not form a homogeneous phase.

Cytoplasmic membrane response to copper and nickel in Acidithiobacillus ferrooxidans.

PubMed

Mykytczuk, N C S; Trevors, J T; Ferroni, G D; Leduc, L G

2011-03-20

Metal tolerance has been found to vary among Acidithiobacillus ferrooxidans strains and this can impact the efficiency of biomining practices. To explain observed strain variability for differences in metal tolerance we examined the effects of Cu(2+) and Ni(2+) concentrations (1-200 mM) on cytoplasmic membrane properties of two A. ferrooxidans type strains (ATCC 23270 and 19859) and four strains isolated from AMD water around Sudbury, Ontario, Canada. Growth rate, membrane fluidity and phase, determined from the fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH), and fatty acid profiles indicated that three different modes of adaptation were present and could separate between strains showing moderate, or high metal tolerance from more sensitive strains. To compensate for the membrane ordering effects of the metals, significant remodelling of the membrane was used to either maintain homeoviscous adaptation in the moderately tolerant strains or to increase membrane fluidity in the sensitive strains. Shifts in the gel-to-liquid crystalline transition temperature in the moderately tolerant strains led to multiple phase transitions, increasing the potential for phase separation and compromised membrane integrity. The metal-tolerant strain however, was able to tolerate increases in membrane order without significant compensation via fatty acid composition. Our multivariate analyses show a common adaptive response which involves changes in the abundant 16:0 and 18:1 fatty acids. However, fatty acid composition and membrane properties showed no difference in response to either copper or nickel suggesting that adaptive response was non-specific and tolerance dependent. We demonstrate that strain variation can be evaluated using differences in membrane properties as intrinsic determinants of metal susceptibility. Copyright © 2010 Elsevier GmbH. All rights reserved.

The MODIS cloud optical and microphysical products: Collection 6 updates and examples from Terra and Aqua.

PubMed

Platnick, Steven; Meyer, Kerry G; King, Michael D; Wind, Galina; Amarasinghe, Nandana; Marchant, Benjamin; Arnold, G Thomas; Zhang, Zhibo; Hubanks, Paul A; Holz, Robert E; Yang, Ping; Ridgway, William L; Riedi, Jérôme

2017-01-01

The MODIS Level-2 cloud product (Earth Science Data Set names MOD06 and MYD06 for Terra and Aqua MODIS, respectively) provides pixel-level retrievals of cloud-top properties (day and night pressure, temperature, and height) and cloud optical properties (optical thickness, effective particle radius, and water path for both liquid water and ice cloud thermodynamic phases-daytime only). Collection 6 (C6) reprocessing of the product was completed in May 2014 and March 2015 for MODIS Aqua and Terra, respectively. Here we provide an overview of major C6 optical property algorithm changes relative to the previous Collection 5 (C5) product. Notable C6 optical and microphysical algorithm changes include: (i) new ice cloud optical property models and a more extensive cloud radiative transfer code lookup table (LUT) approach, (ii) improvement in the skill of the shortwave-derived cloud thermodynamic phase, (iii) separate cloud effective radius retrieval datasets for each spectral combination used in previous collections, (iv) separate retrievals for partly cloudy pixels and those associated with cloud edges, (v) failure metrics that provide diagnostic information for pixels having observations that fall outside the LUT solution space, and (vi) enhanced pixel-level retrieval uncertainty calculations. The C6 algorithm changes collectively can result in significant changes relative to C5, though the magnitude depends on the dataset and the pixel's retrieval location in the cloud parameter space. Example Level-2 granule and Level-3 gridded dataset differences between the two collections are shown. While the emphasis is on the suite of cloud optical property datasets, other MODIS cloud datasets are discussed when relevant.

Heteroaggregation of lipid droplets coated with sodium caseinate and lactoferrin.

PubMed

de Figueiredo Furtado, Guilherme; Michelon, Mariano; de Oliveira, Davi Rocha Bernardes; da Cunha, Rosiane Lopes

2016-11-01

Formation and characterization of droplet heteroaggregates were investigated by mixing two emulsions previously stabilized by proteins oppositely charged. Emulsions were composed of 5vol.% of sunflower oil and 95vol.% of sodium caseinate or lactoferrin aqueous dispersions. They were produced using ultrasound with fixed power (300W) and sonication time (6min). Different volume ratios (0-100%) of sodium caseinate-stabilized emulsion (droplet diameter around 1.75μm) to lactoferrin-stabilized emulsion (droplet diameter around 1.55μm) were mixed under conditions that both proteins showed opposite charges (pH7). Influence of ionic strength (0-400mM NaCl) on the heteroaggregates stability was also evaluated. Creaming stability, zeta potential, microstructure, mean particle diameter and rheological properties of the heteroaggregates were measured. These properties depended on the volume ratio (0-100%) of sodium caseinate to lactoferrin-stabilized emulsion (C:L) and the ionic strength. In the absence of salt, different zeta potential values were obtained, rheological properties (viscosity and elastic moduli) were improved and the largest heteroaggregates were formed at higher content of lactoferrin-stabilized emulsion (60-80%). The system containing 40 and 60vol.% of sodium caseinate and lactoferrin stabilized emulsion, respectively, presented good stability against phase separation besides showing enhanced rheological and size properties due to extensive droplets aggregation. Phase separation was observed only in the absence of sodium caseinate, demonstrating the higher susceptibility of lactoferrin to NaCl. The heteroaggregates produced may be useful functional agents for texture modification and controlled release since different rheological properties and sizes can be achieved depending on protein concentrations. Copyright © 2016 Elsevier Ltd. All rights reserved.

Magnetic imaging of antiferromagnetic and superconducting phases in R bxF e2 -yS e2 crystals

NASA Astrophysics Data System (ADS)

Hazi, J.; Mousavi, T.; Dudin, P.; van der Laan, G.; Maccherozzi, F.; Krzton-Maziopa, A.; Pomjakushina, E.; Conder, K.; Speller, S. C.

2018-02-01

High-temperature superconducting (HTS) cuprate materials, with the ability to carry large electrical currents with no resistance at easily reachable temperatures, have stimulated enormous scientific and industrial interest since their discovery in the 1980's. However, technological applications of these promising compounds have been limited by their chemical and microstructural complexity and the challenging processing strategies required for the exploitation of their extraordinary properties. The lack of theoretical understanding of the mechanism for superconductivity in these HTS materials has also hindered the search for new superconducting systems with enhanced performance. The unexpected discovery in 2008 of HTS iron-based compounds has provided an entirely new family of materials for studying the crucial interplay between superconductivity and magnetism in unconventional superconductors. Alkali-metal-doped iron selenide (AxF e2 -yS e2 , A =alkali metal ) compounds are of particular interest owing to the coexistence of superconductivity at relatively high temperatures with antiferromagnetism. Intrinsic phase separation on the mesoscopic scale is also known to occur in what were intended to be single crystals of these compounds, making it difficult to interpret bulk property measurements. Here, we use a combination of two advanced microscopy techniques to provide direct evidence of the magnetic properties of the individual phases. First, x-ray linear dichroism studies in a photoelectron emission microscope, and supporting multiplet calculations, indicate that the matrix (majority) phase is antiferromagnetic whereas the minority phase is nonmagnetic at room temperature. Second, cryogenic magnetic force microscopy demonstrates unambiguously that superconductivity occurs only in the minority phase. The correlation of these findings with previous microstructural studies and bulk measurements paves the way for understanding the intriguing electronic and magnetic properties of these compounds.

Functional Nanostructured Materials Based on Polymerized Surfactant Liquid Crystal Assemblies Liquid Crystal Assemblies

NASA Astrophysics Data System (ADS)

Gin, Douglas

2003-03-01

The development of materials with controlled nanostructures is one of the most important new areas of scientific research in chemistry and engineering. Our research group has developed a novel approach for making nanostructured polymer materials with unique functional properties using liquid crystals as starting materials. In this approach, we design polymerizable organic building blocks based on lyotropic liquid crystals (LLCs) (i.e., amphiphiles or surfactants) that carry, or can accommodate, a functional property of general interest. Through appropriate molecular design, these monomers self-assemble in the presence of water into fluid, yet ordered phase-separated, water-hydrocarbon assemblies with predictable nanoscale geometries. The architectures of these LLC phases can range from stacked two-dimensional lamellae to hexagonally ordered cylindrical channels with uniform feature sizes in the 1-10 nm range. These LLC phases are then photopolymerized into robust polymer networks with preservation of their small-scale structures. This approach allows us to investigate the effect of nanometer-scale architecture on important bulk properties, as well as to engineer chemical environments on the nanometer-scale for several areas of application. In this talk, new functional materials based on the polymerization of the lyotropic inverted hexagonal phase will be presented as one example of our general approach. Issues in the design and photopolymerization of functional amphiphilic monomers that adopt this LC architecture will be discussed. More importantly, the use of the resulting nanostructured polymer networks in three areas of application will be presented: (1) as templates for the synthesis of functional nanocomposites; (2) as tunable heterogeneous catalysts, and (3) as nanoporous membrane and separation media. In particular, issues pertaining to the contribution of nanoscale architecture to the performance of these systems will be highlighted. Opportunities for tailoring the nanoscale chemical environment and architecture of these materials through molecular design will be presented. Finally, the development of methods for controlling macroscopic orientation through processing will also be discussed.

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.

Study on tensile properties constitutive model of polyurethane fibers with different isocyanate index

NASA Astrophysics Data System (ADS)

You, Gexin; Liu, Xinsen; Chen, Xiri; Yang, Bo; Zhou, Xiuwen

2018-06-01

In this study, a two-element model consisting of a non-linear spring and a viscous dashpot was proposed to simulate tensile curve of polyurethane fibers. The results showed that the two-element model can simulate the tensile curve of the polyurethane fibers better with a simple and applicable feature compared to the existing three-element model and four-element model. The effects of isocyanate index (R) on the hydrogen bond (H-bond) and the micro-phase separation of polyurethane fibers were investigated by Fourier transform infrared spectroscopy and x-ray pyrometer, respectively. The degree of H-bond and micro-phase separation increased first and then decreased as the R value increased, and gain a maximum at the value of 1.76, which is in good agreement with parameters viscosity coefficient η and the initial modulus c in the model.

