liquid miscibility gap: Topics by Science.gov

Sample records for liquid miscibility gap

Impact of sodium chloride on the expansion of a liquid-liquid miscibility gap in an API/water system. Case study of Brivaracetam.

PubMed

Couvrat, Nicolas; Mahieux, Julien; Fours, Baptiste; Cartigny, Yohann; Schenkel, Eric; Aerts, Luc; Quéré, Luc; Coquerel, Gérard

2016-12-30

Brivaracetam, or (2S)-2-[(4R)-2-oxo-4-propyl-pyrrolidin-1-yl] butanamide, is an active pharmaceutical ingredient designed for the treatment of epilepsy. During the development of the IV administration mode, a liquid-liquid miscibility gap has been observed with pure water, isotonic and hypertonic solutions (vehicle at 0.9% w/w and 5%w/w NaCl respectively). The study reveals that the NaCl concentration has a direct impact on the extent of the demixing domain; from a sub-micronic demixing in pure water towards a macroscopic miscibility gap in hypertonic aqueous solutions. The thorough exploration of these heterogeneous equilibria led to define experimental parameters for safe IV injections without risk of liquid - liquid miscibility gap at 37°C. Copyright Â© 2016 Elsevier B.V. All rights reserved.
Investigation of immiscible systems and potential applications

NASA Technical Reports Server (NTRS)

Markworth, A. J.; Oldfield, W.; Duga, J.; Gelles, S. H.

1975-01-01

The droplet coalescence kinetics at 0 g and 1 g were considered for two systems which contained liquid droplets in a host liquid. One of these (Al-In) typified a system containing a liquid phase miscibility gap and the order (oil-water) a mixture of two essentially insoluble liquids. A number of coalescence mechanisms potentially prominent at low g in this system were analyzed and explanations are presented for the observed unusual stability of the emulsion. Ground base experiments were conducted on the coalescence of In droplets in and Al-In alloy during cooling through the miscibility gap at different cooling rates. These were in qualitative agreement with the computer simulation. Potential applications for systems with liquid phase miscibility gaps were explored. Possibilities included superconductors, electrical contact materials, superplastic materials, catalysts, magnetic materials, and others. The role of space processing in their production was also analyzed.
Miscible viscous fingering with chemical reaction involving precipitation.

NASA Astrophysics Data System (ADS)

Bae, Si-Kyun; Nagatsu, Yuichiro; Kato, Yoshihito; Tada, Yutaka

2007-11-01

When a reactive and miscible less-viscous liquid displaces a more-viscous liquid in a Hele-Shaw cell, reactive miscible viscous fingering takes place. The present study has experimentally examined how precipitation produced by chemical reaction affects miscible viscous fingering pattern. A 97 wt % glycerin solution containing iron(III) nitrate (yellow) and a solution containing potassium hexacyano ferrate(II) (colorless) were used as the more- and less-viscous liquids, respectively. In this case, the chemical reaction instantaneously takes place and produces the precipitation being dark blue in color. The experiments were done by varying reactant concentrations, the cell's gap width, and the displacement speed. We compared the patterns involving the precipitation reaction with those in the non-reactive cases. We have found fylfot-like pattern is observed, depending on the experimental condition, which has never been formed in the non-reactive experiments. As the reactant concentrations are increased or the displacement speed is decreased, the effects of the precipitation on the patterns are more pronounced.
Liquid Phase Miscibility Gap Materials

NASA Technical Reports Server (NTRS)

Gelles, S. H.; Markworth, A. J.

1985-01-01

The manner in which the microstructural features of liquid-phase miscibility gap alloys develop was determined. This will allow control of the microstructures and the resultant properties of these alloys. The long-duration low gravity afforded by the shuttle will allow experiments supporting this research to be conducted with minimal interference from buoyancy effects and gravitationally driven convection currents. Ground base studies were conducted on Al-In, Cu-Pb, and Te-Tl alloys to determine the effect of cooling rate, composition, and interfacial energies on the phase separation and solidification processes that influence the development of microstructure in these alloys. Isothermal and directional cooling experiments and simulations are conducted. The ground based activities are used as a technological base from which flight experiments formulated and to which these flight experiments are compared.
Investigations on transparent liquid-miscibility gap systems

NASA Technical Reports Server (NTRS)

Lacy, L. L.; Nishioka, G.; Ross, S.

1979-01-01

Sedimentation and phase separation is a well known occurrence in monotectic or miscibility gap alloys. Previous investigations indicate that it may be possible to prepare such alloys in a low-gravity space environment but recent experiments indicate that there may be nongravity dependent phase separation processes which can hinder the formation of such alloys. Such phase separation processes are studied using transparent liquid systems and holography. By reconstructing holograms into a commercial-particle-analysis system, real time computer analysis can be performed on emulsions with diameters in the range of 5 micrometers or greater. Thus dynamic effects associated with particle migration and coalescence can be studied. Characterization studies on two selected immiscible systems including an accurate determination of phase diagrams, surface and interfacial tension measurements, surface excess and wetting behavior near critical solution temperatures completed.
Contribution to the thermodynamic description of the corium - The U-Zr-O system

NASA Astrophysics Data System (ADS)

Quaini, A.; Guéneau, C.; Gossé, S.; Dupin, N.; Sundman, B.; Brackx, E.; Domenger, R.; Kurata, M.; Hodaj, F.

2018-04-01

In order to understand the stratification process that may occur in the late phase of the fuel degradation during a severe accident in a PWR, the thermodynamic knowledge of the U-Zr-O system is crucial. The presence of a miscibility gap in the U-Zr-O liquid phase may lead to a stratified configuration, which will impact the accidental scenario management. The aim of this work was to obtain new experimental data in the U-Zr-O liquid miscibility gap. New tie-line data were provided at 2567 ± 25 K. The related thermodynamic models were reassessed using present data and literature values. The reassessed model will be implemented in the TAF-ID international database. The composition and density of phases potentially formed during stratification will be predicted by coupling current thermodynamic model with thermal-hydraulics codes.
High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

NASA Astrophysics Data System (ADS)

Eric, R. Hurman; Ozok, Hakan

1994-01-01

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.
Molecular driving forces behind the tetrahydrofuran–water miscibility gap

DOE PAGES

Smith, Micholas Dean; Mostofian, Barmak; Petridis, Loukas; ...

2016-01-06

The tetrahydrofuran water binary system exhibits an unusual closed-loop miscibility gap (transitions from a miscible regime to an immiscible regime back to another miscible regime as the temperature increases). Here, using all-atom molecular dynamics simulations, we probe the structural and dynamical behavior of the binary system in the temperature regime of this gap at four different mass ratios, and we compare the behavior of bulk water and tetrahydrofuran. The changes in structure and dynamics observed in the simulations indicate that the temperature region associated with the miscibility gap is distinctive. Within the miscibility-gap temperature region, the self diffusion of watermore » is significantly altered and the second virial coefficients (pair interaction strengths) show parabolic-like behavior. Altogether, the results suggest that the gap is the result of differing trends with temperature of minor structural changes, which produces interaction virials with parabolic temperature dependence near the miscibility gap.« less
Phase separation kinetics in immiscible liquids

NASA Technical Reports Server (NTRS)

Ng, Lee H.; Sadoway, Donald R.

1987-01-01

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

NASA Technical Reports Server (NTRS)

Sadoway, D. R.

1986-01-01

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

NASA Astrophysics Data System (ADS)

Walker, Travis W.; Logia, Alison N.; Fuller, Gerald G.

2015-05-01

Drops and jets of liquids that are miscible with the surrounding bulk liquid are present in many processes from cleaning surfaces with the aid of liquid soaps to the creation of biocompatible implants for drug delivery. Although the interactions of immiscible drops and jets show similarities to miscible systems, the small, transient interfacial tension associated with miscible systems create distinct outcomes such as intricate droplet shapes and breakup resistant jets. Experiments have been conducted to understand several basic multiphase flow problems involving miscible liquids. Using high-speed imaging of the morphological evolution of the flows, we have been able to show that these processes are controlled by interfacial tensions. Further multiphase flows include investigating miscible jets, which allow the creation of fibers from inelastic materials that are otherwise difficult to process due to capillary breakup. This work shows that stabilization from the diminishing interfacial tensions of the miscible jets allows various elongated morphologies to be formed.
An experimental study of non-isothermal miscible displacements in a Hele-Shaw cell

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

Nagatsu, Yuichiro; Fujita, Norihito; Kato, Yoshihito

Non-isothermal miscible displacements in a radial Hele-Shaw cell were experimentally investigated using a scheme in which room temperature liquids of relatively high viscosity were displaced by high-temperature (80 C), less-viscous liquids. Fundamental characteristics have been presented regarding how the effect of a non-isothermal field on miscible displacement patterns varies in terms of factors such as the viscosity ratio of the more- and less-viscous liquids at 20 C, M{sub 20}, the rate of an increase in the pattern's area, R, and the gap width of the cell, b. The concept of area density was used to quantitatively evaluate the effect ofmore » the non-isothermal fields on the patterns. We have found that the effect of the non-isothermal field on the patterns does not monotonically vary with M{sub 20} and b. In contrast, it increases with R in the present experimental condition. The experimental results can be explained by introducing an assumption in which heat is transferred mainly to the plates of the cell, in other words, the temperature of the more-viscous liquid remains constant, whereas that of the less-viscous liquid spatiotemporally decreases and the viscosity of it increases along with the temperature decrease. Visualization of non-isothermal field in the cell has been done by means of a thermo sheet and the results support the assumption mentioned above. (author)« less
Internal density waves of shock type induced by chemoconvection in miscible reacting liquids

NASA Astrophysics Data System (ADS)

Bratsun, D. A.

2017-10-01

A theoretical explanation of the phenomenon of spontaneous emergence of density waves experimentally observed recently in bilayered systems of miscible liquids placed in a narrow vertical gap of the Hele-Shaw cell in the gravitational field is provided. Upper and lower layers represent aqueous solutions of acids and bases, respectively, whose contact leads to the beginning of a neutralization reaction. The process is accompanied by a strong dependence of the reagent's diffusion coefficients on their concentrations, giving rise to the generation of local density pockets, in which convection develops. The cavities collapse under certain conditions, causing a density jump, which moves faster than typical perturbations in a medium and takes the form of a shock wave. A mathematical model of the phenomenon is proposed, which can be formally reduced to equations of motion of a compressible gas under certain assumptions. Numerical calculations are given and compared with the experimental data.
Drop impact onto a thin film: Miscibility effect

NASA Astrophysics Data System (ADS)

Chen, Ningli; Chen, H.; Amirfazli, A.

2017-09-01

In this work a systematic experimental study was performed to understand the process of liquid drop impact onto a thin film made of a different liquid from drop. The drop and film liquids can be miscible or immiscible. Three general outcomes of deposition, crown formation without splashing, and splashing, were observed in the advancing phase of the drop impact onto a solid surface covered by either a miscible or an immiscible thin film. However, for a miscible film, a larger Weber number and film thickness are needed for the formation of a crown and splashing comparing with immiscible cases. The advancing phase of drop impact onto a thin immiscible film with a large viscosity is similar to that of drop impact onto a dry surface; for a miscible film viscous film, the behavior is far from that of a dry surface. The behavior of liquid lamella in the receding phase of drop impact onto a thin miscible film is reported for the first time. The results show that immiscibility is not a necessary condition for the existence of a receding phase. The existence of a receding phase is highly dependent on the interfacial tension between the drop and the film. The miscibility can significantly affect the receding morphology as it will cause mixing of the two liquids.
Containerless, Low-Gravity Undercooling of Ti-Ce Alloys in the MSFC Drop Tube

NASA Technical Reports Server (NTRS)

Robinson, M. B.; Rathz, T. J.; Li, D.; Williams, G.; Workman, G.

1999-01-01

Previous tests of the classical nucleation theory as applied to liquid-liquid gap miscibility systems found a discrepancy between experiment and theory in the ability to undercool one of the liquids before the L1-L2 separation occurs. To model the initial separation process in a two-phase liquid mixture, different theoretical approaches, such as free-energy gradient and density gradient theories, have been put forth. If there is a large enough interaction between the critical liquid and the crucible, both models predict a wetting temperature (T(sub w)) above which the minority liquid perfectly wets and layers the crucible interface, but only on one side of the immiscibility dome. Materials with compositions on the other side of the dome will have simple surface adsorption by the minority liquid before bulk separation occurs when the coexistence (i.e., binoidal) line in reached. If the interaction between the critical liquid and the crucible were to decrease, T(sub w) would increase, eventually approaching the critical consolute temperature (T(sub cc)). If this situation occurs, then there could be large regions of the miscibility gap where non-perfect wetting conditions prevail resulting in droplets of L1 liquid at the surface having a non-zero contact angle. The resulting bulk structure will then depend on what happens on the surface and the subsequent processing conditions. In the past several decades, many experiments in space have been performed on liquid metal binary immiscible systems for the purpose of determining the effects that different crucibles may have on the wetting and separation process of the liquids. Potard performed experiments that showed different crucible materials could cause the majority phase to preferentially wet the container and thus produce a dispersed microstructure of the minority phase. Several other studies have been performed on immiscibles in a semi-container environment using an emulsion technique. Only one previous study was performed using completely containerless processing of immiscible metals and the results of that investigation are similar to some of the emulsion studies. In all the studies, surface wetting was attributed as the cause for the similar microstructures or the asymmetry in the ability to undercool the liquid below the binoidal on one side of the immiscibility dome. By removing the container completely from the separation process, it was proposed that the loss of the crucible/liquid interaction would produce a large shift in T(sub w) and thus change the wetting characteristics at the surface. By investigating various compositions across the miscibility gap, a change in the type and amount of liquid wetting at the surface of a containerless droplet should change the surface nucleating behavior of the droplet - whether it be the liquid-liquid wetting or the liquid-to-solid transition. Undercooling of the liquid into the metastable region should produce significant differences in the separation process and the microstructure upon solidification. In this study, we attempt to measure these transitions by monitoring the temperature of the sample by optical pyrometry. Microstructural analysis will be made to correlate with the degree of undercooling and the separation mechanisms involved.
Vapor condensation onto a non-volatile liquid drop

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

Inci, Levent; Bowles, Richard K., E-mail: richard.bowles@usask.ca

2013-12-07

Molecular dynamics simulations of miscible and partially miscible binary Lennard–Jones mixtures are used to study the dynamics and thermodynamics of vapor condensation onto a non-volatile liquid drop in the canonical ensemble. When the system volume is large, the driving force for condensation is low and only a submonolayer of the solvent is adsorbed onto the liquid drop. A small degree of mixing of the solvent phase into the core of the particles occurs for the miscible system. At smaller volumes, complete film formation is observed and the dynamics of film growth are dominated by cluster-cluster coalescence. Mixing into the coremore » of the droplet is also observed for partially miscible systems below an onset volume suggesting the presence of a solubility transition. We also develop a non-volatile liquid drop model, based on the capillarity approximations, that exhibits a solubility transition between small and large drops for partially miscible mixtures and has a hysteresis loop similar to the one observed in the deliquescence of small soluble salt particles. The properties of the model are compared to our simulation results and the model is used to study the formulation of classical nucleation theory for systems with low free energy barriers.« less
Flash-point prediction for binary partially miscible mixtures of flammable solvents.

PubMed

Liaw, Horng-Jang; Lu, Wen-Hung; Gerbaud, Vincent; Chen, Chan-Cheng

2008-05-30

Flash point is the most important variable used to characterize fire and explosion hazard of liquids. Herein, partially miscible mixtures are presented within the context of liquid-liquid extraction processes. This paper describes development of a model for predicting the flash point of binary partially miscible mixtures of flammable solvents. To confirm the predictive efficacy of the derived flash points, the model was verified by comparing the predicted values with the experimental data for the studied mixtures: methanol+octane; methanol+decane; acetone+decane; methanol+2,2,4-trimethylpentane; and, ethanol+tetradecane. Our results reveal that immiscibility in the two liquid phases should not be ignored in the prediction of flash point. Overall, the predictive results of this proposed model describe the experimental data well. Based on this evidence, therefore, it appears reasonable to suggest potential application for our model in assessment of fire and explosion hazards, and development of inherently safer designs for chemical processes containing binary partially miscible mixtures of flammable solvents.
Effect of surface ionization on wetting layers

NASA Technical Reports Server (NTRS)

Kayser, R. F.