Crystal nuclei templated nanostructured membranes prepared by solvent crystallization and polymer migration

NASA Astrophysics Data System (ADS)

Wang, Bo; Ji, Jing; Li, Kang

2016-09-01

Currently, production of porous polymeric membranes for filtration is predominated by the phase-separation process. However, this method has reached its technological limit, and there have been no significant breakthrough over the last decade. Here we show, using polyvinylidene fluoride as a sample polymer, a new concept of membrane manufacturing by combining oriented green solvent crystallization and polymer migration is able to obtain high performance membranes with pure water permeation flux substantially higher than those with similar pore size prepared by conventional phase-separation processes. The new manufacturing procedure is governed by fewer operating parameters and is, thus, easier to control with reproducible results. Apart from the high water permeation flux, the prepared membranes also show excellent stable flux after fouling and superior mechanical properties of high pressure load and better abrasion resistance. These findings demonstrate the promise of a new concept for green manufacturing nanostructured polymeric membranes with high performances.

The structure of evaporating and combusting sprays: Measurements and predictions

NASA Technical Reports Server (NTRS)

Shuen, J. S.; Solomon, A. S. P.; Faeth, F. M.

1983-01-01

The structure of particle-laden jets and nonevaporating and evaporating sprays was measured in order to evaluate models of these processes. Three models are being evaluated: (1) a locally homogeneous flow model, where slip between the phases is neglected and the flow is assumed to be in local thermodynamic equilibrium; (2) a deterministic separated flow model, where slip and finite interphase transport rates are considered but effects of particle/drop dispersion by turbulence and effects of turbulence on interphase transport rates are ignored; and (3) a stochastic separated flow model, where effects of interphase slip, turbulent dispersion and turbulent fluctuations are considered using random sampling for turbulence properties in conjunction with random-walk computations for particle motion. All three models use a k-e-g turbulence model. All testing and data reduction are completed for the particle laden jets. Mean and fluctuating velocities of the continuous phase and mean mixture fraction were measured in the evaporating sprays.

Composition and temperature dependence of the dielectric, piezoelectric and elastic properties of pure PZT ceramics.

PubMed

Zhuang, Z Q; Haun, M J; Jang, S J; Cross, L E

1989-01-01

Pure (undoped) piezoelectric lead zirconate titanate (PZT) ceramic samples at compositions across the ferroelectric region of the phase diagram were prepared from sol-gel-derived fine powders. Excess lead oxide was included in the PZT powders to obtain dense (95-96% of theoretical density) ceramics with large grain size (>7 mum) and to control the lead stoichiometry. The dielectric, piezoelectric, and elastic properties were measured from 4.2 to 300 K. At very low temperatures, the extrinsic domain wall and thermal defect motions freeze out. The low-temperature dielectric data can be used to determine coefficients in a phenomenological theory. The extrinsic contribution to the properties can then be separated from the single-domain properties derived from the theory.

Anomalous nanoclusters, anisotropy, and electronic nematicity in the doped manganite L a 1 / 3 C a 2 / 3 Mn O 3

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

Tao, J.; Sun, K.; Tranquada, J. M.

In doped manganites, a superlattice (SL) modulation associated with charge/orbital ordering is accepted as a key component in understanding many intriguing properties. It has been reported that the SL modulation always appears on the a axis of the crystals. Here in this study, by using multiple transmission electron microscopic techniques, we observe a type of anomalous nanocluster in which the SL modulation appears on the c axis of La 1/3Ca 2/3MnO 3. By correlating the thermal evolution of the anomalous nanoclusters to other property measurements, we suggest that strain is responsible for the formation of the anomalous nanoclusters. The phasemore » separation and phase transition scenario in La 1/3Ca 2/3MnO 3 are also described using electronic-liquid-crystal (ELC) phases. Lastly, an ELC phase diagram in La 1/3Ca 2/3MnO 3 is constructed as a function of temperature based on our observations.« less

Dielectric and impedance properties of NiFe1.95R0.05O4 (R = Y, Yb and Lu)

NASA Astrophysics Data System (ADS)

Ugendar, Kodam; Kumar, Hanuma; Markaneyulu, G.; Rani, G. Neeraja

2018-04-01

The dielectric and impedance spectroscopic properties of NiFe1.95R0.05O4 (R = Y, Yb and Lu) were investigated. The materials were prepared by solid state reaction and crystallized in the cubic inverse spinel phase with a very small amount additional phase of RFeO3 (R = Y, Yb and Lu) as secondary phase. The scanning electron micrograph images clearly show grains (˜2μm) which are separated by thin grain boundaries. The presences of all elements were confirmed by the energy dispersive X-ray elemental mapping. The frequency variation of ɛ' shows the dispersion, following the Koop's phenomenological theory, which considers the dielectric structure as an inhomogeneous medium of two-layers of the Maxwell-Wagner type. Impedance spectroscopic analysis indicates the different relaxation mechanisms, which corresponds to bulk grain and grain-boundaries. Their contributions to the electrical conductivity and capacitance of these materials were discussed in detailed.

Anomalous nanoclusters, anisotropy, and electronic nematicity in the doped manganite L a 1 / 3 C a 2 / 3 Mn O 3

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

Tao, J.; Sun, K.; Tranquada, J. M.

2017-06-07

In doped manganites, a superlattice (SL) modulation associated with charge/orbital ordering is accepted as a key component in understanding many intriguing properties. It has been reported that the SL modulation always appears on the a axis of the crystals. Here in this study, by using multiple transmission electron microscopic techniques, we observe a type of anomalous nanocluster in which the SL modulation appears on the c axis of La 1/3Ca 2/3MnO 3. By correlating the thermal evolution of the anomalous nanoclusters to other property measurements, we suggest that strain is responsible for the formation of the anomalous nanoclusters. The phasemore » separation and phase transition scenario in La 1/3Ca 2/3MnO 3 are also described using electronic-liquid-crystal (ELC) phases. Lastly, an ELC phase diagram in La 1/3Ca 2/3MnO 3 is constructed as a function of temperature based on our observations.« less

Andreev rectifier: A nonlocal conductance signature of topological phase transitions

NASA Astrophysics Data System (ADS)

Rosdahl, T. Ö.; Vuik, A.; Kjaergaard, M.; Akhmerov, A. R.

2018-01-01

The proximity effect in hybrid superconductor-semiconductor structures, crucial for realizing Majorana edge modes, is complicated to control due to its dependence on many unknown microscopic parameters. In addition, defects can spoil the induced superconductivity locally in the proximitized system, which complicates measuring global properties with a local probe. We show how to use the nonlocal conductance between two spatially separated leads to probe three global properties of a proximitized system: the bulk superconducting gap, the induced gap, and the induced coherence length. Unlike local conductance spectroscopy, nonlocal conductance measurements distinguish between nontopological zero-energy modes localized around potential inhomogeneities, and true Majorana edge modes that emerge in the topological phase. In addition, we find that the nonlocal conductance is an odd function of bias at the topological phase transition, acting as a current rectifier in the low-bias limit. More generally, we identify conditions for crossed Andreev reflection to dominate the nonlocal conductance and show how to design a Cooper pair splitter in the open regime.

Engineered Multifunctional Surfaces for Fluid Handling

NASA Technical Reports Server (NTRS)

Thomas, Chris; Ma, Yonghui; Weislogel, Mark

2012-01-01

Designs incorporating variations in capillary geometry and hydrophilic and/or antibacterial surface properties have been developed that are capable of passive gas/liquid separation and passive water flow. These designs can incorporate capillary grooves and/or surfaces arranged to create linear and circumferential capillary geometry at the micro and macro scale, radial fin configurations, micro holes and patterns, and combinations of the above. The antibacterial property of this design inhibits the growth of bacteria or the development of biofilm. The hydrophilic property reduces the water contact angle with a treated substrate such that water spreads into a thin layer atop the treated surface. These antibacterial and hydrophilic properties applied to a thermally conductive surface, combined with capillary geometry, create a novel heat exchanger capable of condensing water from a humid, two-phase water and gas flow onto the treated heat exchanger surfaces, and passively separating the condensed water from the gas flow in a reduced gravity application. The overall process to generate the antibacterial and hydrophilic properties includes multiple steps to generate the two different surface properties, and can be divided into two major steps. Step 1 uses a magnetron-based sputtering technique to implant the silver atoms into the base material. A layer of silver is built up on top of the base material. Completion of this step provides the antibacterial property. Step 2 uses a cold-plasma technique to generate the hydrophilic surface property on top of the silver layer generated in Step 1. Completion of this step provides the hydrophilic property in addition to the antibacterial property. Thermally conductive materials are fabricated and then treated to create the antibacterial and hydrophilic surface properties. The individual parts are assembled to create a condensing heat exchanger with antibacterial and hydrophilic surface properties and capillary geometry, which is capable of passive phase separation in a reduced gravity application. The plasma processes for creating antibacterial and hydrophilic surface properties are suitable for applications where water is present on an exposed surface for an extended time, such that bacteria or biofilms could form, and where there is a need to manage the water on the surface. The processes are also suitable for applications where only the hydrophilic property is needed. In particular, the processes are applicable to condensing heat exchangers (CHXs), which benefit from the antibacterial properties as well as the hydrophilic properties. Water condensing onto the control surfaces of the CHX will provide the moist conditions necessary for the growth of bacteria and the formation of biofilms. The antibacterial properties of the base layer (silver) will mitigate and prevent the growth of bacteria and formation of biofilms that would otherwise reduce the CHX performance. In addition, the hydrophilic properties reduce the water contact angle and prevent water droplets from bridging between control surfaces. Overall, the hydrophilic properties reduce the pressure drop across the CHX.

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2014-01-01

The Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model is designed to be modular with different user options depending on the computing time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption on the aqueous phase of particles, activity coefficients, phase separation). Each surrogate can be hydrophilic (condenses only on the aqueous phase of particles), hydrophobic (condenses only on the organic phase of particles) or both (condenses on both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC thermodynamic model for short-range interactions and with the AIOMFAC parameterization for medium and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium and a dynamic representation of the organic aerosol. In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol (OA) is not at equilibrium with the gas phase because the organic phase could be semi-solid (very viscous liquid phase). The condensation or evaporation of organic compounds could then be limited by the diffusion in the organic phase due to the high viscosity. A dynamic representation of secondary organic aerosols (SOA) is used with OA divided into layers, the first layer at the center of the particle (slowly reaches equilibrium) and the final layer near the interface with the gas phase (quickly reaches equilibrium).