1986-01-01

A surface ionization model due to Langmuir is generalized to liquid mixtures of polar and nonpolar components in contact with ionizable substrates. When a predominantly nonpolar mixture is near a miscibility gap, thick wetting layers of the conjugate polar phase form on the substrate. Such charged layers can be much thicker than similar wetting layers stabilized by dispersion forces. This model may explain the 0.4- to 0.6-micron-thick wetting layers formed in stirred mixtures of nitromethane and carbon disulfide in contact with glass.
Dynamic stabilization of the Rayleigh-Taylor instability of miscible liquids and the related "frozen waves"

NASA Astrophysics Data System (ADS)

Wolf, Gerd Gerhard H.

2018-02-01

Superimposed miscible liquids, the heavier one on top, when subjected to vibrations vertical to their interface (dynamic stabilization), can only be maintained for a certain period. A mechanism is presented explaining the resulting process of degradation and "anomalous diffusion" through that interface. Superimposed liquids, the lighter one on top, exposed to horizontal vibrations, develop a saw-tooth-like pattern called "frozen waves." These are subject to conditions similar to those of dynamic stabilization and, if miscible, thus can also only be maintained for a certain period. A further analysis of these processes would be desirable, also in view of their relation to analogue phenomena.
CONTROLLING THE AQUEOUS MISCIBILITY OF IONIC LIQUIDS: A NOVEL AQUEOUS BIPHASIC SYSTEM FROM WATER-MISCIBLE IONIC LIQUID AND A WATER-STRUCTURING SALT. (R828257)

EPA Science Inventory

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Structure functions in decomposing Au-Pt systems

NASA Astrophysics Data System (ADS)

Glas, R.; Blaschko, O.; Rosta, L.

1992-09-01

The evolution of Au-Pt alloys quenched within the miscibility gap is investigated by small-angle neutron-scattering techniques. Moreover, in the vicinity of fundamental Bragg reflections the evolution of ``sideband'' satellites induced by a lattice-parameter modulation connected with the precipitation pattern is investigated by diffuse scattering methods. Structure functions are evaluated for a series of concentrations within the miscibility gap and compared to recent results of the literature.
Activation of porous MOF materials

DOEpatents

Hupp, Joseph T; Farha, Omar K

2013-04-23

A method for the treatment of solvent-containing MOF material to increase its internal surface area involves introducing a liquid into the MOF in which liquid the solvent is miscible, subjecting the MOF to supercritical conditions for a time to form supercritical fluid, and releasing the supercritical conditions to remove the supercritical fluid from the MOF. Prior to introducing the liquid into the MOF, occluded reaction solvent, such as DEF or DMF, in the MOF can be exchanged for the miscible solvent.
Activation of porous MOF materials

DOEpatents

Hupp, Joseph T; Farha, Omar K

2014-04-01

A method for the treatment of solvent-containing MOF material to increase its internal surface area involves introducing a liquid into the MOF in which liquid the solvent is miscible, subjecting the MOF to supercritical conditions for a time to form supercritical fluid, and releasing the supercritical conditions to remove the supercritcal fluid from the MOF. Prior to introducing the liquid into the MOF, occluded reaction solvent, such as DEF or DMF, in the MOF can be exchanged for the miscible solvent.
Liquid-solid equilibria involving spinel, ilmenite, and ferropseudobrookite in the system 'FeO'-Al2O3-TiO2 in contact with metallic iron

NASA Technical Reports Server (NTRS)

Schreifels, W. A.; Muan, A.

1975-01-01

Phase relations in the liquidus temperature region of the system 'FeO'-Al2O3-TiO2 in contact with metallic iron, at a total pressure below 1 atm, have been determined by the quenching technique. Four invariant points have been located, with phase assemblages and temperatures as follows; wuestite, ulvoespinel, nercynite and liquid, 1306 C; ulvoespinel, ilmenite, ferropseudobrookite and liquid, 1340 C; ulvoespinel, hercynite, ferropseudobrookite and liquid, 1367 C; hercynite, ferropseudobrookite, corundum and liquid, 1465 C. The data obtained confirm the presence of a miscibility gap between titanate and aluminate spinels, and provide quantitative data for the effect of Al2O3 on mutual stability relations among spinel, ilmenite, and ferropseudobrookite phases in the presence of liquid at high temperatures and strongly reducing conditions. It is shown that Al2O3 has a strong stabilizing effect on the phase assemblage ferropseudobrookite and spinel relative to ilmenite.
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.
Thermodynamic Modeling of Ag-Ni System Combining Experiments and Molecular Dynamic Simulation

NASA Astrophysics Data System (ADS)

Rajkumar, V. B.; Chen, Sinn-wen

2017-04-01

Ag-Ni is a simple and important system with immiscible liquids and (Ag,Ni) phases. Previously, this system has been thermodynamically modeled utilizing certain thermochemical and phase equilibria information based on conjecture. An attempt is made in this study to determine the missing information which are difficult to measure experimentally. The boundaries of the liquid miscibility gap at high temperatures are determined using a pyrometer. The temperature of the liquid ⇌ (Ag) + (Ni) eutectic reaction is measured using differential thermal analysis. Tie-lines of the Ag-Ni system at 1023 K and 1473 K are measured using a conventional metallurgical method. The enthalpy of mixing of the liquid at 1773 K and the (Ag,Ni) at 973 K is calculated by molecular dynamics simulation using a large-scale atomic/molecular massively parallel simulator. These results along with literature information are used to model the Gibbs energy of the liquid and (Ag,Ni) by a calculation of phase diagrams approach, and the Ag-Ni phase diagram is then calculated.
Nonergodicity in binary alloys

NASA Astrophysics Data System (ADS)

Son, Leonid; Sidorov, Valery; Popel, Pjotr; Shulgin, Dmitry

2015-09-01

For binary liquids with limited miscibility of the components, we provide the corrections to the equation of state which arise from the nonergogic diffusivity. It is shown that these corrections result in lowering of critical miscibility point. In some cases, it may result in a bifurcation of miscibility curve: the mixtures near 50% concentration which are homogeneous at the microscopic level, occur to be too stable to provide a quasi - eutectic triple point. These features provide a new look on the phase diagrams of some binary systems. In present work, we discuss Ga-Pb, Fe-Cu, and Cu-Zr alloys. Our investigation corresponds their complex behavior in liquid state to the shapes of their phase diagrams.
Gradient and size effects on spinodal and miscibility gaps

NASA Astrophysics Data System (ADS)

Tsagrakis, Ioannis; Aifantis, Elias C.

2018-05-01

A thermodynamically consistent model of strain gradient elastodiffusion is developed. Its formulation is based on the enhancement of a robust theory of gradient elasticity, known as GRADELA, to account for a Cahn-Hilliard type of diffusion. Linear stability analysis is employed to determine the influence of concentration and strain gradients on the spinodal decomposition. For finite domains, spherically symmetric conditions are considered, and size effects on spinodal and miscibility gaps are discussed. The theoretical predictions are in agreement with the experimental trends, i.e., both gaps shrink as the grain diameter decreases and they are completely eliminated for crystals smaller than a critical size.
Fluid flow in solidifying monotectic alloys

NASA Technical Reports Server (NTRS)

Ecker, A.; Frazier, D. O.; Alexander, J. Iwan D.

1989-01-01

Use of a two-wavelength holographic technique results in a simultaneous determination of temperature and composition profiles during directional solidification in a system with a miscibility gap. The relationships among fluid flow, phase separation, and mass transport during the solidification of the monotectic alloy are discussed. The primary sources of fluid motion in this system are buoyancy and thermocapillary forces. These forces act together when phase separation results in the formation of droplets (this occurs at the solid-liquid interface and in the bulk melt). In the absence of phase separation, buoyancy results from density gradients related to temperature and compositional gradients in the single-phase bulk melt. The effects of buoyancy are especially evident in association with water- or ethanol-rich volumes created at the solid-liquid growth interface.
Evidence of a miscibility gap in the FeTe1-xSex polycrystalline samples prepared with a melting process

NASA Astrophysics Data System (ADS)

Sala, A.; Palenzona, A.; Bernini, C.; Caglieris, F.; Cimberle, M. R.; Ferdeghini, C.; Lamura, G.; Martinelli, A.; Pani, M.; Hecher, J.; Eisterer, M.; Putti, M.

2014-05-01

The study of overdoped FeTe1-xSex (0.5 < x < 1) polycrystalline superconductor samples is reported. The samples were prepared using a melting technique previously developed by our group. Increasing the Se content a phase separation related to the formation of FeSe inside the Fe(Se,Te) phase happens, as demonstrated by structural analysis and magnetic characterization. The proposed phase separation picture is likely the fingerprint of a miscibility gap in the Fe(Se,Te) system.
Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less
Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less
Oxygen miscibility gap and spin glass formation in the pyrochlore Lu{sub 2}Mo{sub 2}O{sub 7}

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

Clark, L.; Ritter, C.; Harrison, A.

2013-07-15

Rare earth (R) molybdate pyrochlores, R{sub 2}Mo{sub 2}O{sub 7}, are of interest as frustrated magnets. Polycrystalline samples of Lu{sub 2}Mo{sub 2}O{sub 7−x} prepared at 1600 °C display a coexistence of cubic pyrochlore phases. Rietveld fits to powder neutron diffraction data and chemical analyses show that the miscibility gap is between a stoichiometric x=0 and an oxygen-deficient x≈0.4 phase. Lu{sub 2}Mo{sub 2}O{sub 7} behaves as a spin glass material, with a divergence of field cooled and zero field cooled DC magnetic susceptibilities at a spin freezing temperature T{sub f}=16 K, that varies with frequency in AC measurements following a Vogel–Fulcher law.more » Lu{sub 2}Mo{sub 2}O{sub 6.6} is more highly frustrated spin glass and has T{sub f}=20 K. - Graphical abstract: The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system exhibits a miscibility gap between coexisting pyrochlore phases at 1600 °C. Neutron powder diffraction refinement and chemical analysis shows that the gap separates stoichiometric x=0 and oxygen-deficient x≈0.4 phases. Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content. - Highlights: • The cubic Lu{sub 2}Mo{sub 2}O{sub 7−x} system has a miscibility gap between coexisting pyrochlore phases at 1600 °C. • Neutron powder diffraction shows that the gap separates x=0 and oxygen-deficient x≈0.4 phases. • Lu{sub 2}Mo{sub 2}O{sub 7−x} has a frustrated spin glass ground state that is sensitive to the oxygen content.« less
Effect of stirring on the safety of flammable liquid mixtures.

PubMed

Liaw, Horng-Jang; Gerbaud, Vincent; Chen, Chan-Cheng; Shu, Chi-Min

2010-05-15

Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk. Copyright (c) 2010 Elsevier B.V. All rights reserved.
Control of surface adatom kinetics for the growth of high-indium content InGaN throughout the miscibility gap

NASA Astrophysics Data System (ADS)

Moseley, Michael; Lowder, Jonathan; Billingsley, Daniel; Doolittle, W. Alan

2010-11-01

The surface kinetics of InGaN alloys grown via metal-modulated epitaxy (MME) are explored in combination with transient reflection high-energy electron diffraction intensities. A method for monitoring and controlling indium segregation in situ is demonstrated. It is found that indium segregation is more accurately associated with the quantity of excess adsorbed metal, rather than the metal-rich growth regime in general. A modified form of MME is developed in which the excess metal dose is managed via shuttered growth, and high-quality InGaN films throughout the miscibility gap are grown.
On the validity of Stokes-Einstein and Stokes-Einstein-Debye relations in ionic liquids and ionic-liquid mixtures.

PubMed

Köddermann, Thorsten; Ludwig, Ralf; Paschek, Dietmar

2008-09-15

Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations in the neat ionic liquid (IL) [C(2)mim][NTf(2)] and IL/chloroform mixtures are studied by means of molecular dynamics (MD) simulations. For this purpose, we simulate the translational diffusion coefficients of the cations and anions, the rotational correlation times of the C(2)--H bond in the cation C(2)mim(+), and the viscosities of the whole system. We find that the SE and SED relations are not valid for the pure ionic liquid, nor for IL/chloroform mixtures down to the miscibility gap (at 50 wt % IL). The deviations from both relations could be related to dynamical heterogeneities described by the non-Gaussian parameter alpha(t). If alpha(t) is close to zero, at a concentration of 1 wt % IL in chloroform, both relations become valid. Then, the effective radii and volumes calculated from the SE and SED equations can be related to the structures found in the MD simulations, such as aggregates of ion pairs. Overall, similarities are observed between the dynamical properties of supercooled water and those of ionic liquids.
Small Angle Neutron Scattering Studies on Blends of Poly (Styrene-ran-Vinyl Phenol) with Liquid Crystalline Polyurethane

NASA Astrophysics Data System (ADS)

Mehta, Rujul

2005-03-01

Molecular composites, composed of uniformly dispersed rigid-rod liquid crystalline polymer (LCP) molecules in a flexible amorphous polymer matrix, have remained hitherto elusive due to a scarcity of miscible systems containing a LCP and an amorphous polymer. The production of such a blend, with an experimentally accessible miscibility window, has become possible by modifying the architecture of the flexible polymer, so as to induce favorable intermolecular hydrogen bonding. Specifically, liquid crystalline polyurethanes (LCPU) are found to be miscible with a copolymer of styrene and vinyl phenol; with optimum hydrogen bonding between the carbonyl groups of the urethane linkages and the hydroxyl groups present in the styrenic matrix. Availability of a truly miscible molecular composite presents a unique opportunity of studying the confirmation of polymer chains containing rigid-rods that are uniformly dispersed in a flexible coil matrix. A system consisting of the LCPU and the deuterated styrenic copolymer containing 20% vinyl phenol is examined by Small Angle Neutron Scattering at the National Center for Neutron Research at Gaithersburg and Technology, and the Institute of Solid State Research (IFF) at Jülich. Scattering curves for neat dPS-VPh did not fit the Debye-Bueche model; indicating complex structure. A two correlation length Debye-Bueche model was considered to accommodate for this nonlinear behavior. This model utilizes four fitting parameters, including two correlation lengths a1 and a2, corresponding to a Debye-Bueche model and Guinier model.
Simulation of Layered Magma Chambers.

ERIC Educational Resources Information Center

Cawthorn, Richard Grant

1991-01-01

The principles of magma addition and liquid layering in magma chambers can be demonstrated by dissolving colored crystals. The concepts of density stratification and apparent lack of mixing of miscible liquids is convincingly illustrated with hydrous solutions at room temperature. The behavior of interstitial liquids in "cumulus" piles…
Solutal Marangoni flows of miscible liquids drive transport without surface contamination

NASA Astrophysics Data System (ADS)

Kim, Hyoungsoo; Muller, Koen; Shardt, Orest; Afkhami, Shahriar; Stone, Howard A.

2017-11-01

Mixing and spreading of different liquids are omnipresent in nature, life and technology, such as oil pollution on the sea, estuaries, food processing, cosmetic and beverage industries, lab-on-a-chip devices, and polymer processing. However, the mixing and spreading mechanisms for miscible liquids remain poorly characterized. Here, we show that a fully soluble liquid drop deposited on a liquid surface remains as a static lens without immediately spreading and mixing, and simultaneously a Marangoni-driven convective flow is generated, which are counterintuitive results when two liquids have different surface tensions. To understand the dynamics, we develop a theoretical model to predict the finite spreading time and length scales, the Marangoni-driven convection flow speed, and the finite timescale to establish the quasi-steady state for the Marangoni flow. The fundamental understanding of this solutal Marangoni flow may enable driving bulk flows and constructing an effective drug delivery and surface cleaning approach without causing surface contamination by immiscible chemical species.
Oscillatory interfacial instability between miscible fluids

NASA Astrophysics Data System (ADS)

Shevtsova, Valentina; Gaponenko, Yuri; Mialdun, Aliaksandr; Torregrosa, Marita; Yasnou, Viktar

Interfacial instabilities occurring between two fluids are of fundamental interest in fluid dynamics, biological systems and engineering applications such as liquid storage, solvent extraction, oil recovery and mixing. Horizontal vibrations applied to stratified layers of immiscible liquids may generate spatially periodic waving of the interface, stationary in the reference frame of the vibrated cell, referred to as a "frozen wave". We present experimental evidence that frozen wave instability exists between two ordinary miscible liquids of similar densities and viscosities. At the experiments and at the numerical model, two superimposed layers of ordinary liquids, water-alcohol of different concentrations, are placed in a closed cavity in a gravitationally stable configuration. The density and viscosity of these fluids are somewhat similar. Similar to the immiscible fluids this instability has a threshold. When the value of forcing is increased the amplitudes of perturbations grow continuously displaying a saw-tooth structure. The decrease of gravity drastically changes the structure of frozen waves.