[Synthesis of porous spherical silicon oxynitride material and evaluation of its properties in reversed-phase chromatographic separation].

PubMed

Zhong, Hongmin; Zhang, Hua; Wan, Huihui

2013-04-01

Silica has been widely used as HPLC column packing material. However, the fact that base can attack the silanol and dissolve the silica embarrasses the utilization of silica stationary phase in high pH mobile phases (pH >8). In our previous research, the use of porous spherical silicon oxynitride (sph-SiON) material from high temperature nitridation of silica microspheres as stationary phase for HPLC has been explored, and the sph-SiON is stable to alkaline mobile phases and demonstrates excellent separation of a variety of polar compounds in hydrophilic interaction liquid chromatography (HILIC) mode. Herein, the degree of nitridation was studied as a function of temperature of nitridation at 750-1 050 degrees C, yielding the silicon oxynitride with 0.40%-12.0% (mass fraction) nitrogen from elemental analysis. At the temperature of 1 050 degrees C, the nitrogen content increased from 12.0% to 24.5% with the nitridation time increasing from 20 h to 120 h. The sph-SiON is stable when disposed in different pH aqueous solutions for one week. The sph-SiON material can be modified to give hydrophobic surface through the reaction of surface Si-NHx with dimethyloctadecylchlorosilane. Elemental analysis and 13C cross-polarization magic-angle spinning (CP/MAS) NMR spectrum of C18-sph-SiON prove the integration of C18 alkyl groups attached onto the sph-SiON surface. The chromatographic evaluation of C18-sph-SiON in reversed-phase separation mode was performed with alkylbenzenes as hydrophobic probes. Three alkylbenzene compounds can be separated and retained well on C18-sph-SiON even in the mobile phase of methanol/H2O (70/30, v/v) with 78 507 plates/m, and an excellent tailing factor (0.95) can be obtained for ethylbenzene. In comparison with C18-SiO2, C18-sph-SiON shows distinct differences with respect to different classes of analytes, i. e. neutral analyte naphthalene, acidic analyte ibuprofen, and basic analyte amitriptyline.

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

PubMed

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

2015-01-01

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

Phase shift of oscillatory magnetoresistance in a double-cross thin film structure of La0.3Pr0.4Ca0.3MnO3 via strain-engineered elongation of electronic domains

NASA Astrophysics Data System (ADS)

Alagoz, H. S.; Prasad, B.; Jeon, J.; Blamire, M. G.; Chow, K. H.; Jung, J.

2018-02-01

The subtle balance between the competing electronic phases in manganites due to complex interplay between spin, charge, and orbital degrees of freedom could allow one to modify the properties of electronically phase separated systems. In this paper, we show that the phase shift in the oscillatory magnetoresistance ρ (θ ) can be modified by engineering strain driven elongation of electronic domains in La0.3Pr0.4Ca0.3MnO3 (LPCMO) thin films. Strain-driven elongation of magnetic domains can produce different percolation paths and hence different anisotropic magnetoresistance responses. This tunability provides a unique control that is unattainable in conventional 3 d ferromagnetic metals and alloys.

Room temperature ionic liquids: new GC stationary phases with a novel selectivity for flavor and fragrance analyses.

PubMed

Cagliero, Cecilia; Bicchi, Carlo; Cordero, Chiara; Liberto, Erica; Sgorbini, Barbara; Rubiolo, Patrizia

2012-12-14

Ionic liquids (ILs) are of great interest as moderately polar to polar stationary phases for GC, because their selectivity differs markedly from that of conventionally used phases. In the flavor, fragrance and essential oil fields, analysts often deal with complex mixtures of compounds having similar structural and physical characteristics (e.g., mono- and sesquiterpenoids), therefore requiring an interactive combination between chromatographic and mass spectral data for correct identification. New GC stationary phases with different selectivity must therefore be continually tested. Performance and evolution over time of commercially available IL columns versus those commonly used in these fields are here evaluated, mainly in view of their routine use. Chromatographic and separative properties (efficiency, separation capability, inertness and/or activity) of commercially available IL columns were compared to those of columns coated with 5% phenyl-95% methylpolysiloxane, 14% cyanopropyl-86% polysiloxane, and polyethylene glycol, on different complexity samples, including standard mixtures of volatile suspected allergens and pesticides, and cornmint and vetiver essential oils. The results show that IL columns can successfully be used for a wide range of applications characteristic of these fields, mainly because of their unusual selectivity, in particular when separations based on functional groups are required. Moreover, the latest generation of IL columns (IL61 and IL60) presents chromatographic performance comparable to or only slightly lower than that of the conventional columns routinely used in these fields. Copyright © 2012 Elsevier B.V. All rights reserved.

Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a semi-pilot scale auger pyrolyzer

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

Ren, Shoujie; Ye, X. Philip; Borole, Abhijeet P.

To efficiently utilize water-soluble compounds in bio-oil and evaluate the potential effects of these compounds on processes such as microbial electrolysis, our study investigated the physico-chemical properties of bio-oil and the associated aqueous phase generated from switchgrass using a semi-pilot scale auger pyrolyzer. Combining separation and detection strategies with organic solvent extraction, an array of analytical instruments and methods were used to identify and quantify the chemical constituents. Separation of an aqueous phase from crude bio-oil was achieved by adding water (water: crude bio-oil at 4:1 in weight), which resulted in a partition of 61 wt.% of the organic compoundsmore » into a bio-oil aqueous phase (BOAP). GC/MS analysis for BOAP identified over 40 compounds of which 16 were quantified. Acetic acid, propionic acid, and levoglucosan are the major components in BOAP. In addition, a significant portion of chemicals that have the potential to be upgraded to hydrocarbon fuels were extracted to BOAP (77 wt.% of the alcohols, 61 wt.% of the furans, and 52 wt.% of the phenolic compounds in crude bio-oil). Valorization of the BOAP may require conversion methods capable of accommodating a very broad substrate specificity. Ultimately, a better separation strategy is needed to selectively remove the acidic and polar components from crude bio-oil to improve economic feasibility of biorefinery operations.« less

Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a semi-pilot scale auger pyrolyzer

DOE PAGES

Ren, Shoujie; Ye, X. Philip; Borole, Abhijeet P.; ...

2016-03-30

To efficiently utilize water-soluble compounds in bio-oil and evaluate the potential effects of these compounds on processes such as microbial electrolysis, our study investigated the physico-chemical properties of bio-oil and the associated aqueous phase generated from switchgrass using a semi-pilot scale auger pyrolyzer. Combining separation and detection strategies with organic solvent extraction, an array of analytical instruments and methods were used to identify and quantify the chemical constituents. Separation of an aqueous phase from crude bio-oil was achieved by adding water (water: crude bio-oil at 4:1 in weight), which resulted in a partition of 61 wt.% of the organic compoundsmore » into a bio-oil aqueous phase (BOAP). GC/MS analysis for BOAP identified over 40 compounds of which 16 were quantified. Acetic acid, propionic acid, and levoglucosan are the major components in BOAP. In addition, a significant portion of chemicals that have the potential to be upgraded to hydrocarbon fuels were extracted to BOAP (77 wt.% of the alcohols, 61 wt.% of the furans, and 52 wt.% of the phenolic compounds in crude bio-oil). Valorization of the BOAP may require conversion methods capable of accommodating a very broad substrate specificity. Ultimately, a better separation strategy is needed to selectively remove the acidic and polar components from crude bio-oil to improve economic feasibility of biorefinery operations.« less

Applications of alginate in bioseparation of proteins.

PubMed

Jain, Sulakshana; Mondal, Kalyani; Gupta, Munishwar N

2006-01-01

Alginate is a polysaccharide that is a block polymer consisting of block units of guluronic acid and mannuronic acid. It shows inherent biological affinity for a variety of enzymes such as pectinase, lipase, phospholipase D, a and ss amylases and glucoamylase. Taking advantage of its precipitation with Ca2+ and the above-mentioned property, alginate has been used for purification of these enzymes by affinity precipitation, aqueous two phase separation, macroaffinity ligand facilitated three phase partitioning, immobilized metal affinity chromatography and expanded bed affinity chromatography. Thus, this versatile marine resource has tremendous potential in bioseparation of proteins.

Accurate Theoretical Predictions of the Properties of Energetic Materials

DTIC Science & Technology

2008-09-18

decomposition, Monte Carlo, molecular dynamics, supercritical fluids, solvation and separation, quantum Monte Carlo, potential energy surfaces, RDX , TNAZ...labs, who are contributing to the theoretical efforts, providing data for testing of the models, or aiding in the transition of the methods, models...and results to DoD applications. The major goals of the project are: • Models that describe phase transitions and chemical reactions in

Processing of Mixed Oxide Superconductors

DTIC Science & Technology

1990-07-01

rapid changes world wide a major research centre on high Tc superconductors was awarded to Cambridge which involved moving the work and people to a...reports and paper is in the appendices. Separation Ceramic superconductors tend to be mixtures of phases, especially when first discovered. It would...properties of the superconducting state will in principle allow superconducting material to be levitated from the non superconductor and several designs

Relationship of Interfacial Compatibility to Durability of Adhesive - Bonded Joints

DTIC Science & Technology

1981-03-01

same as BR-238, but with the nitrile rubber removed. Because the phenolic matrix resin has different binding properties to the elastomer than do the...primer, which formed phase separated rubber particles having poor mechanical linkage with the matrix resin , resulted in significant loss in shear...having good mechanical linkage with the matrix resin , resulted in good shear strength retention andsignificantly increased toughness. An adhesive

Thermodynamics of Thomas-Fermi screened Coulomb systems

NASA Technical Reports Server (NTRS)

Firey, B.; Ashcroft, N. W.

1977-01-01

We obtain in closed analytic form, estimates for the thermodynamic properties of classical fluids with pair potentials of Yukawa type, with special reference to dense fully ionized plasmas with Thomas-Fermi or Debye-Hueckel screening. We further generalize the hard-sphere perturbative approach used for similarly screened two-component mixtures, and demonstrate phase separation in this simple model of a liquid mixture of metallic helium and hydrogen.

Magnetic dynamic properties of electron-doped La(0.23)Ca(0.77)MnO3 nanoparticles.