Wetting phenomenon in the liquid-vapor phase coexistence of a partially miscible Lennard-Jones binary mixture

NASA Astrophysics Data System (ADS)

Ramírez-Santiago, Guillermo; Díaz-Herrera, Enrique; Moreno Razo, José A.

2004-03-01

We have carried out extensive equilibrium MD simulations to study wetting phenomena in the liquid-vapor phase coexistence of a partially miscible binary LJ mixture. We find that in the temperature range 0.60 ≤ T^* < 0.80, the system separates forming a liquid A-liquid B interface in coexistence with the vapor phase. At higher temperatures, 0.80 ≤ T^* < 1.25 the liquid phases are wet by the vapor phase. By studying the behavior of the surface tension as a function of temperature we estimate the wetting transition temperature (WTT) to be T^*_w≃ 0.80. The adsorption of molecules at the liquid-liquid interface shows a discontinuity at about T^*≃ 0.79 suggesting that the wetting transition is a first order phase transition. These results are in agreement with some experiments carried out in fluid binary mixtures. In addition, we estimated the consolute temperature to be T^* _cons≃ 1.25. The calculated phase diagram of the mixture suggest the existence of a tricritical point.
The effects of forced small-wavelength, finite-bandwidth initial perturbations and miscibility on the turbulent Rayleigh–Taylor instability

DOE PAGES

Roberts, M. S.; Jacobs, J. W.

2015-12-07

Rayleigh–Taylor instability experiments are performed using both immiscible and miscible incompressible liquid combinations having a relatively large Atwood number ofmore » $$A\\equiv ({\\it\\rho}_{2}-{\\it\\rho}_{1})/({\\it\\rho}_{2}+{\\it\\rho}_{1})=0.48$$. The liquid-filled tank is attached to a test sled that is accelerated downwards along a vertical rail system using a system of weights and pulleys producing approximately$1g$$net acceleration. The tank is backlit and images are digitally recorded using a high-speed video camera. The experiments are either initiated with forced initial perturbations or are left unforced. The forced experiments have an initial perturbation imposed by vertically oscillating the liquid-filled tank to produce Faraday waves at the interface. The unforced experiments rely on random interfacial fluctuations, resulting from background noise, to seed the instability. The main focus of this study is to determine the effects of forced initial perturbations and the effects of miscibility on the growth parameter,$${\\it\\alpha}$$. Measurements of the mixing-layer width,$$h$$, are acquired, from which$${\\it\\alpha}$$is determined. It is found that initial perturbations of the form used in this study do not affect measured$${\\it\\alpha}$$values. However, miscibility is observed to strongly affect$${\\it\\alpha}$$, resulting in a factor of two reduction in its value, a finding not previously observed in past experiments. In addition, all measured$${\\it\\alpha}$values are found to be smaller than those obtained in previous experimental studies.« less
Richtmyer-Meshkov instability experiments of miscible and immiscible incompressible fluids

NASA Astrophysics Data System (ADS)

Krivets, Vitaliy; Holt, Brason; Mokler, Matthew; Jacobs, Jeffrey

2017-11-01

Experiments were conducted in a 3 m tall vertical drop tower setup. A flat interface separating two liquids of differing density is formed in the Plexiglas tank with the heavier fluid in the bottom and the lighter one on top. Two liquids pairs were utilized, one - miscible (isopropyl alcohol and a calcium nitrate water mixture) and the other immiscible (silicone oil with the same heavy liquid), both with Atwood near 0.2. The tank is mounted on a rail mounted sled at 2 m initial height where an initial perturbation is generated using vertical periodic motion with 10 Hz frequency and 1 mm displacement, thus producing 3D interfacial waves. An impulsive acceleration, with approximately 100g magnitude, is imparted to the sled by a rail mounted weight released and allowed to fall, impacting the sled from above. Both weight and sled then travel freely down the rails where they are smoothly decelerated at the bottom of drop tower by magnetic brakes. PLIF is used to visualize mixing process by seeding fluorescein in the bottom fluid and illuminating using laser diode from above forming thin vertical sheet. The resulting fluorescent image sequences are captured using a digital camera mounted to the sled operating at a 100 Hz framing rate. Comparisons of the measured growth of the mixing zone for both immiscible and miscible liquid combinations with theoretical models are presented.
Composition-dependent damping and relaxation dynamics in miscible polymer blends above glass transition temperature by anelastic spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Xuebang; Shang, Shuying; Xu, Qiaoling; Liu, Changsong; Zhu, Zhengang; Zhang, Guangzhao

2008-07-01

Anelastic spectroscopy is used to study the composition dependence of the damping and molecular relaxation dynamics in miscible poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends above the glass transition temperature. The ultrahigh damping peak of the relaxation type is shown to be associated with the liquid-liquid transition of PMMA. A higher PEO concentration leads to a higher damping performance and a lower transition temperature. The decreasing activation energy with increasing PEO concentration indicates a drastic increase in molecular mobility. Moreover, the relaxation time reveals a transition from the Vogel-Fulcher-Tamman behavior to the Arrhenius behavior due to the intermolecular guest-host interactions.
Low-gravity fluid dynamics and transport phenomena. Progress in Astronautics and Aeronautics. Vol. 130

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

Koster, J.N.; Sani, R.L.

1990-01-01

Various papers on low-gravity fluid dynamics and transport phenomena are presented. Individual topics addressed include: fluid management in low gravity, nucleate pool boiling in variable gravity, application of energy-stability theory to problems in crystal growth, thermosolutal convection in liquid HgCdTe near the liquidus temperature, capillary surfaces in microgravity, thermohydrodynamic instabilities and capillary flows, interfacial oscillators, effects of gravity jitter on typical fluid science experiments and on natural convection in a vertical cylinder. Also discussed are: double-diffusive convection and its effects under reduced gravity, segregation and convection in dendritic alloys, fluid flow and microstructure development, analysis of convective situations with themore » Soret effect, complex natural convection in low Prandtl number metals, separation physics, phase partitioning in reduced gravity, separation of binary alloys with miscibility gap in the melt, Ostwald ripening in liquids, particle cloud combustion in reduced gravity, opposed-flow flame spread with implications for combustion at microgravity.« less
Low temperature synthesis of Ru-Cu alloy nanoparticles with the compositions in the miscibility gap

NASA Astrophysics Data System (ADS)

Martynova, S. A.; Filatov, E. Yu.; Korenev, S. V.; Kuratieva, N. V.; Sheludyakova, L. A.; Plusnin, P. E.; Shubin, Yu. V.; Slavinskaya, E. M.; Boronin, A. I.

2014-04-01

A complex salt [Ru(NH3)5Cl][Cu(C2O4)2H2O]-the precursor of nanoalloys combining ruthenium and copper was prepared. It crystallizes in the monoclinic space group P21/n. Thermal properties of the prepared salt were examined in different atmospheres (helium, hydrogen, oxygen). Thermal decomposition of the precursor in inert atmosphere was thoroughly examined and the intermediate products were characterized. Experimental conditions for preparation of copper-rich (up to 12 at% of copper) metastable solid solution CuxRu1-x (based on Ru structure) were optimized, what is in sharp contrast to the bimetallic miscibility gap known for the bulk counterparts in a wide composition range. Catalytic properties of copper-ruthenium oxide composite were tested in catalytic oxidation of CO.
Complexation reactions in pyridine and 2,6-dimethylpyridine-water system: The quantum-chemical description and the path to liquid phase separation.

PubMed

Chernia, Zelig; Tsori, Yoav

2018-03-14

Phase separation in substituted pyridines in water is usually described as an interplay between temperature-driven breakage of hydrogen bonds and the associating interaction of the van der Waals force. In previous quantum-chemical studies, the strength of hydrogen bonding between one water and one pyridine molecules (the 1:1 complex) was assigned a pivotal role. It was accepted that the disassembly of the 1:1 complex at a critical temperature leads to phase separation and formation of the miscibility gap. Yet, for over two decades, notable empirical data and theoretical arguments were presented against that view, thus revealing the need in a revised quantum-mechanical description. In the present study, pyridine-water and 2,6-dimethylpyridine-water systems at different complexation stages are calculated using high level Kohn-Sham theory. The hydrophobic-hydrophilic properties are accounted for by the polarizable continuum solvation model. Inclusion of solvation in free energy of formation calculations reveals that 1:1 complexes are abundant in the organically rich solvents but higher level oligomers (i.e., 2:1 dimers with two pyridines and one water molecule) are the only feasible stable products in the more polar media. At the critical temperature, the dissolution of the external hydrogen bonds between the 2:1 dimer and the surrounding water molecules induces the demixing process. The 1:1 complex acts as a precursor in the formation of the dimers but is not directly involved in the demixing mechanism. The existence of the miscibility gap in one pyridine-water system and the lack of it in another is explained by the ability of the former to maintain stable dimerization. Free energy of formation of several reaction paths producing the 2:1 dimers is calculated and critically analyzed.
Complexation reactions in pyridine and 2,6-dimethylpyridine-water system: The quantum-chemical description and the path to liquid phase separation

NASA Astrophysics Data System (ADS)

Chernia, Zelig; Tsori, Yoav

2018-03-01

Phase separation in substituted pyridines in water is usually described as an interplay between temperature-driven breakage of hydrogen bonds and the associating interaction of the van der Waals force. In previous quantum-chemical studies, the strength of hydrogen bonding between one water and one pyridine molecules (the 1:1 complex) was assigned a pivotal role. It was accepted that the disassembly of the 1:1 complex at a critical temperature leads to phase separation and formation of the miscibility gap. Yet, for over two decades, notable empirical data and theoretical arguments were presented against that view, thus revealing the need in a revised quantum-mechanical description. In the present study, pyridine-water and 2,6-dimethylpyridine-water systems at different complexation stages are calculated using high level Kohn-Sham theory. The hydrophobic-hydrophilic properties are accounted for by the polarizable continuum solvation model. Inclusion of solvation in free energy of formation calculations reveals that 1:1 complexes are abundant in the organically rich solvents but higher level oligomers (i.e., 2:1 dimers with two pyridines and one water molecule) are the only feasible stable products in the more polar media. At the critical temperature, the dissolution of the external hydrogen bonds between the 2:1 dimer and the surrounding water molecules induces the demixing process. The 1:1 complex acts as a precursor in the formation of the dimers but is not directly involved in the demixing mechanism. The existence of the miscibility gap in one pyridine-water system and the lack of it in another is explained by the ability of the former to maintain stable dimerization. Free energy of formation of several reaction paths producing the 2:1 dimers is calculated and critically analyzed.
"Bligh and Dyer" and Folch Methods for Solid-Liquid-Liquid Extraction of Lipids from Microorganisms. Comprehension of Solvatation Mechanisms and towards Substitution with Alternative Solvents.

PubMed

Breil, Cassandra; Abert Vian, Maryline; Zemb, Thomas; Kunz, Werner; Chemat, Farid

2017-03-27

Bligh and Dyer (B & D) or Folch procedures for the extraction and separation of lipids from microorganisms and biological tissues using chloroform/methanol/water have been used tens of thousands of times and are "gold standards" for the analysis of extracted lipids. Based on the Conductor-like Screening MOdel for realistic Solvatation (COSMO-RS), we select ethanol and ethyl acetate as being potentially suitable for the substitution of methanol and chloroform. We confirm this by performing solid-liquid extraction of yeast ( Yarrowia lipolytica IFP29 ) and subsequent liquid-liquid partition-the two steps of routine extraction. For this purpose, we consider similar points in the ternary phase diagrams of water/methanol/chloroform and water/ethanol/ethyl acetate, both in the monophasic mixtures and in the liquid-liquid miscibility gap. Based on high performance thin-layer chromatography (HPTLC) to obtain the distribution of lipids classes, and gas chromatography coupled with a flame ionisation detector (GC/FID) to obtain fatty acid profiles, this greener solvents pair is found to be almost as effective as the classic methanol-chloroform couple in terms of efficiency and selectivity of lipids and non-lipid material. Moreover, using these bio-sourced solvents as an alternative system is shown to be as effective as the classical system in terms of the yield of lipids extracted from microorganism tissues, independently of their apparent hydrophilicity.
Size effects on melting and wetting in the Ga-Pb nano-alloy

NASA Astrophysics Data System (ADS)

Allione, M.; Kofman, R.; Celestini, F.; Lereah, Y.

2009-04-01

Ga-Pb alloys with 15 at% Pb mean concentration have been prepared at the nanoscale by means of evaporation-condensation technique in ultra high vacuum conditions. Transmission electron microscope images indicate that at room temperature, the system is a two-components breath figure composed of liquid Ga nanodrops containing Pb nanocrystals. Some thermodynamic properties of this nano-alloy are investigated for different temperatures and particle sizes. The results obtained put in evidence a large modification of the Ga-Pb bulk phase diagram: a decrease of the melting temperatures of the two components as well as the ones of the miscibility gap. Changes in the microscopic structure of the system as a function of temperature have been investigated and a full wetting transition from a dry to a completely wet state has been put in evidence.
Enhanced sampling simulation analysis of the structure of lignin in the THF–water miscibility gap

DOE PAGES

Smith, Micholas Dean; Petridis, Loukas; Cheng, Xiaolin; ...

2016-01-26

Using temperature replica-exchange molecular dynamics, we characterize a globule-to-coil transition for a softwood-like lignin biopolymer in a tetrahydrofuran (THF)-water cosolvent system at temperatures at which the cosolvent undergoes a de-mixing transition. The lignin is found to be in a coil state, similar to that in the high-temperature miscible region. Analysis of the transition kinetics indicates that THF acts in a surfactant-like fashion. In conclusion, the present study thus suggests that THF-water based pretreatments may efficiently remove lignin from biomass even at relatively low (non-water boiling) temperatures.
An investigation of the thermodynamic miscibility between VeTPGS and polymers.

PubMed

Li, Jinjiang; Chiappetta, Doris

2008-02-28

Within the past decade, more than half of the drug candidates generated are poorly water soluble and therefore overcoming the low aqueous solubility of drug candidates becomes critical for product development. Vitamin E TPGS (VeTPGS), a non-ionic surfactant, has been used in both liquid and solid dosage forms to solubilize compounds and improve their bioavailability. To prepare solid dosage forms using VeTPGS, VeTPGS is often mixed with other excipients, mostly polymers. However, there is still a lack of understanding of miscibility between VeTPGS and polymers from a thermodynamic point of view. In this paper, the miscibility of VeTPGS with polymers has been studied in the light of the Flory-Huggins (F-H) theory with an objective to understand the effect of dispersion forces (solubility parameter) and nondispersive interactions on the miscibility between VeTPGS and polymers. A series of polymers with similar solubility parameters and structure similarity were selected. Binary blends of polymers and VeTPGS were prepared using a vapor evaporation technique followed by XRPD, DSC, and SEM characterization. Results suggest that the miscibility between VeTPGS and PMMA is very likely due to a specific interaction between the hydrophobic portion of VeTPGS (Vitamin E) and PMMA.
Thermodynamic properties of hematite — ilmenite — geikielite solid solutions

NASA Astrophysics Data System (ADS)

Ghiorso, Mark S.