PubMed

Dolgin, B; Puzniak, R; Mogilyansky, D; Wisniewski, A; Markovich, V; Jung, G

2013-02-20

Magnetic properties of basically antiferromagnetic La(0.23)Ca(0.77)MnO(3) particles with average sizes of 12 and 60 nm have been investigated in a wide range of magnetic fields and temperature. Particular attention has been paid to magnetization dynamics through measurements of the temperature dependence of ac-susceptibility at various frequencies, the temperature and field dependence of thermoremanent and isothermoremanent magnetization originating from nanoparticles shells, and the time decay of the remanent magnetization. Experimental results and their analysis reveal the major role in magnetic behaviour of investigated antiferromagnetic nanoparticles played by the glassy component, associated mainly with the formation of the collective state formed by ferromagnetic clusters in frustrated coordination at the surfaces of interacting antiferromagnetic nanoparticles. Magnetic behaviour of nanoparticles has been ascribed to a core-shell scenario. Magnetic transitions have been found to play an important role in determining the dynamic properties of the phase separated state of coexisting different magnetic phases.

Development of high temperature nickel-base alloys for jet engine turbine bucket applications

NASA Technical Reports Server (NTRS)

Quigg, R. J.; Scheirer, S. T.

1965-01-01

A program has been initiated to develop a material with superior properties at elevated temperatures for utilization in turbine blade applications. A nickel-base superalloy can provide the necessary high temperature strength by using the maximum capability of the three available strengthening mechanisms - intermetallic gamma prime precipitation (Ni3Al), solid solution strengthening with refractory and precious metals, and stable carbide formations through the addition of strong carbide forming elements. A stress rupture test at 2000 deg F and 15,000 psi was formulated to approximate the desired properties. By adding varying amounts of refractory metals (Mo, W and Ta) it was possible to statistically analyze the effects of each in a basic superalloy composition containing fixed amounts of Co, Cr, C, B, Sr, and Ni at three separate levels of AL and Ta. Metallographic analysis correlated with the mechanical properties of the alloys; those with few strengthening phases were weak and ductile and those with excessive amounts of intermetallic phases present in undesirable morphologies were brittle.

Application of Statistical Thermodynamics To Predict the Adsorption Properties of Polypeptides in Reversed-Phase HPLC.

PubMed

Tarasova, Irina A; Goloborodko, Anton A; Perlova, Tatyana Y; Pridatchenko, Marina L; Gorshkov, Alexander V; Evreinov, Victor V; Ivanov, Alexander R; Gorshkov, Mikhail V

2015-07-07

The theory of critical chromatography for biomacromolecules (BioLCCC) describes polypeptide retention in reversed-phase HPLC using the basic principles of statistical thermodynamics. However, whether this theory correctly depicts a variety of empirical observations and laws introduced for peptide chromatography over the last decades remains to be determined. In this study, by comparing theoretical results with experimental data, we demonstrate that the BioLCCC: (1) fits the empirical dependence of the polypeptide retention on the amino acid sequence length with R(2) > 0.99 and allows in silico determination of the linear regression coefficients of the log-length correction in the additive model for arbitrary sequences and lengths and (2) predicts the distribution coefficients of polypeptides with an accuracy from 0.98 to 0.99 R(2). The latter enables direct calculation of the retention factors for given solvent compositions and modeling of the migration dynamics of polypeptides separated under isocratic or gradient conditions. The obtained results demonstrate that the suggested theory correctly relates the main aspects of polypeptide separation in reversed-phase HPLC.

Particle-laden swirling free jets: Measurements and predictions

NASA Technical Reports Server (NTRS)

Bulzan, D. L.; Shuen, J.-S.; Faeth, G. M.

1987-01-01

A theoretical and experimental investigation of single-phase and particle-laden weakly swirling jets was conducted. The jets were injected vertically downward from a 19 mm diameter tube with swirl numbers ranging from 0 to 0.33. The particle-laden jets had a single loading ratio (0.2) with particles having a SMD of 39 microns. Mean and fluctuating properties of both phases were measured using nonintrusive laser based methods while particle mass flux was measured using an isokinetic sampling probe. The continuous phase was analyzed using both a baseline kappa-epsilon turbulence model and an extended version with modifications based on the flux Richardson number to account for effects of streamline curvature. To highlight effects of interphase transport rates and particle/turbulence interactions, effects of the particles were analyzed as follows: (1) locally homogeneous flow (LHF) analysis, where interphase transport rates are assumed to be infinitely fast; (2) deterministic separated flow (DSF) analysis, where finite interphase transport rates are considered but particle/turbulence interactions are ignored; and (3) stochastic separated flow (SSF) analysis, where both effects are considered using random-walk computations.

Miscibility Studies on Polymer Blends Modified with Phytochemicals

NASA Astrophysics Data System (ADS)

Chandrasekaran, Neelakandan; Kyu, Thein

2009-03-01

The miscibility studies related to an amorphous poly(amide)/poly(vinyl pyrrolidone) [PA/PVP] blend with a crystalline phytochemical called ``Mangiferin'' is presented. Phytochemicals are plant derived chemicals which intrinsically possess multiple salubrious properties that are associated with prevention of diseases such as cancer, diabetes, cardiovascular disease, and hypertension. Incorporation of phytochemicals into polymers has shown to have very promising applications in wound healing, drug delivery, etc. The morphology of these materials is crucial to applications like hemodialysis, which is governed by thermodynamics and kinetics of the phase separation process. Hence, miscibility studies of PA/PVP blends with and without mangiferin have been carried out using dimethyl sulfoxide as a common solvent. Differential scanning calorimetry studies revealed that the binary PA/PVP blends were completely miscible at all compositions. However, the addition of mangiferin has led to liquid-liquid phase separation and liquid-solid phase transition in a composition dependent manner. Fourier transformed infrared spectroscopy was undertaken to determine specific interaction between the polymer constituents and the role of possible hydrogen bonding among three constituents will be discussed.

Hidden phase in a two-dimensional Sn layer stabilized by modulation hole doping

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

Ming, Fangfei; Mulugeta Amare, Daniel; Tu, Weisong

Semiconductor surfaces and ultrathin interfaces exhibit an interesting variety of two-dimensional quantum matter phases, such as charge density waves, spin density waves and superconducting condensates. Yet, the electronic properties of these broken symmetry phases are extremely difficult to control due to the inherent difficulty of doping a strictly two-dimensional material without introducing chemical disorder. Here we successfully exploit a modulation doping scheme to uncover, in conjunction with a scanning tunnelling microscope tip-assist, a hidden equilibrium phase in a hole-doped bilayer of Sn on Si(111). This new phase is intrinsically phase separated into insulating domains with polar and nonpolar symmetries. Itsmore » formation involves a spontaneous symmetry breaking process that appears to be electronically driven, notwithstanding the lack of metallicity in this system. This modulation doping approach allows access to novel phases of matter, promising new avenues for exploring competing quantum matter phases on a silicon platform.« less

Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

NASA Astrophysics Data System (ADS)

Tournier, Robert F.

2018-01-01

Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

Hidden phase in a two-dimensional Sn layer stabilized by modulation hole doping

DOE PAGES

Ming, Fangfei; Mulugeta Amare, Daniel; Tu, Weisong; ...

2017-03-07

Semiconductor surfaces and ultrathin interfaces exhibit an interesting variety of two-dimensional quantum matter phases, such as charge density waves, spin density waves and superconducting condensates. Yet, the electronic properties of these broken symmetry phases are extremely difficult to control due to the inherent difficulty of doping a strictly two-dimensional material without introducing chemical disorder. Here we successfully exploit a modulation doping scheme to uncover, in conjunction with a scanning tunnelling microscope tip-assist, a hidden equilibrium phase in a hole-doped bilayer of Sn on Si(111). This new phase is intrinsically phase separated into insulating domains with polar and nonpolar symmetries. Itsmore » formation involves a spontaneous symmetry breaking process that appears to be electronically driven, notwithstanding the lack of metallicity in this system. This modulation doping approach allows access to novel phases of matter, promising new avenues for exploring competing quantum matter phases on a silicon platform.« less

Pre-Combustion Carbon Dioxide Capture by a New Dual Phase Ceramic-Carbonate Membrane Reactor

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

Lin, Jerry Y. S.

2015-01-31

This report documents synthesis, characterization and carbon dioxide permeation and separation properties of a new group of ceramic-carbonate dual-phase membranes and results of a laboratory study on their application for water gas shift reaction with carbon dioxide separation. A series of ceramic-carbonate dual phase membranes with various oxygen ionic or mixed ionic and electronic conducting metal oxide materials in disk, tube, symmetric, and asymmetric geometric configurations was developed. These membranes, with the thickness of 10 μm to 1.5 mm, show CO 2 permeance in the range of 0.5-5×10 -7 mol·m -2·s -1·Pa -1 in 500-900°C and measured CO 2/N 2more » selectivity of up to 3000. CO 2 permeation mechanism and factors that affect CO 2 permeation through the dual-phase membranes have been identified. A reliable CO 2 permeation model was developed. A robust method was established for the optimization of the microstructures of ceramic-carbonate membranes. The ceramic-carbonate membranes exhibit high stability for high temperature CO 2 separations and water gas shift reaction. Water gas shift reaction in the dual-phase membrane reactors was studied by both modeling and experiments. It is found that high temperature syngas water gas shift reaction in tubular ceramic-carbonate dual phase membrane reactor is feasible even without catalyst. The membrane reactor exhibits good CO 2 permeation flux, high thermal and chemical stability and high thermal shock resistance. Reaction and separation conditions in the membrane reactor to produce hydrogen of 93% purity and CO 2 stream of >95% purity, with 90% CO 2 capture have been identified. Integration of the ceramic-carbonate dual-phase membrane reactor with IGCC process for carbon dioxide capture was analyzed. A methodology was developed to identify optimum operation conditions for a membrane tube of given dimensions that would treat coal syngas with targeted performance. The calculation results show that the dual-phase membrane reactor could improve IGCC process efficiency but the cost of the membrane reactor with membranes having current CO 2 permeance is high. Further research should be directed towards improving the performance of the membranes and developing cost-effective, scalable methods for fabrication of dual-phase membranes and membrane reactors.« less

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-08-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, Cj*, by including water and other inorganics in the absorbing phase. Such a Cj* definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.

Effect of Nd doping on structural, dielectric and thermodynamic properties of PZT (65/35) ceramic

NASA Astrophysics Data System (ADS)

Mohiddon, Md Ahamad; Kumar, Abhishek; Yadav, K. L.