1990-11-01

A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe{2+/ s }Ti{4+/1- s }) A (Fe{2+/1- s }Ti{4+/s}) B O3]-geikielite [(Mg{2+/ t }Ti{4+/1- t }) A (Mg{2+/1- t }Ti{4+/ t }) B O3]-hematite [(Fe3+) A (Fe3+) B O3]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0≤s, t≤1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of theRbar 3c - Rbar 3 transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg-Fe2+ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe2+-Fe3+ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (-1488.5 and -822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe-Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternaryRbar 3 - Rbar 3c second-order transition.
Nonconvective mixing of miscible ionic liquids.

PubMed

Frost, Denzil S; Machas, Michael; Perea, Brian; Dai, Lenore L

2013-08-13

Ionic liquids (ILs) are ionic compounds that are liquid at room temperature. We studied the spontaneous mixing behavior between two ILs, ethylammonium nitrate (EAN) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), and observed notable phenomena. Experimental studies showed that the interface between the two ILs was unusually long-lived, despite the ILs being miscible with one another. Molecular dynamics (MD) simulations supported these findings and provided insight into the micromixing behavior of the ILs. We found that not only did the ions experience slow diffusion as they mix but also exhibited significant ordering into distinct regions. We suspect that this ordering disrupted concentration gradients in the direction normal to the interface, thus hindering diffusion in this direction and allowing the macroscopic interface to remain for long periods of time. Intermolecular interactions responsible for this behavior included the O-NH interaction between the EAN ions and the carbon chain-carbon chain interactions between the [BMIM](+) cations, which associate more strongly in the mixed state than in the pure IL state.
Liquidus Diagram of the Ba-Y-Cu-O System in the Vicinity of the Ba2YCu3O6+x Phase Field

PubMed Central

Wong-Ng, Winnie; Cook, Lawrence P.

1998-01-01

This paper describes the melting equilibria in the vicinity of the high Tc phase Ba2YCu3O6+x, including evidence for two Ba-Y-Cu-O immiscible liquids. Melting equilibria have been investigated in purified air using a combination of differential thermal analysis (DTA), thermogravimetric analysis (TGA), powder x-ray diffraction (XRD), MgO wick entrapment of liquid for analysis, scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDS), and hydrogen reduction for determination of copper oxidation state. For relatively barium-rich compositions, it was necessary to prepare the starting materials under controlled atmosphere conditions using BaO. A liquidus diagram was derived from quantitative data for the melts involved in various melting reactions. In general the 1/2(Y2O3) contents of the melts participating in these equilibria were low (mole fraction <4 %). The primary phase field of Ba2YCu3O6+x occurs at a mole fraction of <2.0 % 1/2Y2O3 and lies very close along the BaO-CuOx edge, extending from a mole fraction of ≈43 % CuO to a mole fraction of ≈76 % CuO. It is divided by a liquid miscibility gap and extends on either side about this gap. The topological sequence of melting reactions associated with the liquidus is presented as a function of temperature. Implications for the growth of Ba2YCu3O6+x crystals are discussed. PMID:28009382
Novel Shapes of Miscible Interfaces Observed

NASA Technical Reports Server (NTRS)

Balasubramaniam, Ramaswamy; Rashidnia, Nasser

2001-01-01

The dynamics of miscible displacements in a cylindrical tube are being investigated experimentally and numerically, with a view to understand the complex processes that occur, for example, in enhanced oil recovery, hydrology, and filtration. We have observed complex shapes of the interface between two liquids that mix with each other when the less viscous liquid is displaced by the more viscous one in a tube. A less viscous fluid that displaces a more viscous fluid is known to propagate in the form of a "finger," and a flight experiment proposed by Maxworthy et al. to investigate the miscible-interface dynamics is currently being developed by NASA. From the current theory of miscible displacements, which was developed for a porous medium satisfying Darcy's law, it can be shown that in the absence of gravity the interface between the fluids is destabilized and thus susceptible to fingering only when a more viscous fluid is displaced by a less viscous one. Therefore, if the interface is initially flat and the more viscous fluid displaces the less viscous fluid, the interface ought to be stable and remain flat. However, numerical simulations by Chen and Meiburg for such displacement in a cylindrical tube show that the interface is unstable and a finger of the more viscous fluid is indeed formed. Preliminary experiments performed at the NASA Glenn Research Center show that not only can fingering occur when the more viscous fluid displaces a less viscous one in a cylindrical tube, but also that under certain conditions the advancing finger achieves a sinuous or snakelike shape. These experiments were performed using silicone oils in a vertical pipette of small diameter. In the initial configuration, the more viscous fluid rested on top of the less viscous one, and the interface was nominally flat. A dye was added to the upper liquid for ease of observation of the interface between the fluids. The flow was initiated by draining the lower fluid from the bottom of the pipette, at speeds less than 0.1 mm/sec.
FNAS modify matric and transparent experiments

NASA Technical Reports Server (NTRS)

Smith, Guy A.; Kosten, Sue E.; Workman, Gary L.

1992-01-01

Monotectic alloy materials are created by rapid melt/rapid solidification processing on the NASA KC-135. Separation of the uniform liquid into two liquids may occur by either of two processes; spinodal decomposition or nucleation followed by growth. In the first case, the liquid is unstable to composition waves, which form and grow, giving liquids of two different compositions. In the latter process discrete particles of the second liquid phase form via thermal fluctuations and then grow by diffusion. The two processes are very different, with the determining process being dictated by temperature, composition, and thermodynamic characteristics of the alloy. The first two quantities are process variables, while the third is determined by electronic interactions between the atoms in the alloy. In either case the initial alloy decomposition is followed by coarsening, resulting in growth of the particle size at nearly constant volume fraction. In particular, reduced gravity experiments on monotectic solutions have shown a number of interesting results in the KC-135. Monotectic solutions exhibit a miscibility gap in the liquid state, and consequently, gravity driven forces can dominate the solidification parameters at 1 g. In reduced gravity however, the distribution of the phases is different, resulting in new and interesting microstructures. The Rapid Melt/Rapid Quench Furnace allows one to melt a sample and resolidify it in one parabola of the KC-135's flight path, thus eliminating any accumulative influence of multiple parabolas to affect the microstructure of the material.
Effect of solvent evaporation and coagulation on morphology development of asymmetric membranes

NASA Astrophysics Data System (ADS)

Chandrasekaran, Neelakandan; Kyu, Thein

2008-03-01

Miscibility behavior of blends of amorphous polyamide (PA) and polyvinylpyrrolidone (PVP) was studied in relation to membrane formation. Dimethylsulfoxide (DMSO) and water were used as solvent and non-solvent, respectively. Differential scanning calorimetry and cloud point measurements revealed that the binary PA/PVP blends as well as the ternary PA/PVP/DMSO system were completely miscible at all compositions. However, the addition of non-solvent (water) to this ternary system has led to phase separation. Visual turbidity study was used to establish a ternary liquid-liquid phase diagram of the PA-PVP/DMSO/water system. Scanning Electron Microscopy (SEM) showed the development of finger-like and sponge-like cross sectional morphologies during coagulation. Effects of polymer concentration, PA/PVP blend ratio, solvent/non-solvent quality, and evaporation time on the resulting membrane morphology will be discussed.
CFD study of mixing miscible liquid with high viscosity difference in a stirred tank

NASA Astrophysics Data System (ADS)

Madhania, S.; Cahyani, A. B.; Nurtono, T.; Muharam, Y.; Winardi, S.; Purwanto, W. W.

2018-03-01

The mixing process of miscible liquids with high viscosity difference is crucial role even though the solution mutually dissolved. This paper describes the mixing behaviour of the water-molasses system in a conical-bottomed cylindrical stirred tank (D = 0.28 m and H = 0.395 m) equipped with a side-entry Marine propeller (d = 0.036 m) under the turbulence regime using a three-dimensional and transient CFD-simulation. The objective of this work is to compare the solution strategies was applied in the computational analysis to capture the detail phenomena of mixing two miscible liquid with high viscosity difference. Four solution strategies that have been used are the RANS Standards k-ε (SKE) model as the turbulence model coupled with the Multiple Reference Frame (MRF) method for impeller motion, the RANS Realizable k-ε (RKE) combine with the MRF, the Large Eddy Simulation (LES) coupled with the Sliding Mesh (SM) method and the LES-MRF combination. The transient calculations were conducted with Ansys Fluent 17.1 version. The mixing behaviour and the propeller characteristic are to be compared and discussed in this work. The simulation results show the differences of flow pattern and the molasses distribution profile for every solution strategy. The variation of the flow pattern which happened in each solution strategy showing an instability of the mixing process in stirred tank. The LES-SM strategy shows the realistic direction of flow than another solution strategies.
Liquidus Temperatures and Solidification Behavior in the Copper-Niobium System

NASA Technical Reports Server (NTRS)

Li, D.; Robinson, M. B.; Rathz, T. J.; Williams, G.

1998-01-01

The copper-niobium phase diagram has been under active debate; thus, a corroboratory experimental study is needed. In this investigation, the melts of Cu-Nb alloys at compositions ranging from 5 lo 86 wt% Nb were processed in different environments and solidified at relatively low rates of 50-75 C/s to determine liquidus temperatures and to study solidification behavior. For all samples processed under very clean conditions, only Nb dendrites in a Cu matrix were observed; while in the presents of oxygen impurities, the alloys containing 5-35 wt% Nb exhibited microstructure of Nb-rich spheroids and Nb dendrites in the Cu matrix. The results obtained from clean conditions are in fair agreement with the Cu-Nb phase diagram having an S-shaped, near-horizontal appearances of the liquidus. The formation of Nb-rich droplets at slow cooling rates is discussed in terms of a stable liquid miscibility gap induced by oxygen.

Synthesis and phase behavior of end-functionalized associating polymers

NASA Astrophysics Data System (ADS)

Wrue, Michelle H.

We have explored polymer blend phase behavior in the presence of multiple hydrogen bonding end-groups. This work details the synthesis of functionalized polymers and their subsequent use in miscibility studies. The synthesis of end-functionalized hydrogen bonding polymers and the investigation of their physical properties and miscibility is presented. Mono-functional and telechelic ureidopyrimidinone (UPy) functionalized polymers were prepared by two main routes: post-polymerization functionalization (of commercially available or synthesized polymers); and polymerization of monomers using a functionalized initiator. UPy-functionalized polymers were prepared with a variety of polymer backbones including poly(ethylene oxide)s; poly(butadiene)s, poly(dimethyl siloxanxe)s; poly(styrene)s and poly(methyl methacrylate)s. The most successful route to polymers with UPy end-groups was atom transfer radical polymerization (ATRP) using a UPy-functionalized initiator, followed by atom transfer radical coupling (ATRC). The incorporation of ureidopyrimidinone end-groups was shown to affect the physical properties of the polymer backbone. Parent polymers that were liquids became viscous liquids or waxy solids upon UPy-functionalization of chain end. UPy-functionalization of a hydroxyl-terminated polybutadiene (HO-PB-OH) resulted in a waxy solid while the HO-PB-OH precursor was a viscous liquid. The thermal properties of functionalized polymers also differed from those of the unfunctionalized parent polymers. Hot-stage optical microscopy revealed that UPy-functionalized PEO displayed a depressed melting point relative to the analogous unfunctionalized precursor. Differential scanning calorimetry was also used to investigate the synthesized UPy-polymers. UPy-functionalized polystyrenes and poly(methyl methacrylate)s showed an increased T g compared to the equivalent homopolymer standards. This increased Tg was determined to be dependent upon the fraction of UPy groups present and chemical cleavage of the end-groups resulted in Tgs near those observed for polymer standards of comparable molecular weight. Aggregation of UPy end-groups in solution was observed using gel permeation chromatography. Aggregation was only observed for telechelic samples of low molecular weight, indicating that the aggregation of end-groups is dependent upon the concentration of the end-groups. The effect of UPy end-groups on blend miscibility was studied in solution using laser light scattering and in the melt state was using laser light scattering, optical microscopy and differential scanning calorimetry. The incorporation of associating groups onto one end of either blend component decreases miscibility relative to unfunctionalized parent blends. Lower miscibility was also observed for blends in which both components were mono-functionalized with associating end-groups. The largest decrease in miscibility was observed for blends containing telechelic UPy-functionalized polymers, which were immiscible across the entire composition range.
Mutual diffusion of binary liquid mixtures containing methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride

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

Guevara-Carrion, Gabriela; Janzen, Tatjana; Muñoz-Muñoz, Y. Mauricio

Mutual diffusion coefficients of all 20 binary liquid mixtures that can be formed out of methanol, ethanol, acetone, benzene, cyclohexane, toluene, and carbon tetrachloride without a miscibility gap are studied at ambient conditions of temperature and pressure in the entire composition range. The considered mixtures show a varying mixing behavior from almost ideal to strongly non-ideal. Predictive molecular dynamics simulations employing the Green-Kubo formalism are carried out. Radial distribution functions are analyzed to gain an understanding of the liquid structure influencing the diffusion processes. It is shown that cluster formation in mixtures containing one alcoholic component has a significant impactmore » on the diffusion process. The estimation of the thermodynamic factor from experimental vapor-liquid equilibrium data is investigated, considering three excess Gibbs energy models, i.e., Wilson, NRTL, and UNIQUAC. It is found that the Wilson model yields the thermodynamic factor that best suits the simulation results for the prediction of the Fick diffusion coefficient. Four semi-empirical methods for the prediction of the self-diffusion coefficients and nine predictive equations for the Fick diffusion coefficient are assessed and it is found that methods based on local composition models are more reliable. Finally, the shear viscosity and thermal conductivity are predicted and in most cases favorably compared with experimental literature values.« less
Colloidal gas-liquid condensation of polystyrene latex particles with intermediate kappa a values (5 to 160, a > kappa(-1)).

PubMed

Ishikawa, Masamichi; Kitano, Ryota

2010-02-16

Polystyrene latex particles showed gas-liquid condensation under the conditions of large particle radius (a > kappa(-1)) and intermediate kappa a, where kappa is the Debye-Hückel parameter and a is the particle radius. The particles were dissolved in deionized water containing ethanol from 0 to 77 vol %, settled to the bottom of the glass plate within 1 h, and then laterally moved toward the center of a cell over a 20 h period in reaching a state of equilibrium condensation. All of the suspensions that were 1 and 3 microm in diameter and 0.01-0.20 vol % in concentration realized similar gas-liquid condensation with clear gas-liquid boundaries. In 50 vol % ethanol solvent, additional ethanol was added to enhance the sedimentation force so as to restrict the particles in a monoparticle layer thickness. The coexistence of gas-liquid-solid (crystalline solid) was microscopically recognized from the periphery to the center of the condensates. A phase diagram of the gas-liquid condensation was created as a function of KCl concentration at a particle diameter of 3 microm, 0.10 vol % concentration, and 50:50 water/ethanol solvent at room temperature. The miscibility gap was observed in the concentration range from 1 to 250 microM. There was an upper limit of salt concentration where the phase separation disappeared, showing nearly critical behavior of macroscopic density fluctuation from 250 microM to 1 mM. These results add new experimental evidence to the existence of colloidal gas-liquid condensation and specify conditions of like-charge attraction between particles.
Miscible viscous fingering involving production of gel by chemical reactions

NASA Astrophysics Data System (ADS)

Nagatsu, Yuichiro; Hoshino, Kenichi

2015-11-01

We have experimentally investigated miscible viscous fingering with chemical reactions producing gel. Here, two systems were employed. In one system, sodium polyacrylate (SPA) solution and aluminum ion (Al3 +) solution were used as the more and less viscous liquids, respectively. In another system, SPA solution and ferric ion (Fe3 +) solution were used as the more and less viscous liquids, respectively. In the case of Al3 +, displacement efficiency was smaller than that in the non-reactive case, whereas in the case of Fe3 +, the displacement efficiency was larger. We consider that the difference in change of the patterns in the two systems will be caused by the difference in the properties of the gels. Therefore, we have measured the rheological properties of the gels by means of a rheometer. We discuss relationship between the VF patterns and the rheological measurement.
Electro-optical properties of low viscosity driven holographic polymer dispersed liquid crystals

NASA Astrophysics Data System (ADS)

Moon, K. R.; Bae, S. Y.; Kim, B. K.