2007-05-01

The influence of neodymium (Nd) addition on the phase formation and dielectric properties of Pb(Zr 0.65Ti 0.35)O 3 composition prepared from mixed oxide method was analyzed. Pellets were sintered in air and PbZrO 3 (PZ) atmosphere separately. Non-perovskite ZrO 2 phase was observed in samples which were sintered in air, also grain size was found to decrease with Nd doping in non-PZ environment samples. Decrease in transition temperature by 80 °C with increasing Nd concentration was observed in both set of samples. Maximum dielectric constant and dielectric losses are found to decrease with Nd doping. Complex impedance analysis revealed that grain boundary resistance increases with Nd doping. Thermodynamic parameters such as change in enthalpy, free energy and change in entropy were studied.

Topologically Diverse Human Membrane Proteins Partition to Liquid-Disordered Domains in Phase-Separated Lipid Vesicles.

PubMed

Schlebach, Jonathan P; Barrett, Paul J; Day, Charles A; Kim, Ji Hun; Kenworthy, Anne K; Sanders, Charles R

2016-02-23

The integration of membrane proteins into "lipid raft" membrane domains influences many biochemical processes. The intrinsic structural properties of membrane proteins are thought to mediate their partitioning between membrane domains. However, whether membrane topology influences the targeting of proteins to rafts remains unclear. To address this question, we examined the domain preference of three putative raft-associated membrane proteins with widely different topologies: human caveolin-3, C99 (the 99 residue C-terminal domain of the amyloid precursor protein), and peripheral myelin protein 22. We find that each of these proteins are excluded from the ordered domains of giant unilamellar vesicles containing coexisting liquid-ordered and liquid-disordered phases. Thus, the intrinsic structural properties of these three topologically distinct disease-linked proteins are insufficient to confer affinity for synthetic raft-like domains.

Liquid crystal Janus emulsion droplets: preparation, tumbling, and swimming.

PubMed

Jeong, Joonwoo; Gross, Adam; Wei, Wei-Shao; Tu, Fuquan; Lee, Daeyeon; Collings, Peter J; Yodh, A G

2015-09-14

This study introduces liquid crystal (LC) Janus droplets. We describe a process for the preparation of these droplets, which consist of nematic LC and polymer compartments. The process employs solvent-induced phase separation in emulsion droplets generated by microfluidics. The droplet morphology was systematically investigated and demonstrated to be sensitive to the surfactant concentration in the background phase, the compartment volume ratio, and the possible coalescence of multiple Janus droplets. Interestingly, the combination of a polymer and an anisotropic LC introduces new functionalities into Janus droplets, and these properties lead to unusual dynamical behaviors. The different densities and solubilities of the two compartments produce gravity-induced alignment, tumbling, and directional self-propelled motion of Janus droplets. LC Janus droplets with remarkable optical properties and dynamical behaviors thus offer new avenues for applications of Janus colloids and active soft matter.

In situ product removal in fermentation systems: improved process performance and rational extractant selection.

PubMed

Dafoe, Julian T; Daugulis, Andrew J

2014-03-01

The separation of inhibitory compounds as they are produced in biotransformation and fermentation systems is termed in situ product removal (ISPR). This review examines recent ISPR strategies employing several classes of extractants including liquids, solids, gases, and combined extraction systems. Improvement through the simple application of an auxiliary phase are tabulated and summarized to indicate the breadth of recent ISPR activities. Studies within the past 5 years that have highlighted and have discussed "second phase" properties, and that have an effect on fermentation performance, are particular focus of this review. ISPR, as a demonstrably effective processing strategy, continues to be widely adopted as more applications are explored; however, focus on the properties of extractants and their rational selection based on first principle considerations will likely be key to successfully applying ISPR to more challenging target molecules.

Phase separation and large deviations of lattice active matter

NASA Astrophysics Data System (ADS)

Whitelam, Stephen; Klymko, Katherine; Mandal, Dibyendu

2018-04-01

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

Emulsifying properties of acidic subunits of soy 11S globulin.

PubMed

Liu, M; Lee, D S; Damodaran, S

1999-12-01

The emulsifying properties of the acidic subunits (AS11S) isolated from soy glycinin (11S) have been studied. The isolated AS11S existed in solution mainly as a dimer species. Circular dichroic analysis indicated only a slight increase in aperiodic structure and no significant difference in beta-sheet structure when compared with those of soy 11S. At similar experimental conditions, the emulsifying properties of AS11S were superior to those of soy 11S and heat-denatured 11S. Emulsions prepared with 1% AS11S remained very stable without any visible oil separation for more than a month under gentle agitating conditions, whereas those prepared with 1% 11S collapsed and separated into phases within 2-3 days. The AS11S-stabilized emulsions were very stable below 0.15 M ionic strength. Studies on the rate of adsorption and surface tension reduction at the air-water interface showed that AS11S was significantly more surface active than soy 11S. It is proposed that, because the mass fraction of acidic subunits in soy 11S is approximately 60% and it is relatively easy to separate the acidic subunits from soy 11S, it may be industrially feasible to develop an economical process to isolate functional acidic subunits for use in emulsion-based food products.

Synthesis of the thermoelectric nanopowder recovered from the used thermoelectric modules.

PubMed

Lee, Kun-Jae; Jin, Yun-Ho; Kong, Man-Sik

2014-10-01

We fabricated the thermoelectric powder using the used thermoelectric modules in a vehicle. As a starting material, the used thermoelectric modules were collected and separated to substrate, electrode, solder, and thermoelectric parts by a thermal process. The separation process was performed in a wet process at the critical temperature. The solder in the module was the neighbor part of the thermoelectric material with the lowest melting temperature in the module. We focused on the thermal property of the solder to separate the thermoelectric chips in the module. After the separation process, we prepared the pure thermoelectric material by the chemical etching for an impurity removal. Also the thermoelectric nanopowder was fabricated by a chemical reduction reaction using the recycled thermoelectric materials. The recovered nanopowder was confirmed to the phase of bismuth telluride (Bi2Te3) with the particle size of -15 nm.

A solution-processed binary cathode interfacial layer facilitates electron extraction for inverted polymer solar cells.

PubMed

Zhang, Xinyuan; Li, Zhiqi; Liu, Chunyu; Guo, Jiaxin; Shen, Liang; Guo, Wenbin

2018-03-15

The charge transfer and separation are significantly affected by the electron properties of the interface between the electron-donor layer and the carrier-transporting layer in polymer solar cells (PSCs). In this study, we investigate the electron extraction mechanism of PSCs with a low temperature solution-processed ZnO/PEI as electron transport layer. The incorporation of PEI layer can decrease the work function of ZnO and reduce interfacial barrier, which facilitates electron extraction and suppresses bimolecular recombination, leading to a significant performance enhancement. Furthermore, PEI layer can induce phase separation and passivite inorganic surface trap states as well as shift the interfacial energy offset between metal oxide and organic materials. This work offers a simple and effective way to improve the charge transporting property of organic photovoltaic devices. Copyright © 2017 Elsevier Inc. All rights reserved.

Malic Acid Carbon Dots: From Super-resolution Live-Cell Imaging to Highly Efficient Separation.

PubMed

Zhi, Bo; Cui, Yi; Wang, Shengyang; Frank, Benjamin P; Williams, Denise N; Brown, Richard P; Melby, Eric S; Hamers, Robert J; Rosenzweig, Zeev; Fairbrother, D Howard; Orr, Galya; Haynes, Christy L

2018-06-15

As-synthesized malic acid carbon dots are found to possess photoblinking properties that are outstanding and superior compared to those of conventional dyes. Considering their excellent biocompatibility, malic acid carbon dots are suitable for super-resolution fluorescence localization microscopy under a variety of conditions, as we demonstrate in fixed and live trout gill epithelial cells. In addition, during imaging experiments, the so-called "excitation wavelength-dependent" emission was not observed for individual as-made malic acid carbon dots, which motivated us to develop a time-saving and high-throughput separation technique to isolate malic acid carbon dots into fractions of different particle size distributions using C 18 reversed-phase silica gel column chromatography. This post-treatment allowed us to determine how particle size distribution influences the optical properties of malic acid carbon dot fractions, that is, optical band gap energies and photoluminescence behaviors.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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

PubMed

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

2016-08-01

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

Singularity perturbed zero dynamics of nonlinear systems

NASA Technical Reports Server (NTRS)

Isidori, A.; Sastry, S. S.; Kokotovic, P. V.; Byrnes, C. I.

1992-01-01

Stability properties of zero dynamics are among the crucial input-output properties of both linear and nonlinear systems. Unstable, or 'nonminimum phase', zero dynamics are a major obstacle to input-output linearization and high-gain designs. An analysis of the effects of regular perturbations in system equations on zero dynamics shows that whenever a perturbation decreases the system's relative degree, it manifests itself as a singular perturbation of zero dynamics. Conditions are given under which the zero dynamics evolve in two timescales characteristic of a standard singular perturbation form that allows a separate analysis of slow and fast parts of the zero dynamics.

Graphene-based materials: fabrication and application for adsorption in analytical chemistry.

PubMed

Wang, Xin; Liu, Bo; Lu, Qipeng; Qu, Qishu

2014-10-03

Graphene, a single layer of carbon atoms densely packed into a honeycomb crystal lattice with unique electronic, chemical, and mechanical properties, is the 2D allotrope of carbon. Owing to the remarkable properties, graphene and graphene-based materials are likely to find potential applications as a sorbent in analytical chemistry. The current review focuses predominantly on the recent development of graphene-based materials and demonstrates their enhanced performance in adsorption of organic compounds, metal ions, and solid phase extraction as well as in separation science since mostly 2012. Copyright © 2014 Elsevier B.V. All rights reserved.

Deterministic phase slips in mesoscopic superconducting rings

PubMed Central

Petković, I.; Lollo, A.; Glazman, L. I.; Harris, J. G. E.

2016-01-01

The properties of one-dimensional superconductors are strongly influenced by topological fluctuations of the order parameter, known as phase slips, which cause the decay of persistent current in superconducting rings and the appearance of resistance in superconducting wires. Despite extensive work, quantitative studies of phase slips have been limited by uncertainty regarding the order parameter's free-energy landscape. Here we show detailed agreement between measurements of the persistent current in isolated flux-biased rings and Ginzburg–Landau theory over a wide range of temperature, magnetic field and ring size; this agreement provides a quantitative picture of the free-energy landscape. We also demonstrate that phase slips occur deterministically as the barrier separating two competing order parameter configurations vanishes. These results will enable studies of quantum and thermal phase slips in a well-characterized system and will provide access to outstanding questions regarding the nature of one-dimensional superconductivity. PMID:27882924

Deterministic phase slips in mesoscopic superconducting rings.