2015-04-01

Relative diffraction efficiency (RDE), operating voltage, and response times are most important performance characteristics of holographic polymer dispersed liquid crystals (HPDLC). Two types of triallyl isocyanurate (TI) having different structures were incorporated into the conventional transmission grating of HPDLC. Premix viscosity decreased by 13-18% with up to 3% TI, beyond which it increased. TI eliminated induction period and augmented initial grating formation rate at all contents. Saturation RDE increased over 200% while threshold voltage and rise time decreased to about half and 2/3, respectively up to 3% TI, beyond which the tendencies were reversed. Among the two TIs, low viscosity monomer (TA) showed high RDE, while high miscibility monomer (TE) low characteristic voltages and short response times. It is concluded that grating formation is largely favored by low viscosity, while interface tensions and electro-optical performances by miscibility at similar viscosities.
A transition in the viscous fingering instability in miscible fluids

NASA Astrophysics Data System (ADS)

Videbaek, Thomas; Nagel, Sidney R.

2017-11-01

The viscous fingering instability in a quasi-two dimensional Hele-Shaw cell is an example of complex structure formation from benign initial conditions. When the invading fluid has the lesser viscosity, the interface between the two fluids is unstable to finger formation. Here, we study the instability between pairs of miscible fluids in a circular cell with fluid injected at its center. As the injection rate is decreased, diffusion will smooth out the discontinuity in the gap-averaged viscosity at the interface between the fluids. At high injection rates (i.e., high Péclet number, Pe), fingering is associated with three-dimensional structure within the gap between the confining plates. On lowering Pe, we find a sharp transition in the finger morphology at a critical value, Pec (ηi /ηo) 1 / 2 , with ηi (ηo) being the viscosity of the inner (outer) fluid; at this point, the width of the fingers jumps, the length of the fingers shrinks towards zero and the three-dimensional structure goes from half filling to fully filling the gap. Thus, by controlling the viscosity contrast at the interface, one can alter and even completely suppress the instability.
Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D Li xFePO 4 Nanoparticles from Surface Wetting and Coherency Strain

DOE PAGES

Welland, Michael J.; Karpeyev, Dmitry; O’Connor, Devin T.; ...

2015-09-10

We study the mesoscopic effects which suppress phase-segregation in Li xFePO 4 nanoparticles using a multiphysics phase-field model implement on a high performance cluster. We simulate 3D spherical particles of radii from 3nm to 40nm and examine the equilibrium microstructure and voltage profiles as a they depend on size and overall lithiation. The model includes anisotropic, concentration-dependent elastic moduli, misfit strain, and facet dependent surface wetting within a Cahn-Hilliard formulation. Here, we find that the miscibility gap vanishes for particles of radius ~ 5 nm, and the solubility limits change with overall particle lithiation. The corresponding voltage plateau, indicative ofmore » phase-segregation, changes in extent and also vanishes. Surface wetting is found to have a strong effect on stabilizing a variety of microstructures, exaggerating the shifting of solubility limits, and shortening the voltage plateau.« less
Validated Test Method 5030C: Purge-and-Trap for Aqueous Samples

EPA Pesticide Factsheets

This method describes a purge-and-trap procedure for the analysis of volatile organic compoundsin aqueous samples & water miscible liquid samples. It also describes the analysis of high concentration soil and waste sample extracts prepared in Method 5035.
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.
Giant Plasma Membrane Vesicles: An Experimental Tool for Probing the Effects of Drugs and Other Conditions on Membrane Domain Stability.

PubMed

Gerstle, Zoe; Desai, Rohan; Veatch, Sarah L

2018-01-01

Giant plasma membrane vesicles (GPMVs) are isolated directly from living cells and provide an alternative to vesicles constructed of synthetic or purified lipids as an experimental model system for use in a wide range of assays. GPMVs capture much of the compositional protein and lipid complexity of intact cell plasma membranes, are filled with cytoplasm, and are free from contamination with membranes from internal organelles. GPMVs often exhibit a miscibility transition below the growth temperature of their parent cells. GPMVs labeled with a fluorescent protein or lipid analog appear uniform on the micron-scale when imaged above the miscibility transition temperature, and separate into coexisting liquid domains with differing membrane compositions and physical properties below this temperature. The presence of this miscibility transition in isolated GPMVs suggests that a similar phase-like heterogeneity occurs in intact plasma membranes under growth conditions, albeit on smaller length scales. In this context, GPMVs provide a simple and controlled experimental system to explore how drugs and other environmental conditions alter the composition and stability of phase-like domains in intact cell membranes. This chapter describes methods to generate and isolate GPMVs from adherent mammalian cells and to interrogate their miscibility transition temperatures using fluorescence microscopy. © 2018 Elsevier Inc. All rights reserved.
“Bligh and Dyer” and Folch Methods for Solid–Liquid–Liquid Extraction of Lipids from Microorganisms. Comprehension of Solvatation Mechanisms and towards Substitution with Alternative Solvents

PubMed Central

Breil, Cassandra; Abert Vian, Maryline; Zemb, Thomas; Kunz, Werner; Chemat, Farid

2017-01-01

Bligh and Dyer (B & D) or Folch procedures for the extraction and separation of lipids from microorganisms and biological tissues using chloroform/methanol/water have been used tens of thousands of times and are “gold standards” for the analysis of extracted lipids. Based on the Conductor-like Screening MOdel for realistic Solvatation (COSMO-RS), we select ethanol and ethyl acetate as being potentially suitable for the substitution of methanol and chloroform. We confirm this by performing solid–liquid extraction of yeast (Yarrowia lipolytica IFP29) and subsequent liquid–liquid partition—the two steps of routine extraction. For this purpose, we consider similar points in the ternary phase diagrams of water/methanol/chloroform and water/ethanol/ethyl acetate, both in the monophasic mixtures and in the liquid–liquid miscibility gap. Based on high performance thin-layer chromatography (HPTLC) to obtain the distribution of lipids classes, and gas chromatography coupled with a flame ionisation detector (GC/FID) to obtain fatty acid profiles, this greener solvents pair is found to be almost as effective as the classic methanol–chloroform couple in terms of efficiency and selectivity of lipids and non-lipid material. Moreover, using these bio-sourced solvents as an alternative system is shown to be as effective as the classical system in terms of the yield of lipids extracted from microorganism tissues, independently of their apparent hydrophilicity. PMID:28346372
First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

NASA Astrophysics Data System (ADS)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-04-01

Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.
Spiral pattern in a radial displacement in a Hele-Shaw cell

NASA Astrophysics Data System (ADS)

Ban, Mitsumasa; Nagatsu, Yuichiro; Hayashi, Atsushi; Kato, Yoshihiro; Tada, Yutaka

2008-11-01

When a reactive and miscible less-viscous liquid displaces a more-viscous liquid in a Hele-Shaw cell, reactive miscible viscous fingering takes place. We have experimentally shown that the pattern created by the displacement of a more-viscous fluid by a less-viscous one in a radial Hele-Shaw cell develops not radially but spirally when a more-viscous sodium polyacrylate solution is displaced by a less-viscous trivalent iron ion (Fe^3+) solution with a sufficiently high concentration of Fe^3+. Another experiment in order to investigate the mechanism of spiral pattern formation revealed that an instantaneous chemical reaction takes place between the two fluids and at high Fe^3+ concentrations it produces a film of the gel at the contact plane. The gel is formed by three-dimensional network structures between the polyacrylate solution and the trivalent iron ion (Fe^3+) solution. We have proposed a physical model that the gel's film is responsible for the form of the spiral pattern.
Contraction of an air disk caught between two different liquids

NASA Astrophysics Data System (ADS)

Thoraval, M.-J.; Thoroddsen, S. T.

2013-12-01

When a drop impacts a pool of liquid it entraps a thin disk of air under its center. This disk contracts rapidly into a bubble to minimize surface energy. Herein we use ultra-high-speed imaging to measure the contraction speed of this disk when the drop and pool are of different liquids. For miscible liquids the contraction rate is governed by the weaker of the two surface tensions. Some undulations are observed on the edge of the disk for a water drop impacting a pool of water, but not on a pool of lower surface tension. Similar results are observed for a pair of immiscible liquids.
Estimation of minimum miscibility pressure (MMP) of CO2 and liquid n-alkane systems using an improved MRI technique.

PubMed

Liu, Yu; Jiang, Lanlan; Song, Yongchen; Zhao, Yuechao; Zhang, Yi; Wang, Dayong

2016-02-01

Minimum miscible pressure (MMP) of gas and oil system is a key parameter for the injection system design of CO2 miscible flooding. Some industrial standard approaches such as the experiment using a rising bubble apparatus (RBA), the slim tube tests (STT), the pressure-density diagram (PDD), etc. have been applied for decades to determine the MMP of gas and oil. Some theoretical or experiential calculations of the MMP were also applied to the gas-oil miscible system. In the present work, an improved technique based on our previous research for the estimation of the MMP by using magnetic resonance imaging (MRI) was proposed. This technique was then applied to the CO2 and n-alkane binary and ternary systems to observe the mixing procedure and to study the miscibility. MRI signal intensities, which represent the proton concentration of n-alkane in both the hydrocarbon rich phase and the CO2 rich phase, were plotted as a reference for determining the MMP. The accuracy of the MMP obtained by using this improved technique was enhanced comparing with the data obtained from our previous works. The results also show good agreement with other established techniques (such as the STT) in previous published works. It demonstrates increases of MMPs as the temperature rise from 20 °C to 37.8 °C. The MMPs of CO2 and n-alkane systems are also found to be proportional to the carbon number in the range of C10 to C14. Copyright © 2015 Elsevier Inc. All rights reserved.
Multicomponent homogeneous alloys and method for making same

DOEpatents

Dutta, Partha S.; Miller, Thomas R.

2003-09-02

The present application discloses a method for preparing a homogeneous ternary or quaternary alloy from a quaternary melt. The method includes providing a family of phase diagrams for the quaternary melt which shows (i) composition/temperature data, (ii) tie lines connecting equilibrium liquid and solid compositions, and (iii) isotherms representing boundaries of a miscibility gap. Based on the family of phase diagrams, a quaternary melt composition and an alloy growth temperature is selected. A quaternary melt having the selected quaternary melt composition is provided and a ternary or quaternary alloy is grown from the quaternary melt at the selected alloy growth temperature. A method for making homogeneous ternary or quaternary alloy from a ternary or quaternary melt is also disclosed, as are homogeneous quaternary single-crystal alloys which are substantially free from crystal defects and which have the formula A.sub.x B.sub.1-x C.sub.y D.sub.1-y, x and y being the same or different and in the range of 0.001 to 0.999.
Liquidus Temperatures and Solidification Behavior in the Copper-Niobium System

NASA Technical Reports Server (NTRS)

Li, D.; Robinson, M. B.; Rathz, T. J.; Williams, G.

1998-01-01

The copper-niobium phase diagram has been under active debate; thus, a corroboratory experimental study is needed. In this investigation, the melts of Cu-Nb alloys at compositions ranging from 5 to 86 wt pct Nb were processed in different environments and solidified at relatively low cooling rates of 50 to 75 C/s to determine liquidus temperatures and to study solidification behavior. For all samples processed under very clean conditions, only Nb dendrites in a Cu matrix were observed; while in the presence of oxygen impurities the alloys containing 5 to 35 wt pct Nb exhibited microstructure of Nb-rich spheroids and Nb dendrites in the Cu matrix. The results obtained from clean conditions are in fair agreement with the Cu-Nb phase diagram having an S-shaped, near-horizontal appearance of the liquidus. The formation of Nb- rich droplets at slow cooling rates is discussed in terms of a stable liquid miscibility gap induced by oxygen.
The Cu-Li-Sn Phase Diagram: Isopleths, Liquidus Projection and Reaction Scheme

PubMed Central

Flandorfer, Hans

2016-01-01

The Cu-Li-Sn phase diagram was constructed based on XRD and DTA data of 60 different alloy compositions. Eight ternary phases and 14 binary solid phases form 44 invariant ternary reactions, which are illustrated by a Scheil-Schulz reaction scheme and a liquidus projection. Phase equilibria as a function of concentration and temperature are shown along nine isopleths. This report together with an earlier publication of our group provides for the first time comprehensive investigations of phase equilibria and respective phase diagrams. Most of the phase equilibria could be established based on our experimental results. Only in the Li-rich part where many binary and ternary compounds are present estimations had to be done which are all indicated by dashed lines. A stable ternary miscibility gap could be found which was predicted by modelling the liquid ternary phase in a recent work. The phase diagrams are a crucial input for material databases and thermodynamic optimizations regarding new anode materials for high-power Li-ion batteries. PMID:27788175
Combined Exposure of Methylene Chloride and Carbon Monoxide in Smoking and Nonsmoking Paint Strippers.

DTIC Science & Technology

1983-12-01

colorless volatile liquid whose solubility in water is minimal. It is completely miscible with most organic solvents (1). It is nonflammable and has a...University oi Utah will provide you, without charge, emergency and temporary medical tratament not otherwise covered by Insurance. Furthermore, if your
Statistical Moments in Variable Density Incompressible Mixing Flows

DTIC Science & Technology

2015-08-28

front tracking method: Verification and application to simulation of the primary breakup of a liquid jet . SIAM J. Sci. Comput., 33:1505–1524, 2011. [15... elliptic problem. In case of failure, Generalized Minimal Residual (GMRES) method [78] is used instead. Then update face velocities as follows: u n+1...of the ACM Solid and Physical Modeling Symposium, pages 159–170, 2008. [51] D. D. Joseph. Fluid dynamics of two miscible liquids with diffusion and

A test-tube model for rainfall

NASA Astrophysics Data System (ADS)

Wilkinson, Michael

2014-05-01

If the temperature of a cell containing two partially miscible liquids is changed very slowly, so that the miscibility is decreased, microscopic droplets nucleate, grow and migrate to the interface due to their buoyancy. The system may show an approximately periodic variation of the turbidity of the mixture, as the mean droplet size fluctuates. These precipitation events are analogous to rainfall. This paper considers a theoretical model for these experiments. After nucleation the initial growth is by Ostwald ripening, followed by a finite-time runaway growth of droplet sizes due to larger droplets sweeping up smaller ones. The model predicts that the period \\Delta t and the temperature sweep rate ξ are related by \\Delta t\\sim C \\xi^{-3/7} , and is in good agreement with experiments. The coefficient C has a power-law divergence approaching the critical point of the miscibility transition: C\\sim (T-T_{\\text{c}})^{-\\eta} , and the critical exponent η is determined. It is argued that while the mechanism does not provide a quantitative description of terrestrial rainfall, it may be a faithful model for precipitation on other planets.
Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

PubMed

Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

2016-08-23

Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements.
Bridging the gap between atomic microstructure and electronic properties of alloys: The case of (In,Ga)N

NASA Astrophysics Data System (ADS)

Chan, J. A.; Liu, J. Z.; Zunger, Alex

2010-07-01

The atomic microstructure of alloys is rarely perfectly random, instead exhibiting differently shaped precipitates, clusters, zigzag chains, etc. While it is expected that such microstructural features will affect the electronic structures (carrier localization and band gaps), theoretical studies have, until now, been restricted to investigate either perfectly random or artificial “guessed” microstructural features. In this paper, we simulate the alloy microstructures in thermodynamic equilibrium using the static Monte Carlo method and study their electronic structures explicitly using a pseudopotential supercell approach. In this way, we can bridge atomic microstructures with their electronic properties. We derive the atomic microstructures of InGaN using (i) density-functional theory total energies of ˜50 ordered structures to construct a (ii) multibody cluster expansion, including strain effects to which we have applied (iii) static Monte Carlo simulations of systems consisting of over 27000 atoms to determine the equilibrium atomic microstructures. We study two types of alloy thermodynamic behavior: (a) under lattice incoherent conditions, the formation enthalpies are positive and thus the alloy system phase-separates below the miscibility-gap temperature TMG , (b) under lattice coherent conditions, the formation enthalpies can be negative and thus the alloy system exhibits ordering tendency. The microstructure is analyzed in terms of structural motifs (e.g., zigzag chains and InnGa4-nN tetrahedral clusters). The corresponding electronic structure, calculated with the empirical pseudopotentials method, is analyzed in terms of band-edge energies and wave-function localization. We find that the disordered alloys have no electronic localization but significant hole localization, while below the miscibility gap under the incoherent conditions, In-rich precipitates lead to strong electron and hole localization and a reduction in the band gap.
Lunar and Planetary Science XXXV: Terrestrial Planets: Building Blocks and Differentiation