PubMed

Petković, I; Lollo, A; Glazman, L I; Harris, J G E

2016-11-24

The properties of one-dimensional superconductors are strongly influenced by topological fluctuations of the order parameter, known as phase slips, which cause the decay of persistent current in superconducting rings and the appearance of resistance in superconducting wires. Despite extensive work, quantitative studies of phase slips have been limited by uncertainty regarding the order parameter's free-energy landscape. Here we show detailed agreement between measurements of the persistent current in isolated flux-biased rings and Ginzburg-Landau theory over a wide range of temperature, magnetic field and ring size; this agreement provides a quantitative picture of the free-energy landscape. We also demonstrate that phase slips occur deterministically as the barrier separating two competing order parameter configurations vanishes. These results will enable studies of quantum and thermal phase slips in a well-characterized system and will provide access to outstanding questions regarding the nature of one-dimensional superconductivity.

Adjustability of resonance frequency by external magnetic field and bias electric field of sandwich magnetoelectric PZT/NFO/PZT composites

NASA Astrophysics Data System (ADS)

Xu, Ling-Fang; Feng, Xing; Sun, Kang; Liang, Ze-Yu; Xu, Qian; Liang, Jia-Yu; Yang, Chang-Ping

2017-07-01

Sandwich magnetoelectric composites of PZT/NFO/PZT (PNP) have been prepared by laminating PZT5, NiFe2O4, and PZT5 ceramics in turn with polyvinyl alcohol (PVA) paste. A systematic study of structural, magnetic and ferroelectric properties is undertaken. Structural studies carried out by X-ray diffraction indicate formation of cubic perovskite phase of PZT5 ceramic and cubic spinel phase of NiFe2O4 ceramic. As increasing the content of PZT5 phase, ferroelectric loops and magnetic loops of PNP composites showed increasing remnant electric polarizations and decreasing remnant magnetic moments separately. Both external magnetic fields and bias voltages could regulate the basal radial resonance frequency of the composites, which should be originated with the transformation and coupling of the stress between the piezoelectric phase and magnetostrictive phase. Such magnetoelectric composite provides great opportunities for electrostatically tunable devices.

Deterministic phase slips in mesoscopic superconducting rings

DOE PAGES

Petković, Ivana; Lollo, A.; Glazman, L. I.; ...

2016-11-24

The properties of one-dimensional superconductors are strongly influenced by topological fluctuations of the order parameter, known as phase slips, which cause the decay of persistent current in superconducting rings and the appearance of resistance in superconducting wires. Despite extensive work, quantitative studies of phase slips have been limited by uncertainty regarding the order parameter’s free-energy landscape. Here we show detailed agreement between measurements of the persistent current in isolated flux-biased rings and Ginzburg–Landau theory over a wide range of temperature, magnetic field and ring size; this agreement provides a quantitative picture of the free-energy landscape. Furthermore, we also demonstrate thatmore » phase slips occur deterministically as the barrier separating two competing order parameter configurations vanishes. These results will enable studies of quantum and thermal phase slips in a well-characterized system and will provide access to outstanding questions regarding the nature of one-dimensional superconductivity.« less

Role of structurally and magnetically modified nanoclusters in colossal magnetoresistance

PubMed Central

Tao, Jing; Niebieskikwiat, Dario; Jie, Qing; Schofield, Marvin A.; Wu, Lijun; Li, Qiang; Zhu, Yimei

2011-01-01

It is generally accepted that electronic and magnetic phase separation is the origin of many of exotic properties of strongly correlated electron materials, such as colossal magnetoresistance (CMR), an unusually large variation in the electrical resistivity under applied magnetic field. In the simplest picture, the two competing phases are those associated with the material state on either side of the phase transition. Those phases would be paramagnetic insulator and ferromagnetic metal for the CMR effect in doped manganites. It has been speculated that a critical component of the CMR phenomenon is nanoclusters with quite different properties than either of the terminal phases during the transition. However, the role of these nanoclusters in the CMR effect remains elusive because the physical properties of the nanoclusters are hard to measure when embedded in bulk materials. Here we show the unexpected behavior of the nanoclusters in the CMR compound La1-xCaxMnO3 (0.4 ≤ x < 0.5) by directly correlating transmission electron microscopy observations with bulk measurements. The structurally modified nanoclusters at the CMR temperature were found to be ferromagnetic and exhibit much higher electrical conductivity than previously proposed. Only at temperatures much below the CMR transition, the nanoclusters are antiferromagnetic and insulating. These findings substantially alter the current understanding of these nanoclusters on the material’s functionality and would shed light on the microscopic study on the competing spin-lattice-charge orders in strongly correlated systems. PMID:22160678

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

NASA Technical Reports Server (NTRS)

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

1990-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography.

PubMed

Xie, Sheng-Ming; Zhang, Mei; Fei, Zhi-Xin; Yuan, Li-Ming

2014-10-10

Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In₃O(obb)₃(HCO₂)(H₂O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented. Copyright © 2014 Elsevier B.V. All rights reserved.

Electronic transition in La1-xSrxTiO3

NASA Astrophysics Data System (ADS)

Hays, C. C.; Zhou, J.-S.; Markert, J. T.; Goodenough, J. B.

1999-10-01

The transition with increasing x in La1-xSrxTiO3 from an antiferromagnetic, p-type polaronic conductor to an n-type metal with an enhanced Pauli paramagnetism was investigated by monitoring changes in structure, magnetic properties, and, under different hydrostatic pressures, the resistance and thermoelectric power of ceramic samples. We conclude that LaTiO3 is an itinerant-electron antiferromagnet and the transition is first order with a phase separation associated with cooperative oxygen-atom displacements that segregate strongly correlated states from Fermi-liquid states. The Néel temperature TN~145 K decreases precipitously to 100 K at the phase limit x=0.045+/-0.005 the two-phase domain extends over the compositions 0.045<=x<=0.08.

Insulator coated magnetic nanoparticulate composites with reduced core loss and method of manufacture thereof

NASA Technical Reports Server (NTRS)

Zhang, Yide (Inventor); Wang, Shihe (Inventor); Xiao, Danny (Inventor)

2004-01-01

A series of bulk-size magnetic/insulating nanostructured composite soft magnetic materials with significantly reduced core loss and its manufacturing technology. This insulator coated magnetic nanostructured composite is comprises a magnetic constituent, which contains one or more magnetic components, and an insulating constituent. The magnetic constituent is nanometer scale particles (1-100 nm) coated by a thin-layered insulating phase (continuous phase). While the intergrain interaction between the immediate neighboring magnetic nanoparticles separated by the insulating phase (or coupled nanoparticles) provide the desired soft magnetic properties, the insulating material provides the much demanded high resistivity which significantly reduces the eddy current loss. The resulting material is a high performance magnetic nanostructured composite with reduced core loss.

A 3-D open-framework material with intrinsic chiral topology used as a stationary phase in gas chromatography.

PubMed

Xie, Sheng-Ming; Zhang, Xin-Huan; Zhang, Ze-Jun; Zhang, Mei; Jia, Jia; Yuan, Li-Ming

2013-04-01

Compared with liquid chromatography and capillary electrophoresis, the diversity of gas chromatography chiral stationary phases is rather limited. Here, we report the fabrication of Co(D-Cam)1/2(bdc)1/2(tmdpy) (D-Cam = D-camphoric acid; bdc = 1,4-benzenedicarboxylate; tmdpy = 4,4'-trimethylenedipyridine)-coated open tubular columns for high-resolution gas chromatographic separation of compounds. The Co(D-Cam)1/2(bdc)1/2(tmdpy) compound possesses a 3-D framework containing enantiopure building blocks embedded in intrinsically chiral topological nets. In this study, two fused-silica open tubular columns with different inner diameters and lengths, including column A (30 m × 530 μm i.d.) and column B (2 m × 75 μm i.d.), were prepared by a dynamic coating method using Co-(D-Cam)1/2(bdc)1/2(tmdpy) as the stationary phase. The chromatographic properties of the two columns were investigated using n-dodecane as the test compound at 120 °C. The number of theoretical plates (plates/m) of the two metal-organic framework columns was 1,450 and 3,100, respectively. The separation properties were evaluated using racemates, isomers, alkanes, alcohols, and Grob's test mixture. The limit of detection and limit of quantification were found to be 0.125 and 0.417 ng for citronellal enantiomers, respectively. Repeatability (n = 6) showed lower than 0.25 % relative standard deviation (RSD) for retention times and lower than 2.2 % RSD for corrected peak areas. The experimental results showed that the stationary phase has excellent selectivity and also possesses good recognition ability toward these organic compounds, especially chiral compounds.

Surface-bonded ionic liquid stationary phases in high-performance liquid chromatography--a review.

PubMed

Pino, Verónica; Afonso, Ana M

2012-02-10

Ionic liquids (ILs) are a class of ionic, nonmolecular solvents which remain in liquid state at temperatures below 100°C. ILs possess a variety of properties including low to negligible vapor pressure, high thermal stability, miscibility with water or a variety of organic solvents, and variable viscosity. IL-modified silica as novel high-performance liquid chromatography (HPLC) stationary phases have attracted considerable attention for their differential behavior and low free-silanol activity. Indeed, around 21 surface-confined ionic liquids (SCIL) stationary phases have been developed in the last six years. Their chromatographic behavior has been studied, and, despite the presence of a positive charge on the stationary phase, they showed considerable promise for the separation of neutral solutes (not only basic analytes), when operated in reversed phase mode. This aspect points to the potential for truly multimodal stationary phases. This review attempts to summarize the state-of-the-art about SCIL phases including their preparation, chromatographic behavior, and analytical performance. Copyright © 2011 Elsevier B.V. All rights reserved.

Versatile ligands for high-performance liquid chromatography: An overview of ionic liquid-functionalized stationary phases.

PubMed

Zhang, Mingliang; Mallik, Abul K; Takafuji, Makoto; Ihara, Hirotaka; Qiu, Hongdeng

2015-08-05

Ionic liquids (ILs), a class of unique substances composed purely by cation and anions, are renowned for their fascinating physical and chemical properties, such as negligible volatility, high dissolution power, high thermal stability, tunable structure and miscibility. They are enjoying ever-growing applications in a great diversity of disciplines. IL-modified silica, transforming the merits of ILs into chromatographic advantages, has endowed the development of high-performance liquid chromatography (HPLC) stationary phase with considerable vitality. In the last decade, IL-functionalized silica stationary phases have evolved into a series of branches to accommodate to different HPLC modes. An up-to-date overview of IL-immobilized stationary phases is presented in this review, and divided into five parts according to application mode, i.e., ion-exchange, normal-phase, reversed-phase, hydrophilic interaction and chiral recognition. Specific attention is channeled to synthetic strategies, chromatographic behavior and separation performance of IL-functionalized silica stationary phases. Copyright © 2015 Elsevier B.V. All rights reserved.

Quenched bond randomness: Superfluidity in porous media and the strong violation of universality

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

Falicov, A.; Berker, A.N.

1997-04-01

The effects of quenched bond randomness are most readily studied with superfluidity immersed in a porous medium. A lattice model for {sup 3}He-{sup 4}He mixtures and incomplete {sup 4}He fillings in aerogel yields the signature effect of bond randomness, namely the conversion of symmetry-breaking first-order phase transitions into second-order phase transitions, the A-line reaching zero temperature, and the elimination of non-symmetry-breaking first-order phase transitions. The model recognizes the importance of the connected nature of aerogel randomness and thereby yields superfluidity at very low {sup 4}He concentrations, a phase separation entirely within the superfluid phase, and the order-parameter contrast between mixturesmore » and incomplete fillings, all in agreement with experiments. The special properties of the helium mixture/aerogel system are distinctly linked to the aerogel properties of connectivity, randomness, and tenuousness, via the additional study of a regularized {open_quote}jungle-gym{close_quotes} aerogel. Renormalization-group calculations indicate that a strong violation of the empirical universality principle of critical phenomena occurs under quenched bond randomness. It is argued that helium/aerogel critical properties reflect this violation and further experiments are suggested. Renormalization-group analysis also shows that, adjoiningly to the strong universality violation (which hinges on the occurrence or non-occurrence of asymptotic strong coupling-strong randomness under resealing), there is a new {open_quotes}hyperuniversality{close_quotes} at phase transitions with asymptotic strong coupling-strong randomness behavior, for example assigning the same critical exponents to random-bond tricriticality and random-field criticality.« less

Electron irradiation induced phase separation in a sodium borosilicate glass

NASA Astrophysics Data System (ADS)

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

2004-06-01

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

Investigation of a possible electronic phase separation in the magnetic semiconductors Ga1 -xMnxAs and Ga1 -xMnxP by means of fluctuation spectroscopy

NASA Astrophysics Data System (ADS)

Lonsky, Martin; Teschabai-Oglu, Jan; Pierz, Klaus; Sievers, Sibylle; Schumacher, Hans Werner; Yuan, Ye; Böttger, Roman; Zhou, Shengqiang; Müller, Jens

2018-02-01

We present systematic temperature-dependent resistance noise measurements on a series of ferromagnetic Ga1 -xMnxAs epitaxial thin films covering a large parameter space in terms of the Mn content x and other variations regarding sample fabrication. We infer that the electronic noise is dominated by switching processes related to impurities in the entire temperature range. While metallic compounds with x >2 % do not exhibit any significant change in the low-frequency resistance noise around the Curie temperature TC, we find indications for an electronic phase separation in films with x <2 % in the vicinity of TC, manifesting itself in a maximum in the noise power spectral density. These results are compared with noise measurements on an insulating Ga1 -xMnxP reference sample, for which the evidence for an electronic phase separation is even stronger and a possible percolation of bound magnetic polarons is discussed. Another aspect addressed in this work is the effect of ion-irradiation-induced disorder on the electronic properties of Ga1 -xMnxAs films and, in particular, whether any electronic inhomogeneities can be observed in this case. Finally, we put our findings into the context of the ongoing debate on the electronic structure and the development of spontaneous magnetization in these materials.

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

Ning, Yongquan, E-mail: luckyning@nwpu.edu.cn; Huang, Shibo; Fu, M.W.

Microstructural characterization, formation mechanism and fracture behavior of the needle δ phase in Fe–Ni–Cr type superalloys with high Nb content (GH4169, equivalent to Inconel 718) have been quantitatively investigated in this research. The typical microstructures of δ phases with the stick, mixed and needle shapes obviously present in Inconel 718 after the isothermal upsetting at the temperature of 980–1060 °C with the initial strain rate of 10{sup −3}–10{sup −1} s{sup −1}. It is found that the shape of the δ phase has a great effect on the mechanical properties of the alloy, viz., the stick δ phase behaves good plasticitymore » and the needle δ phase has good strength. In addition, the needle δ phase can be used to control the grain size as it can prevent grain growth. The combined effect of the localized necking and microvoid coalescence leads to the final ductile fracture of the GH4169 components with the needle δ phase. Both dislocation motion and atom diffusion are the root-cause for the needle δ phase to be firstly separated at grain boundary and then at sub-boundary. The formation mechanism of the needle δ phase is the new finding in this research. Furthermore, it is the primary mechanism for controlling the needle δ phase in Fe–Ni–Cr type superalloys with high Nb content. - Highlights: • Shape of the δ phase takes great effect on mechanical property. • Needle δ phase plays a great role to prevent grain growth. • Needle δ phase can enhance the fracture strength. • Microstructure mechanism of the needle δ phase has been investigated. • Fracture behavior of the needle δ phase has been studied.« less

Self-organized criticality in single-neuron excitability

NASA Astrophysics Data System (ADS)

Gal, Asaf; Marom, Shimon

2013-12-01

We present experimental and theoretical arguments, at the single-neuron level, suggesting that neuronal response fluctuations reflect a process that positions the neuron near a transition point that separates excitable and unexcitable phases. This view is supported by the dynamical properties of the system as observed in experiments on isolated cultured cortical neurons, as well as by a theoretical mapping between the constructs of self-organized criticality and membrane excitability biophysics.

Hierarchically porous materials from layer-by-layer photopolymerization of high internal phase emulsions.

PubMed

Sušec, Maja; Ligon, Samuel Clark; Stampfl, Jürgen; Liska, Robert; Krajnc, Peter

2013-06-13

A combination of high internal phase emulsion (HIPE) templating and additive manufacturing technology (AMT) is applied for creating hierarchical porosity within an acrylate and acrylate/thiol-based polymer network. The photopolymerizable formulation is optimized to produce emulsions with a volume fraction of droplet phase greater than 80 vol%. Kinetic stability of the emulsions is sufficient enough to withstand in-mold curing or computer-controlled layer-by-layer stereolithography without phase separation. By including macroscale cellular cavities within the build file, a level of controlled porosity is created simultaneous to the formation of the porous microstructure of the polyHIPE. The hybrid HIPE-AMT technique thus provides hierarchically porous materials with mechanical properties tailored by the addition of thiol chain transfer agent. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication and investigation of three-dimensional ferroelectric capacitors for the application of FeRAM

NASA Astrophysics Data System (ADS)

Yeh, Chia-Pin; Lisker, Marco; Kalkofen, Bodo; Burte, Edmund P.

2016-03-01

Ferroelectric capacitors made by lead zirconate titanate (PZT) thin films and iridium electrodes are fabricated on three-dimensional structures and their properties are investigated. The iridium films are grown by Plasma Enhanced MOCVD at 300°C, while the PZT films are deposited by thermal MOCVD at different process temperatures between 450°C and 550°C. The step coverage and composition uniformity of the PZT films on trench holes and lines are investigated. Phase separation of PZT films has been observed on both 3D and planar structures. No clear dependences of the crystallization and composition of PZT on 3D structure topography have been found. STEM EDX line scans show a uniform Zr/(Zr+Ti) concentration ratio along the 3D profile but the variation of the Pb/(Zr+Ti) concentration ratio is large because of the phase separation. 3D ferroelectric capacitors show good ferroelectric properties but have much higher leakage currents than 2D ferroelectric capacitors. Nevertheless, during cycling tests the degradation of the remnant polarization between 2D and 3D capacitors is similar after 109 switching cycles. In addition, the sidewalls and bottoms of the 3D structures seem to have comparable remnant polarizations with the horizontal top surfaces.

Preliminary study on gas separation performance of flat sheet mixed matrix (PVDF/Zeolite)

NASA Astrophysics Data System (ADS)

Rahman, Sunarti Abd; Abdalla Suliman Haron, Gamal; Krishna Roshan Kanasan, Raj; Hasbullah, Hasrinah

2018-04-01

Membrane separation has attracted a lot of attention over the last years mainly due to its separation ability, operational capability and economical viability. Mixed matrix membrane (MMM) combines the superior transport and selectivity properties of inorganic membrane materials and the excellent fabrication properties of organic polymers. This emerging technology can be utilized to purify biogas which can be used in a variety of applications. In this study, flat sheet mixed matrix membranes were synthesized with different percentages of N-Mehtyl-2-pyrrolidone (NMP) as solvent, Polyvinylidene Fluoride (PVDF) as the polymer matrix and zeolite 4A as the dispersed fine particles, membrane A (80: 20: 0), membrane B (80: 18: 2), membrane C (80: 15: 5), and membrane D (75: 15: 10) respectively. The membranes were fabricated using dry/wet phase inversion method. The membrane’s performance in terms of permeability and selectivity was examined using the single gas permeation device. The general trend was that, the permeability of the two gases (CO2/CH4) decreased with the increase of the pressure (0.5, 1, 1.5) bar. Membrane D was found to be suitable to separate the pair gas (CO2/CH4) as the permeability was 65623.412, Barrer and 15587.508, Barrer respectively, and its selectivity for was 4.21 at 0.5 bar.

Incorporating fluorinated moieties in fully conjugated donor-acceptor block copolymers

NASA Astrophysics Data System (ADS)

Lee, Youngmin; Wang, Qing; Gomez, Enrique D.