NASA Technical Reports Server (NTRS)

2004-01-01

The session "Terrestrial Planets: Building Blocks and Differentiation: included the following topics:Magnesium Isotopes in the Earth, Moon, Mars, and Pallasite Parent Body: High-Precision Analysis of Olivine by Laser-Ablation Multi-Collector ICPMS; Meteoritic Constraints on Collision Rates in the Primordial Asteroid Belt and Its Origin; New Constraints on the Origin of the Highly Siderophile Elements in the Earth's Upper Mantle; Further Lu-Hf and Sm-Nd Isotopic Data on Planetary Materials and Consequences for Planetary Differentiation; A Deep Lunar Magma Ocean Based on Neodymium, Strontium and Hafnium Isotope Mass Balance Partial Resetting on Hf-W System by Giant Impacts; On the Problem of Metal-Silicate Equilibration During Planet Formation: Significance for Hf-W Chronometry ; Solid Metal-Liquid Metal Partitioning of Pt, Re, and Os: The Effect of Carbon; Siderophile Element Abundances in Fe-S-Ni-O Melts Segregated from Partially Molten Ordinary Chondrite Under Dynamic Conditions; Activity Coefficients of Silicon in Iron-Nickel Alloys: Experimental Determination and Relevance for Planetary Differentiation; Reinvestigation of the Ni and Co Metal-Silicate Partitioning; Metal/Silicate Paritioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition; and Closure of the Fe-S-Si Liquid Miscibility Gap at High Pressure and Its Implications for Planetary Core Formation.
Liquidus Projections of Bi-Se-Ga and Bi-Se-Te Ternary Systems

NASA Astrophysics Data System (ADS)

Lin, Po-han; Chen, Sinn-wen; Hwang, Jenn-dong; Chu, Hsu-shen

2016-12-01

This study determines the liquidus projections of both Bi-Se-Ga and Bi-Se-Te ternary systems which are constituent ternary systems of promising Bi-Se-Te-Ga thermoelectric materials. Ternary Bi-Se-Ga and Bi-Se-Te alloys are prepared. Their primary solidification phases are experimentally determined, and thermal analysis experiments are carried out. The liquidus projections are determined based on the ternary experimental results and phase diagrams of constituent binary systems. The Bi-Se-Ga system includes seven primary solidification phases, Bi, Ga, GaSe, Ga2Se3, Se, Bi2Se3, and (Bi2)n(Bi2Se3)m. In the Bi-Se-Te system, there are five primary solidification phases, Bi, (Bi2)n(Bi2Te3)m, Bi2(Se,Te)3, (Se,Te), and (Bi2)n(Bi2Se3)m. Both the (Bi2)n(Bi2Te3)m and (Bi2)n(Bi2Se3)m phases are not a single phase, but a collection of series undetermined phases. Large miscibility gaps are observed in the Bi-Se-Ga system. The temperatures of the invariant reactions, Liquid + Bi + GaSe = Ga and Liquid + Ga2Se3 = Bi + GaSe, are at 495 K (222 °C) and 533 K (260 °C), respectively.
Damping of Quasi-stationary Waves Between Two Miscible Liquids

NASA Technical Reports Server (NTRS)

Duval, Walter M. B.

2002-01-01

Two viscous miscible liquids with an initially sharp interface oriented vertically inside a cavity become unstable against oscillatory external forcing due to Kelvin-Helmholtz instability. The instability causes growth of quasi-stationary (q-s) waves at the interface between the two liquids. We examine computationally the dynamics of a four-mode q-s wave, for a fixed energy input, when one of the components of the external forcing is suddenly ceased. The external forcing consists of a steady and oscillatory component as realizable in a microgravity environment. Results show that when there is a jump discontinuity in the oscillatory excitation that produced the four-mode q-s wave, the interface does not return to its equilibrium position, the structure of the q-s wave remains imbedded between the two fluids over a long time scale. The damping characteristics of the q-s wave from the time history of the velocity field show overdamped and critically damped response; there is no underdamped oscillation as the flow field approaches steady state. Viscous effects serve as a dissipative mechanism to effectively damp the system. The stability of the four-mode q-s wave is dependent on both a geometric length scale as well as the level of background steady acceleration.
Growth mechanism of GaAs1-xSbx ternary alloy thin film on MOCVD reactor using TMGa, TDMAAs and TDMASb

NASA Astrophysics Data System (ADS)

Suhandi, A.; Tayubi, Y. R.; Arifin, P.

2016-04-01

Metal Organic Chemical Vapor Deposition (MOCVD) is a method for growing a solid material (in the form of thin films, especially for semiconductor materials) using vapor phase metal organic sources. Studies on the growth mechanism of GaAs1-xSbx ternary alloy thin solid film in the range of miscibility-gap using metal organic sources trimethylgallium (TMGa), trisdimethylaminoarsenic (TDMAAs), and trisdimethylaminoantimony (TDMASb) on MOCVD reactor has been done to understand the physical and chemical processes involved. Knowledge of the processes that occur during alloy formation is very important to determine the couple of growth condition and growth parameters are appropriate for yield high quality GaAs1-xSbx alloy. The mechanism has been studied include decomposition of metal organic sources and chemical reactions that may occur, the incorporation of the alloy elements forming and the contaminants element that are formed in the gown thin film. In this paper presented the results of experimental data on the growth of GaAs1-xSbx alloy using Vertical-MOCVD reactor to demonstrate its potential in growing GaAs1-xSbx alloy in the range of its miscibility gap.
Removing sulphur oxides from a fluid stream

DOEpatents

Katz, Torsten; Riemann, Christian; Bartling, Karsten; Rigby, Sean Taylor; Coleman, Luke James Ivor; Lail, Marty Alan

2014-04-08

A process for removing sulphur oxides from a fluid stream, such as flue gas, comprising: providing a non-aqueous absorption liquid containing at least one hydrophobic amine, the liquid being incompletely miscible with water; treating the fluid stream in an absorption zone with the non-aqueous absorption liquid to transfer at least part of the sulphur oxides into the non-aqueous absorption liquid and to form a sulphur oxide-hydrophobic amine-complex; causing the non-aqueous absorption liquid to be in liquid-liquid contact with an aqueous liquid whereby at least part of the sulphur oxide-hydrophobic amine-complex is hydrolyzed to release the hydrophobic amine and sulphurous hydrolysis products, and at least part of the sulphurous hydrolysis products is transferred into the aqueous liquid; separating the aqueous liquid from the non-aqueous absorption liquid. The process mitigates absorbent degradation problems caused by sulphur dioxide and oxygen in flue gas.
Equilibrating high-molecular-weight symmetric and miscible polymer blends with hierarchical back-mapping.

PubMed

Ohkuma, Takahiro; Kremer, Kurt; Daoulas, Kostas

2018-05-02

Understanding properties of polymer alloys with computer simulations frequently requires equilibration of samples comprised of microscopically described long molecules. We present the extension of an efficient hierarchical backmapping strategy, initially developed for homopolymer melts, to equilibrate high-molecular-weight binary blends. These mixtures present significant interest for practical applications and fundamental polymer physics. In our approach, the blend is coarse-grained into models representing polymers as chains of soft blobs. Each blob stands for a subchain with N b microscopic monomers. A hierarchy of blob-based models with different resolution is obtained by varying N b . First the model with the largest N b is used to obtain an equilibrated blend. This configuration is sequentially fine-grained, reinserting at each step the degrees of freedom of the next in the hierarchy blob-based model. Once the blob-based description is sufficiently detailed, the microscopic monomers are reinserted. The hard excluded volume is recovered through a push-off procedure and the sample is re-equilibrated with molecular dynamics (MD), requiring relaxation on the order of the entanglement time. For the initial method development we focus on miscible blends described on microscopic level through a generic bead-spring model, which reproduces hard excluded volume, strong covalent bonds, and realistic liquid density. The blended homopolymers are symmetric with respect to molecular architecture and liquid structure. To parameterize the blob-based models and validate equilibration of backmapped samples, we obtain reference data from independent hybrid simulations combining MD and identity exchange Monte Carlo moves, taking advantage of the symmetry of the blends. The potential of the backmapping strategy is demonstrated by equilibrating blend samples with different degree of miscibility, containing 500 chains with 1000 monomers each. Equilibration is verified by comparing chain conformations and liquid structure in backmapped blends with the reference data. Possible directions for further methodological developments are discussed.
Equilibrating high-molecular-weight symmetric and miscible polymer blends with hierarchical back-mapping

NASA Astrophysics Data System (ADS)

Ohkuma, Takahiro; Kremer, Kurt; Daoulas, Kostas

2018-05-01

Understanding properties of polymer alloys with computer simulations frequently requires equilibration of samples comprised of microscopically described long molecules. We present the extension of an efficient hierarchical backmapping strategy, initially developed for homopolymer melts, to equilibrate high-molecular-weight binary blends. These mixtures present significant interest for practical applications and fundamental polymer physics. In our approach, the blend is coarse-grained into models representing polymers as chains of soft blobs. Each blob stands for a subchain with N b microscopic monomers. A hierarchy of blob-based models with different resolution is obtained by varying N b. First the model with the largest N b is used to obtain an equilibrated blend. This configuration is sequentially fine-grained, reinserting at each step the degrees of freedom of the next in the hierarchy blob-based model. Once the blob-based description is sufficiently detailed, the microscopic monomers are reinserted. The hard excluded volume is recovered through a push-off procedure and the sample is re-equilibrated with molecular dynamics (MD), requiring relaxation on the order of the entanglement time. For the initial method development we focus on miscible blends described on microscopic level through a generic bead-spring model, which reproduces hard excluded volume, strong covalent bonds, and realistic liquid density. The blended homopolymers are symmetric with respect to molecular architecture and liquid structure. To parameterize the blob-based models and validate equilibration of backmapped samples, we obtain reference data from independent hybrid simulations combining MD and identity exchange Monte Carlo moves, taking advantage of the symmetry of the blends. The potential of the backmapping strategy is demonstrated by equilibrating blend samples with different degree of miscibility, containing 500 chains with 1000 monomers each. Equilibration is verified by comparing chain conformations and liquid structure in backmapped blends with the reference data. Possible directions for further methodological developments are discussed.
Salting-out assisted liquid-liquid extraction for the determination of biogenic amines in fruit juices and alcoholic beverages after derivatization with 1-naphthylisothiocyanate and high performance liquid chromatography.

PubMed

Jain, Archana; Gupta, Manju; Verma, Krishna K

2015-11-27

A new method for determining biogenic amines in fruit juices and alcoholic beverages is described involving reaction of biogenic amines with 1-naphthylisothiocyanate followed by extraction of 1-naphthylthiourea derivatives with water-miscible organic solvent acetonitrile when solvents phase separation occurred using ammonium sulphate, a process called salting-out assisted liquid-liquid extraction. The extract was analyzed by high-performance liquid chromatography with UV detection at 254nm. The new reagent avoided many of the inconveniences as observed with existing derivatizing agents, such as dansyl chloride and benzoyl chloride, in regard to their inselectivity, instability, adverse effect of excess reagent, and necessity to remove excess reagent. The procedure has been optimized with respect to reaction time and temperature, water-miscible extraction solvent, and salt for solvents phase separation. Use of reagent as dispersed phase in aqueous medium produced derivatives in high yield. A linear calibration was obtained between the amount of biogenic amines in range 1-1000μgL(-1) and peak areas of corresponding thioureas formed; the correlation coefficient was 0.9965, and the limit of detection and limit of quantification found were 1.1μgL(-1) and 3.2μgL(-1), respectively. The pre-concentration method gave an average enrichment factor of 94. The application of the method has been demonstrated in the determination of biogenic amines in commercial samples of fruit juices and alcoholic beverages. In spiking experiments to real samples, the average recovery found by the present method was 94.5% that agreed well with 95.8% obtained by established comparison methods. Copyright © 2015 Elsevier B.V. All rights reserved.
Method for forming energetic nanopowders

DOEpatents

Lee, Kien-Yin; Asay, Blaine W.; Kennedy, James E.

2013-10-15

A method for the preparation of neat energetic powders, having nanometer dimensions, is described herein. For these neat powder, a solution of a chosen energetic material is prepared in an aprotic solvent and later combined with liquid hexane that is miscible with such solvent. The energetic material chosen is less soluble in the liquid hexane than in the aprotic solvent and the liquid hexane is cooled to a temperature that is below that of the solvent solution. In order to form a precipitate of said neat powders, the solvent solution is rapidly combined with the liquid hexane. When the resulting precipitate is collected, it may be dried and filtered to yield an energetic nanopowder material.
Nonergodicity of microfine binary systems

NASA Astrophysics Data System (ADS)

Son, L. D.; Sidorov, V. E.; Popel', P. S.; Shul'gin, D. B.

2016-02-01

The correction to the equation of state that is related to the nonergodicity of diffusion dynamics is discussed for a binary solid solution with a limited solubility. It is asserted that, apart from standard thermodynamic variables (temperature, volume, concentration), this correction should be taken into account in the form of the average local chemical potential fluctuations associated with microheterogeneity in order to plot a phase diagram. It is shown that a low value of this correction lowers the miscibility gap and that this gap splits when this correction increases. This situation is discussed for eutectic systems and Ga-Pb, Fe-Cu, and Cu-Zr alloys.
40 CFR 158.2120 - Microbial pesticides product analysis data requirements table.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Certification of limits R MP EP -- Physical and Chemical Characteristics 830.6302 Color R TGAI TGAI -- 830.6303....6319 Miscibility R MP EP 2 830.6320 Corrosion Characteristics R MP EP 3 830.7000 pH R TGAI TGAI -- 830... pesticides are packaged in metal, plastic, or paper containers. 4. Only required for liquid forms of...
First-principles calculations, experimental study, and thermodynamic modeling of the Al-Co-Cr system.

PubMed

Liu, Xuan L; Gheno, Thomas; Lindahl, Bonnie B; Lindwall, Greta; Gleeson, Brian; Liu, Zi-Kui

2015-01-01

The phase relations and thermodynamic properties of the condensed Al-Co-Cr ternary alloy system are investigated using first-principles calculations based on density functional theory (DFT) and phase-equilibria experiments that led to X-ray diffraction (XRD) and electron probe micro-analysis (EPMA) measurements. A thermodynamic description is developed by means of the calculations of phase diagrams (CALPHAD) method using experimental and computational data from the present work and the literature. Emphasis is placed on modeling the bcc-A2, B2, fcc-γ, and tetragonal-σ phases in the temperature range of 1173 to 1623 K. Liquid, bcc-A2 and fcc-γ phases are modeled using substitutional solution descriptions. First-principles special quasirandom structures (SQS) calculations predict a large bcc-A2 (disordered)/B2 (ordered) miscibility gap, in agreement with experiments. A partitioning model is then used for the A2/B2 phase to effectively describe the order-disorder transitions. The critically assessed thermodynamic description describes all phase equilibria data well. A2/B2 transitions are also shown to agree well with previous experimental findings.
Density and Adiabatic Compressibility of the Immiscible Molten AgBr+LiCl Mixture

NASA Astrophysics Data System (ADS)

Stepanov, Victor P.; Kulik, Nina P.