Fully conjugated donor-acceptor block copolymers are promising candidates for photovoltaics due to their ability to microphase separate at length scales commensurate with exciton diffusion lengths. These materials can also serve as model systems to study the relationship between molecular structure, microstructure, and optoelectronic properties of conjugated polymers. The development of new donor-acceptor block copolymers relies on the manipulation of the chemical structure to fine tune properties and improve overall performance when employed in photovoltaic devices. To this end, we have demonstrated the incorporation of fluorinated moieties in conjugated block copolymers. The introduction of fluorine, a strong electron withdrawing element, is known to influence phase separation and the bandgap, and as a result, optoelectronic properties. Fluorine was introduced to the acceptor block of poly(3-hexylthiophene-2,5-diyl)-block-poly((9,9-bis(2-octyl)fluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5 ',5?-diyl) (P3HT- b-PFTBT). PFTBTs were prepared with di-fluorinated and mono-fluorinated TBT. We find that fluorination impacts the bandgap, morphology and performance in devices.

Competing spin density wave, collinear, and helical magnetism in Fe 1 + x Te

DOE PAGES

Stock, C.; Rodriguez, E. E.; Bourges, P.; ...

2017-04-07

The Fe 1+xTe phase diagram consists of two distinct magnetic structures with collinear order present at low interstitial iron concentrations and a helical phase at large values of x with these phases separated by a Lifshitz point. In this paper, we use unpolarized single-crystal diffraction to confirm the helical phase for large interstitial iron concentrations and polarized single-crystal diffraction to demonstrate the collinear order for the iron-deficient side of the Fe 1+xTe phase diagram. Polarized neutron inelastic scattering shows that the fluctuations associated with this collinear order are predominately transverse at low-energy transfers, consistent with a localized magnetic moment picture.more » We then apply neutron inelastic scattering and polarization analysis to investigate the dynamics and structure near the boundary between collinear and helical orders in the Fe 1+xTe phase diagram. We first show that the phase separating collinear and helical orders is characterized by a spin density wave with a single propagation wave vector of (~0.45, 0, 0.5). We do not observe harmonics or the presence of a charge density wave. The magnetic fluctuations associated with this wave vector are different from the collinear phase, being strongly longitudinal in nature and correlated anisotropically in the (H,K) plane. The excitations preserve the C 4 symmetry of the lattice but display different widths in momentum along the two tetragonal directions at low-energy transfers. Finally, while the low-energy excitations and minimal magnetic phase diagram can be understood in terms of localized interactions, we suggest that the presence of the density wave phase implies the importance of electronic and orbital properties.« less

Competing spin density wave, collinear, and helical magnetism in Fe 1 + x Te

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

Stock, C.; Rodriguez, E. E.; Bourges, P.

The Fe 1+xTe phase diagram consists of two distinct magnetic structures with collinear order present at low interstitial iron concentrations and a helical phase at large values of x with these phases separated by a Lifshitz point. In this paper, we use unpolarized single-crystal diffraction to confirm the helical phase for large interstitial iron concentrations and polarized single-crystal diffraction to demonstrate the collinear order for the iron-deficient side of the Fe 1+xTe phase diagram. Polarized neutron inelastic scattering shows that the fluctuations associated with this collinear order are predominately transverse at low-energy transfers, consistent with a localized magnetic moment picture.more » We then apply neutron inelastic scattering and polarization analysis to investigate the dynamics and structure near the boundary between collinear and helical orders in the Fe 1+xTe phase diagram. We first show that the phase separating collinear and helical orders is characterized by a spin density wave with a single propagation wave vector of (~0.45, 0, 0.5). We do not observe harmonics or the presence of a charge density wave. The magnetic fluctuations associated with this wave vector are different from the collinear phase, being strongly longitudinal in nature and correlated anisotropically in the (H,K) plane. The excitations preserve the C 4 symmetry of the lattice but display different widths in momentum along the two tetragonal directions at low-energy transfers. Finally, while the low-energy excitations and minimal magnetic phase diagram can be understood in terms of localized interactions, we suggest that the presence of the density wave phase implies the importance of electronic and orbital properties.« less

Competing spin density wave, collinear, and helical magnetism in Fe1 +xTe

NASA Astrophysics Data System (ADS)

Stock, C.; Rodriguez, E. E.; Bourges, P.; Ewings, R. A.; Cao, H.; Chi, S.; Rodriguez-Rivera, J. A.; Green, M. A.

2017-04-01

The Fe1 +xTe phase diagram consists of two distinct magnetic structures with collinear order present at low interstitial iron concentrations and a helical phase at large values of x with these phases separated by a Lifshitz point. We use unpolarized single-crystal diffraction to confirm the helical phase for large interstitial iron concentrations and polarized single-crystal diffraction to demonstrate the collinear order for the iron-deficient side of the Fe1 +xTe phase diagram. Polarized neutron inelastic scattering shows that the fluctuations associated with this collinear order are predominately transverse at low-energy transfers, consistent with a localized magnetic moment picture. We then apply neutron inelastic scattering and polarization analysis to investigate the dynamics and structure near the boundary between collinear and helical orders in the Fe1 +xTe phase diagram. We first show that the phase separating collinear and helical orders is characterized by a spin density wave with a single propagation wave vector of (˜0.45 , 0, 0.5). We do not observe harmonics or the presence of a charge density wave. The magnetic fluctuations associated with this wave vector are different from the collinear phase, being strongly longitudinal in nature and correlated anisotropically in the (H ,K ) plane. The excitations preserve the C4 symmetry of the lattice but display different widths in momentum along the two tetragonal directions at low-energy transfers. While the low-energy excitations and minimal magnetic phase diagram can be understood in terms of localized interactions, we suggest that the presence of the density wave phase implies the importance of electronic and orbital properties.

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.

Characterization of structural stability of palm oil esters-based nanocosmeceuticals loaded with tocotrienol

PubMed Central

2013-01-01

Background Palm oil esters (POEs) are esters derived from palm oil and oleyl alcohol have great potential in the cosmetic and pharmaceutical industries due to the excellent wetting behavior of the esters without the oily feel. The role of oil-in-water nanoemulsions loaded with tocotrienol sedimentation behavior was studied. LUMiFuge® 116 particle separation analyzer was used to investigate the sedimentation behavior of POEs/tocotrienol/xanthan gum nanoemulsion system during centrifugation. Analyzing the sedimentation kinetics of dispersions in a centrifugal field also yields information about the rheological behavior and structural stability. Methods Experiments were performed in an analytical centrifuge at 11×g to 1140×g (LUMiFuge® 116 particle separation analyzer). The samples in the LUMiFuge® 116 particle separation analyzer were centrifuged at 3000 rpm for 15 h at 32°C. Sample volume of 2 cm3 was used. The rheological property of nanoemulsions was investigated using oscillatory measurements test. A rotational/oscillatory viscometer, Kinexus Rheometer (Malvern Instrument, UK) was used. All measurements were performed with a stainless steel cone-plate sensor at 25.0 ± 0.1°C with 4°/40 mm. Results The stable nanoemulsions showed sedimentation rates at earth gravity of 5.2, 3.0 and 2.6 mm/month for 10%, 20% and 30% (w/w) oil phase, respectively. Rheological behavior is an important target during the design of palm oil esters-based nanocosmeceuticals. The presence of a network structure was indicated by measurements which showed G’ to be greater than G”. This result implied the predominant elastic response and high storage stability of the nanoemulsion. It was also observed that the increase in oil phase concentration led to the profile which strongly indicated that the solid like elastic property; where the values of phase angle, δ of these nanoemulsions was lower than 45°. Conclusions The nanoemulsions with higher oil phase concentration (30% (w/w)) showed greater elasticity which implied strong dynamic rigidity of the nanoemulsion. It was the most stable with longest shelf-life. PMID:24059593

Thermal Characterization of Fe3O4 Nanoparticles Formed from Poorly Crystalline Siderite

NASA Technical Reports Server (NTRS)

Lauer, H. V., Jr.; Ming, D. W.; Golden, D. C.

2005-01-01

Increasing interest in environmental geochemistry has led to the recognition that crystals with sizes in the nanometer range (e.g., colloids and nanoscale precipitates) and poorly crystalline compounds (e.g., ferrihydrites) may comprise the majority of reactive mineral surface area near the Earth s surface. When the diameters of individual particles are in the range of 100 nm or less, the surface energy contribution to the free energy modifies phase stability. This results in stabilization of polymorphs not normally encountered in the macrocrystal domain. These phases potentially have very different surface-site geometries, adsorptive properties, and growth mechanisms, and exhibit size-dependent kinetic behavior. Thus nanophases dramatically modify the physical and chemical properties of soils and sediments. In a more general sense, the characteristics of nanocrystals are of intense technological interest because small particle size confers novel chemical, optical, and electronic properties. Thus, nanocrystalline materials are finding applications as catalytic substrates, gas phase separation materials, and even more importantly in the field of medicine. This is an opportune time for mineral physicists working on nanocrystalline materials to develop collaborative efforts with materials scientists, chemists, and others working on nanophase materials of technological interest (e.g., for magnetic memories). Our objective in this study was to synthesize submicron (<200 nm) magnetite and to study their thermal and particle size properties.

Characterization of Mechanical Properties of Tissue Scaffolds by Phase Contrast Imaging and Finite Element Modeling.

PubMed

Bawolin, Nahshon K; Dolovich, Allan T; Chen, Daniel X B; Zhang, Chris W J

2015-08-01

In tissue engineering, the cell and scaffold approach has shown promise as a treatment to regenerate diseased and/or damaged tissue. In this treatment, an artificial construct (scaffold) is seeded with cells, which organize and proliferate into new tissue. The scaffold itself biodegrades with time, leaving behind only newly formed tissue. The degradation qualities of the scaffold are critical during the treatment period, since the change in the mechanical properties of the scaffold with time can influence cell behavior. To observe in time the scaffold's mechanical properties, a straightforward method is to deform the scaffold and then characterize scaffold deflection accordingly. However, experimentally observing the scaffold deflection is challenging. This paper presents a novel study on characterization of mechanical properties of scaffolds by phase contrast imaging and finite element modeling, which specifically includes scaffold fabrication, scaffold imaging, image analysis, and finite elements (FEs) modeling of the scaffold mechanical properties. The innovation of the work rests on the use of in-line phase contrast X-ray imaging at 20 KeV to characterize tissue scaffold deformation caused by ultrasound radiation forces and the use of the Fourier transform to identify movement. Once deformation has been determined experimentally, it is then compared with the predictions given by the forward solution of a finite element model. A consideration of the number of separate loading conditions necessary to uniquely identify the material properties of transversely isotropic and fully orthotropic scaffolds is also presented, along with the use of an FE as a form of regularization.