2017-04-01

The adiabatic compressibility, β, of the immiscible liquid mixture 0.52 LiCl+0.48 AgBr (the top of the miscibility gap) was experimentally investigated in the temperature range from the melting point to the critical mixing temperature using the sound velocity values, u, measured by the pulse method, and the density quantities, ρ, which were determined using the hydrostatic weight procedure based on the relationship β=u- 2ρ- 1. It is shown that the coefficients of the temperature dependencies for the compressibility and density of the upper and lower equilibrium phases have opposite signs because of the superposition of the intensity of the thermal motion of the ions and the change in the composition of the phases. The differences, ∆β and ∆ρ, in the magnitudes of the compressibility and density for the equilibrium phases decrease with temperature elevation. The temperature dependencies of the compressibility and density difference are described using the empirical equations ∆β≈(Tc-T)0.438 and ∆ρ≈(Tc-T)0.439.
TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: phase diagrams and molecular dynamic simulations.

PubMed

Taha, Mohamed; Lee, Ming-Jer

2013-06-28

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

NASA Technical Reports Server (NTRS)

Hopper, R. W.

1976-01-01

The equilibrium stability criterion for diffuse interfaces in a two-component solution with a miscibility gap requires that the interdiffusion flux vanish. If the system is continuously deformed, convective fluxes disrupt the equilibrium in the interface regions and induce a counter diffusive flux, which is dissipative and contributes to the apparent viscosity of the mixture. Chemical free energy is recoverably stored, causing viscoelastic phenomena. Both effects are significant.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Meng; Yi, Ming; Tian, Wei

Here, the complex interdigitated phases have greatly frustrated attempts to document the basic features of the superconductivity in the alkali metal intercalated iron chalcogenides. Here, using elastic neutron scattering, energy-dispersive x-ray spectroscopy, and resistivity measurements, we elucidate the relations of these phases in Rb xFe ySe 2-zS z. We find (i) the iron content is crucial in stabilizing the stripe antiferromagnetic (AF) phase with rhombic iron vacancy order (y ≈ 1.5), the block AF phase with root 5 x root 5 iron vacancy order (y ≈ 1.6), and the iron vacancy-free phase (y ≈ 2); and (ii) the iron vacancy-freemore » superconducting phase (z = 0) evolves into an iron vacancy-free metallic phase with sulfur substitution (z > 1.5) due to the progressive decrease of the electronic correlation strength. Both the stripe AF phase and the block AF phase are Mott insulators. The iron-rich compounds (y > 1.6) undergo a first order transition from an iron vacancy disordered phase at high temperatures into the √5 x √5 iron vacancy ordered phase and the iron vacancy-free phase below T s. Our data demonstrate that there are miscibility gaps between these three phases. The existence of the miscibility gaps in the iron content is a key to understanding the relationship between these complicated phases.« less
Optical Studies of model binary miscibility gap system

NASA Technical Reports Server (NTRS)

Lacy, L. L.; Witherow, W. K.; Facemire, B. R.; Nishioka, G. M.

1982-01-01

In order to develop a better understanding of separation processes in binary miscibility gap metal alloys, model transparent fluid systems were studied. The system selected was diethylene glycol-ethyl salicylate which has convenient working temperatures (288 to 350 K), low toxicity, and is relatively easy to purify. The system is well characterized with respect to its phase diagram, density, surface and interfacial tensions, viscosity and other pertinent physical properties. Studies of migration of the dispersed phase in a thermal gradient were performed using conventional photomicroscopy. Velocities of the droplets of the dispersed phase were measured and compared to calculated rates which included both Stokes and thermal components. A holographic microscopy system was used to study growth, coalescence, and particle motions. Sequential holograms allowed determination of particle size distribution changes with respect to time and temperature. Holographic microscopy is capable of recording particle densities up to 10 to the 7th power particles/cu cm and is able to resolve particles of the order of 2 to 3 microns in diameter throughout the entire volume of the test cell. The reconstructed hologram produces a wavefront that is identical to the original wavefront as it existed when the hologram was made. The reconstructed wavefront is analyzed using a variety of conventional optical methods.

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.
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.
A Variational Statistical-Field Theory for Polar Liquid Mixtures

NASA Astrophysics Data System (ADS)

Zhuang, Bilin; Wang, Zhen-Gang

Using a variational field-theoretic approach, we derive a molecularly-based theory for polar liquid mixtures. The resulting theory consists of simple algebraic expressions for the free energy of mixing and the dielectric constant as functions of mixture composition. Using only the dielectric constants and the molar volumes of the pure liquid constituents, the theory evaluates the mixture dielectric constants in good agreement with the experimental values for a wide range of liquid mixtures, without using adjustable parameters. In addition, the theory predicts that liquids with similar dielectric constants and molar volumes dissolve well in each other, while sufficient disparity in these parameters result in phase separation. The calculated miscibility map on the dielectric constant-molar volume axes agrees well with known experimental observations for a large number of liquid pairs. Thus the theory provides a quantification for the well-known empirical ``like-dissolves-like'' rule. Bz acknowledges the A-STAR fellowship for the financial support.
Phase equilibrium measurements on nine binary mixtures

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

Wilding, W.V.; Giles, N.F.; Wilson, L.C.

1996-11-01

Phase equilibrium measurements have been performed on nine binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following systems at two temperatures each: (aminoethyl)piperazine + diethylenetriamine; 2-butoxyethyl acetate + 2-butoxyethanol; 2-methyl-2-propanol + 2-methylbutane; 2-methyl-2-propanol + 2-methyl-2-butene; methacrylonitrile + methanol; 1-chloro-1,1-difluoroethane + hydrogen chloride; 2-(hexyloxy)ethanol + ethylene glycol; butane + ammonia; propionaldehyde + butane. Equilibrium vapor and liquid phase compositions were derived form the PTx data using the Soave equation of state to represent the vapor phase and the Wilson or the NRTL activity coefficient model to represent the liquid phase. A large immiscibility region existsmore » in the butane + ammonia system at 0 C. Therefore, separate vapor-liquid-liquid equilibrium measurements were performed on this system to more precisely determine the miscibility limits and the composition of the vapor phase in equilibrium with the two liquid phases.« less
Initial temperatures effect on the mixing efficiency and flow modes in T-shaped micromixer

NASA Astrophysics Data System (ADS)

Lobasov, A. S.; Shebeleva, A. A.

2017-09-01

Flow patterns and mixing of liquids with different initial temperatures in T-shaped micromixers are numerically investigated on the Reynolds number range from 1 to 250. The temperature of the one of mixing media was set equal to 20°C, while the temperature of the another mixing media was varied from 10°C to 50°C its effect on the flow structure and the mixing was studied. The dependences of the mixing efficiency and the pressure difference in this mixer on the difference in initial temperatures of miscible fluids and the Reynolds number were obtained. It was shown that the presence of a difference in initial temperatures of miscible fluids leads to a shift of flow regimes and the flow and mixing of two fluids with different initial temperatures can be considered as self-similar pattern with regard to the reduced Reynolds number.
Novel Diffusivity Measurement Technique

NASA Technical Reports Server (NTRS)

Rashidnia, Nasser

2001-01-01

A common-path interferometer (CPI) system was developed to measure the diffusivity of liquid pairs. The CPI is an optical technique that can be used to measure changes in the gradient of the refraction index of transparent materials. This system uses a shearing interferometer that shares the same optical path from a laser light source to the final imaging plane. Hence, the molecular diffusion coefficient of liquids can be determined using the physical relations between changes in the optical path length and the liquid phase properties. The data obtained with this interferometer were compared with similar results from other techniques and demonstrated that the instrument is superior in measuring the diffusivity of miscible liquids while keeping the system very compact and robust. CPI can also be used for studies in interface dynamics and other diffusion-dominated-process applications.
High pressure liquid chromatographic gradient mixer

DOEpatents

Daughton, Christian G.; Sakaji, Richard H.

1985-01-01

A gradient mixer which effects the continuous mixing of any two miscible solvents without excessive decay or dispersion of the resultant isocratic effluent or of a linear or exponential gradient. The two solvents are fed under low or high pressure by means of two high performance liquid chromatographic pumps. The mixer comprises a series of ultra-low dead volume stainless steel tubes and low dead volume chambers. The two solvent streams impinge head-on at high fluxes. This initial nonhomogeneous mixture is then passed through a chamber packed with spirally-wound wires which cause turbulent mixing thereby homogenizing the mixture with minimum "band-broadening".
High-pressure liquid chromatographic gradient mixer

DOEpatents

Daughton, C.G.; Sakaji, R.H.

1982-09-08

A gradient mixer effects the continuous mixing of any two miscible solvents without excessive decay or dispersion of the resultant isocratic effluent or of a linear or exponential gradient. The two solvents are fed under low or high pressure by means of two high performance liquid chromatographic pumps. The mixer comprises a series of ultra-low dead volume stainless steel tubes and low dead volume chambers. The two solvent streams impinge head-on at high fluxes. This initial nonhomogeneous mixture is then passed through a chamber packed with spirally-wound wires which cause turbulent mixing thereby homogenizing the mixture with minimum band-broadening.
Fullerene-Free Organic Solar Cells with an Efficiency of 10.2% and an Energy Loss of 0.59 eV Based on a Thieno[3,4-c]Pyrrole-4,6-dione-Containing Wide Band Gap Polymer Donor.

PubMed

Hadmojo, Wisnu Tantyo; Wibowo, Febrian Tri Adhi; Ryu, Du Yeol; Jung, In Hwan; Jang, Sung-Yeon

2017-09-27

Although the combination of wide band gap polymer donors and narrow band gap small-molecule acceptors achieved state-of-the-art performance as bulk heterojunction (BHJ) active layers for organic solar cells, there have been only several of the wide band gap polymers that actually realized high-efficiency devices over >10%. Herein, we developed high-efficiency, low-energy-loss fullerene-free organic solar cells using a weakly crystalline wide band gap polymer donor, PBDTTPD-HT, and a nonfullerene small-molecule acceptor, ITIC. The excessive intermolecular stacking of ITIC is efficiently suppressed by the miscibility with PBDTTPD-HT, which led to a well-balanced nanomorphology in the PBDTTPD-HT/ITIC BHJ active films. The favorable optical, electronic, and energetic properties of PBDTTPD-HT with respect to ITIC achieved panchromatic photon-to-current conversion with a remarkably low energy loss (0.59 eV).
In situ high temperature X-Ray diffraction study of the phase equilibria in the UO2-PuO2-Pu2O3 system

NASA Astrophysics Data System (ADS)

Belin, Renaud C.; Strach, Michal; Truphémus, Thibaut; Guéneau, Christine; Richaud, Jean-Christophe; Rogez, Jacques

2015-10-01

The region of the U-Pu-O phase diagram delimited by the compounds UO2-PuO2-Pu2O3 is known to exhibit a miscibility gap at low temperature. Consequently, MOX fuels with a composition entering this region could decompose into two fluorite phases and thus exhibit chemical heterogeneities. The experimental data on this domain found in the literature are scarce and usually provided using DTA that is not suitable for the investigation of such decomposition phenomena. In the present work, new experimental data, i.e. crystallographic phases, lattice parameters, phase fractions and temperature of phase separation, were measured in the composition range 0.14 < Pu/(U + Pu) < 0.62 and 1.85 < O/(U + Pu) < 2 from 298 to 1750 K using a novel in situ high temperature X-ray diffraction apparatus. A very good agreement is found between the temperature of phase separation determined from our results and using the thermodynamic model of the U-Pu-O system based on the CALPHAD method. Also, the combined use of thermodynamic calculations and XRD results refinement proved helpful in the determination of the O/M ratio of the samples during cooling. The methodology used in the current work might be useful to investigate other oxides systems exhibiting a miscibility gap.
Undercooling, Liquid Separation and Solidification of Cu-Co Alloys

NASA Technical Reports Server (NTRS)

Robinson, M. B.; Li, D.; Rathz, J.; Williams, G.

1998-01-01

Large undercooling can induce not only various solidification pathways, but also a precursor reaction, or liquid separation. This paper deals with the latter effect of undercooling using examples of the Cu-Co system which has a flattened liquidus. Bulk Cu-Co alloys (about 7mm diameter) at compositions ranging from 10 to 90 wt pct Co were highly undercooled using a fluxing technique. Except for Cu-90 wt pct Co, liquid separation was directly observed as undercooling exceeded a critical value depending on the composition. It was also confirmed by a microstructural transition from dendrites to droplets above the critical undercooling. Finally, theoretical calculations regarding the metastable miscibility boundary and maximum droplet radius were made to analyze the experimental results.
Liquid lens based on electrowetting: a new adaptive component for imaging applications in consumer electronics

NASA Astrophysics Data System (ADS)

Crassous, Jerome; Gabay, Claude; Liogier, Gaetan; Berge, Bruno

2004-12-01

A new technology for focus variation with direct electric control without moving part will be presented. The technology relies on an interface between two non-miscible transparent liquids, which can be deformed by electrowetting. This technology has been developed since 10 years in the lab and starts to be available commercially, with the following characteristics: large amplitude of dioptric correction (20 dioptries for a 5mm pupil size), fast response, small power consumption and good transmission in the visible range, clear pupil 1-10mm diameter. This paper will show the basic principle, as well as the physical limitations and optical aberrations due to differential thermal expansion of the two liquids in the cell. Experimental measurements made with a Schack Hartmann wave front analyzer will be presented, as well as numerical simulations of the liquid-liquid interface. Applications will be discussed, mainly in consumer electronics.
CO 2 Storage and Enhanced Oil Recovery: Bald Unit Test Site, Mumford Hills Oil Field, Posey County, Indiana

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

Frailey, Scott M.; Krapac, Ivan G.; Damico, James R.

2012-03-30

The Midwest Geological Sequestration Consortium (MGSC) carried out a small-scale carbon dioxide (CO 2) injection test in a sandstone within the Clore Formation (Mississippian System, Chesterian Series) in order to gauge the large-scale CO 2 storage that might be realized from enhanced oil recovery (EOR) of mature Illinois Basin oil fields via miscible liquid CO 2 flooding.
Structure-property relationships of Thai silk-microcrystalline cellulose biocomposite materials fabricated from ionic liquid.

PubMed

DeFrates, Kelsey; Markiewicz, Theodore; Callaway, Kayla; Xue, Ye; Stanton, John; Salas-de la Cruz, David; Hu, Xiao

2017-11-01

Biomaterials made from natural proteins and polysaccharides have become increasingly popular in the biomedical field due to their good biocompatibility and tunable biodegradability. However, the low miscibility of polysaccharides with proteins presents challenges in the creation of protein-polysaccharide composite materials. In this study, neat 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid was used to regenerate Thailand gold Bombyx mori silk and microcrystalline cellulose blended films. This solvent was found to not only effectively dissolve both natural polymers, but also preserve the structure and integrity of the polymers. A single glass transition temperature for each blend was found in DSC curves, indicating good miscibility between the Thai silk and cellulose molecules. The structural composition as well as the morphology and thermal stability of blend films were then determined using FTIR, SEM and TGA. It was found that by varying the ratio of Thai silk to cellulose, the thermal and physical properties of the material could be tuned. Blended films tended to be more thermally stable which could be due to the presence of hydrophobic-hydrophobic or electrostatic interactions between the silk and cellulose. These studies offered a new pathway to understand the tunable properties of protein-polysaccharide composite biomaterials with controllable physical and biological properties. Copyright © 2017 Elsevier B.V. All rights reserved.
Anti-Wear Performance and Mechanism of an Oil-Miscible Ionic Liquid as a Lubricant Additive

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

Qu, Jun; Bansal, Dinesh G; Yu, Bo

2012-01-01

An ionic liquid (IL) trihexyltetradecylphosphonium bis(2-ethylhexyl) phosphate has been investigated as a potential anti-wear lubricant additive. Unlike most other ILs that have very low solubility in non-polar fluids, this IL is fully miscible with various hydrocarbon oils. In addition, it is thermally stable up to 347 oC, showed no corrosive attack to cast iron in ambient environment, and has excellent wettability on solid surfaces (e.g., contact angle on cast iron <8o). Most importantly, this phosphonium-based IL has demonstrated effective anti-scuffing and anti-wear characteristics when blended with lubricating oils. For example, a 5 wt.% addition into a synthetic base oil eliminatedmore » the scuffing failure experienced by the neat oil and, as a result, reduced the friction coefficient by 60% and the wear rate by three orders of magnitude. A synergistic effect on wear protection was observed with the current anti-wear additive when added into a fully-formulated engine oil. Nanostructure examination and composition analysis revealed a tribo-boundary film and subsurface plastic deformation zone for the metallic surface lubricated by the IL-containing lubricants. This protective boundary film is believed to be responsible for the IL s anti-scuffing and anti-wear functionality.« less
Effects of G-Jitter on Interfacial Dynamics of Two Miscible Liquids: Application of MIM

NASA Technical Reports Server (NTRS)

Duval, Walter M. B.; Tryggvason, Bjarni V.

2000-01-01

We designed an experiment to examine the effects of g-jitter on mixing of two miscible liquids using the Microgravity Vibration Isolation Mount (MIM). The global bifurcation of the interface was observed with the MIM operating alternatively to either transmit the g-jitter, isolate from the g-jitter or to provide controlled vibration levels with well defined amplitude and frequency content. With the MIM in isolation mode, the interface remains stationary indicating buoyancy induced convection is negligibly small such that mixing occurs via intrinsic mass diffusion without the masking effect of vibration driven convection. Analytical and computational results are in agreement with the experimental findings. Operation of the MIM in forced mode with conditions typical of g-jitter shows that vibration induced convective flows can excite instability mechanisms such as Kelvin-Helmholtz to generate large amplitude quasi-stationary waves oriented vertically for various cases with Stokes-Reynolds number in the range of 0.003 to 0.5. The two and four mode quasi-stationary waves are also predicted with a mathematical model. Though unplanned, the effect of a primary thruster filing was captured and shown to cause a catastrophic bifurcation, enhancing local mass transport. In light of the findings, experiments planned for the International Space Station should consider the potential effects of g-jitter.
Phosphonium-Organophosphate Ionic Liquids as Lubricant Additives: Effects of Cation Structure on Physicochemical and Tribological Characteristics

DOE PAGES

Barnhill, William C.; Qu, Jun; Luo, Huimin; ...

2014-11-17

In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less
Super-hydrophobic fluorine containing aerogels

DOEpatents

Coronado, Paul R [Livermore, CA; Poco, John F [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2007-05-01

An aerogel material with surfaces containing fluorine atoms which exhibits exceptional hydrophobicity, or the ability to repel liquid water. Hydrophobic aerogels are efficient absorbers of solvents from water. Solvents miscible with water are separated from it because the solvents are more volatile than water and they enter the porous aerogel as a vapor across the liquid water/solid interface. Solvents that are immisicble with water are separated from it by selectively wetting the aerogel. The hydrophobic property is achieved by formulating the aerogel using fluorine containing molecules either directly by addition in the sol-gel process, or by treating a standard dried aerogel using the vapor of fluorine containing molecules.
Phase Behavior of Ritonavir Amorphous Solid Dispersions during Hydration and Dissolution.

PubMed

Purohit, Hitesh S; Taylor, Lynne S

2017-12-01

The aim of this research was to study the interplay of solid and solution state phase transformations during the dissolution of ritonavir (RTV) amorphous solid dispersions (ASDs). RTV ASDs with polyvinylpyrrolidone (PVP), polyvinylpyrrolidone vinyl acetate (PVPVA) and hydroxypropyl methylcellulose acetate succinate (HPMCAS) were prepared at 10-50% drug loading by solvent evaporation. The miscibility of RTV ASDs was studied before and after exposure to 97% relative humidity (RH). Non-sink dissolution studies were performed on fresh and moisture-exposed ASDs. RTV and polymer release were monitored using ultraviolet-visible spectroscopy. Techniques including fluorescence spectroscopy, confocal imaging, scanning electron microscopy (SEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and nanoparticle tracking analysis (NTA) were utilized to monitor solid and the solution state phase transformations. All RTV-PVP and RTV-PVPVA ASDs underwent moisture-induced amorphous-amorphous phase separation (AAPS) on high RH storage whereas RTV-HPMCAS ASDs remained miscible. Non-sink dissolution of PVP- and PVPVA-based ASDs at low drug loadings led to rapid RTV and polymer release resulting in concentrations in excess of amorphous solubility, liquid-liquid phase separation (LLPS) and amorphous nanodroplet formation. High drug loading PVP- and PVPVA-based ASDs did not exhibit LLPS upon dissolution as a consequence of extensive AAPS in the hydrated ASD matrix. All RTV-HPMCAS ASDs led to LLPS upon dissolution. RTV ASD dissolution is governed by a competition between the dissolution rate and the rate of phase separation in the hydrated ASD matrix. LLPS was observed for ASDs where the drug release was polymer controlled and only ASDs that remained miscible during the initial phase of dissolution led to LLPS. Techniques such as fluorescence spectroscopy, confocal imaging and SEM were useful in understanding the phase behavior of ASDs upon hydration and dissolution and were helpful in elucidating the mechanism of generation of amorphous nanodroplets.
Emulsified Zero-Valent Nano-Scale Iron Treatment of Chlorinated Solvent DNAPL Source Areas

DTIC Science & Technology

2010-04-01

The EZVI is composed of food-grade surfactant, biodegradable oil , water, and ZVI particles (either nano- or micro-scale iron), which form...emulsion particles (Figure 2-1). Each emulsion particle or droplet contains ZVI particles in water surrounded by an oil -liquid membrane. Since the...exterior oil membrane of the emulsion droplet has hydrophobic properties similar to that of DNAPL, the droplets are miscible with DNAPL. It is believed

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.
Apparatus and method for pumping hot, erosive slurry of coal solids in coal derived, water immiscible liquid

DOEpatents

Ackerman, Carl D.

1983-03-29

An apparatus for and method of pumping hot, erosive slurry of coal solids in a coal derived, water immiscible liquid to higher pressure involves the use of a motive fluid which is miscible with the liquid of the slurry. The apparatus includes a pump 12, a remote check valve 14 and a chamber 16 between and in fluid communication with the pump 12 and check valve 14 through conduits 18,20. Pump 12 exerts pressure on the motive fluid and thereby on the slurry through a concentration gradient of coal solids within chamber 16 to alternately discharge slurry under pressure from the outlet port of check valve 14 and draw slurry in through the inlet port of check valve 14.
Band gap bowing in NixMg1−xO

PubMed Central

Niedermeier, Christian A.; Råsander, Mikael; Rhode, Sneha; Kachkanov, Vyacheslav; Zou, Bin; Alford, Neil; Moram, Michelle A.

2016-01-01

Epitaxial transparent oxide NixMg1−xO (0 ≤ x ≤ 1) thin films were grown on MgO(100) substrates by pulsed laser deposition. High-resolution synchrotron X-ray diffraction and high-resolution transmission electron microscopy analysis indicate that the thin films are compositionally and structurally homogeneous, forming a completely miscible solid solution. Nevertheless, the composition dependence of the NixMg1−xO optical band gap shows a strong non-parabolic bowing with a discontinuity at dilute NiO concentrations of x < 0.037. Density functional calculations of the NixMg1−xO band structure and the density of states demonstrate that deep Ni 3d levels are introduced into the MgO band gap, which significantly reduce the fundamental gap as confirmed by optical absorption spectra. These states broaden into a Ni 3d-derived conduction band for x > 0.074 and account for the anomalously large band gap narrowing in the NixMg1−xO solid solution system. PMID:27503808
Miscibility at the immiscible liquid/liquid interface: A molecular dynamics study of thermodynamics and mechanism

NASA Astrophysics Data System (ADS)

Karnes, John J.; Benjamin, Ilan

2018-01-01

Molecular dynamics simulations are used to study the dissolution of water into an adjacent, immiscible organic liquid phase. Equilibrium thermodynamic and structural properties are calculated during the transfer of water molecule(s) across the interface using umbrella sampling. The net free energy of transfer agrees reasonably well with experimental solubility values. We find that water molecules "prefer" to transfer into the adjacent phase one-at-a-time, without co-transfer of the hydration shell, as in the case of evaporation. To study the dynamics and mechanism of transfer of water to liquid nitrobenzene, we collected over 400 independent dissolution events. Analysis of these trajectories suggests that the transfer of water is facilitated by interfacial protrusions of the water phase into the organic phase, where one water molecule at the tip of the protrusion enters the organic phase by the breakup of a single hydrogen bond.
Liquid Chromatography Applications to Determination of Sorption on Aquifer Materials

DTIC Science & Technology

1989-11-01

and D. R. Nielsen. Modeling tritium and chloride 36 transport through an aggregated oxisol . Water Resources Res. 19 691-700 (1983). P. Nkedi-Kizza, J. W...describing ion exchange during transport through an aggregated oxisol . Water Resources Res. 20 1123-1130 (1984). P. Nkedi-Kizza, P. S. C. Rao, R. E. Jessup...and J. M. Davidson. Ion exchange and diffusive mass transfer during miscible displacement through an aggregated oxisol . Soil Sci. Soc. Am. J. 46 471
The Dissolution of an Interfween Miscible Liquids

NASA Technical Reports Server (NTRS)

Vlad, D.H.; Maher, J.V.

1999-01-01

The disappearance of the surface tension of the interface of a binary mixture, measured using the dynamic surface light scattering technique, is slower for a binary mixture of higher density contrast. A comparison with a naive diffusion model, expected to provide a lower limit for the speed of dissolution in the absence of gravity shows that the interfacial surface tension disappears much slower than even by diffusion with the effect becoming much more pronounced when density contrast between the liquid phases is increased. Thus, the factor most likely to be responsible for this anomalously slow dissolution is gravity. A mechanism could be based on the competition between diffusive relaxation and sedimentation at the dissolving interface.
Miscibility and Morphology of Poly(lactic ACID)/POLY(Β-HYDROXYBUTYRATE) Blends

NASA Astrophysics Data System (ADS)

Tri Phuong, Nguyen; Guinault, Alain; Sollogoub, Cyrille

2011-01-01

The miscibility and morphology of poly(lactic)acid (PLA)/polyβ-hydroxybutyrate (PHB) prepared by melt blending method were investigated by Fourier transform infrared (FTIR), Differential scanning calorimetry (DSC), melt rheology and scanning electron microscopy (SEM) observations. FTIR and DSC methods present some limits to examine the miscibility state of PLA/PHB blends. This drawback can be overcome with the Cole-Cole method by observing the η" = f(η') curves to confirm the miscibility of semicrystalline PLA/ semicrystalline PHB blends. MEB micrographs of fractured surface of blends were also used to investigate the miscibility of these blends.
Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents.

PubMed

Bozym, David J; Uralcan, Betül; Limmer, David T; Pope, Michael A; Szamreta, Nicholas J; Debenedetti, Pablo G; Aksay, Ilhan A

2015-07-02

We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon-electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5-10 mol% (i.e., ∼1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low-dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.
Using CO2 Prophet to estimate recovery factors for carbon dioxide enhanced oil recovery

USGS Publications Warehouse

Attanasi, Emil D.

2017-07-17

IntroductionThe Oil and Gas Journal’s enhanced oil recovery (EOR) survey for 2014 (Koottungal, 2014) showed that gas injection is the most frequently applied method of EOR in the United States and that carbon dioxide (CO2 ) is the most commonly used injection fluid for miscible operations. The CO2-EOR process typically follows primary and secondary (waterflood) phases of oil reservoir development. The common objective of implementing a CO2-EOR program is to produce oil that remains after the economic limit of waterflood recovery is reached. Under conditions of miscibility or multicontact miscibility, the injected CO2 partitions between the gas and liquid CO2 phases, swells the oil, and reduces the viscosity of the residual oil so that the lighter fractions of the oil vaporize and mix with the CO2 gas phase (Teletzke and others, 2005). Miscibility occurs when the reservoir pressure is at least at the minimum miscibility pressure (MMP). The MMP depends, in turn, on oil composition, impurities of the CO2 injection stream, and reservoir temperature. At pressures below the MMP, component partitioning, oil swelling, and viscosity reduction occur, but the efficiency is increasingly reduced as the pressure falls farther below the MMP. CO2-EOR processes are applied at the reservoir level, where a reservoir is defined as an underground formation containing an individual and separate pool of producible hydrocarbons that is confined by impermeable rock or water barriers and is characterized by a single natural pressure system. A field may consist of a single reservoir or multiple reservoirs that are not in communication but which may be associated with or related to a single structural or stratigraphic feature (U.S. Energy Information Administration [EIA], 2000). The purpose of modeling the CO2-EOR process is discussed along with the potential CO2-EOR predictive models. The data demands of models and the scope of the assessments require tradeoffs between reservoir-specific data that can be assembled and simplifying assumptions that allow assignment of default values for some reservoir parameters. These issues are discussed in the context of the CO2 Prophet EOR model, and their resolution is demonstrated with the computation of recovery-factor estimates for CO2-EOR of 143 reservoirs in the Powder River Basin Province in southeastern Montana and northeastern Wyoming.
Structure functions in decomposing CuRh systems

NASA Astrophysics Data System (ADS)

Prem, M.; Blaschko, O.; Rosta, L.

1997-02-01

The time evolution of a CuRh alloy quenched within the miscibility gap is investigated by small and wide angle neutron scattering techniques. Near fundamental Bragg reflections diffuse satellites arising from a lattice parameter modulation induced by the precipitation pattern are investigated. The results show that in CuRh the precipitation morphology and its time evolution are quite different from decomposition characteristics recently observed in the system AuPt. The results are discussed and related to the larger lattice misfit present in CuRh in comparison to AuPt.
On the universality of Marangoni-driven spreading

NASA Astrophysics Data System (ADS)

Visser, Claas; van Capelleveen, Bram; Koldeweij, Robin; Lohse, Detlef

2017-11-01

When two liquids of different surface tensions come into contact, the liquid with lower surface tension spreads over the other. Here we measure the dynamics of this Marangoni-driven spreading in the drop-drop geometry, revealing universal behavior with respect to the control parameters as well as other geometries (such as spreading over a flat interface). The distance L over which the low-surface-tension liquid has covered the high-surface-tension droplet is measured as a function of time t, surface tension difference between the liquids Δσ , and viscosity η, revealing power-law behavior L(t) tα . The exponent α is discussed for the early and late spreading regimes. Spreading inhibition is observed at high viscosity, for which the threshold is discussed. Finally, we show that our results collapse onto a single curve of dimensionless L(t) as a function of dimensionless time, which also captures previous results for different geometries, surface tension modifiers, and miscibility. As this curve spans 7 orders of magnitude, Marangoni-induced spreading can be considered a universal phenomenon for many practically encountered liquid-liquid systems.
Fast, simple and efficient salting-out assisted liquid-liquid extraction of naringenin from fruit juice samples prior to their enantioselective determination by liquid chromatography.

PubMed

Magiera, Sylwia; Kwietniowska, Ewelina

2016-11-15

In this study, an easy, simple and efficient method for the determination of naringenin enantiomers in fruit juices after salting-out-assisted liquid-liquid extraction (SALLE) and high-performance liquid chromatography (HPLC) with diode-array detection (DAD) was developed. The sample treatment is based on the use of water-miscible acetonitrile as the extractant and acetonitrile phase separation under high-salt conditions. After extraction, juice samples were incubated with hydrochloric acid in order to achieve hydrolysis of naringin to naringenin. The hydrolysis parameters were optimized by using a half-fraction factorial central composite design (CCD). After sample preparation, chromatographic separation was obtained on a Chiralcel® OJ-RH column using the mobile phase consisting of 10mM aqueous ammonium acetate:methanol:acetonitrile (50:30:20; v/v/v) with detection at 288nm. The average recovery of the analyzed compounds ranged from 85.6 to 97.1%. The proposed method was satisfactorily used for the determination of naringenin enantiomers in various fruit juices samples. Copyright © 2016 Elsevier Ltd. All rights reserved.
Effect of binder liquid type on spherical crystallization.

PubMed

Maghsoodi, Maryam; Hajipour, Ali

2014-11-01

Spherical crystallization is a process of formation of agglomerates of crystals held together by binder liquid. This research focused on understanding the effect of type of solvents used as binder liquid on the agglomeration of crystals. Carbamazepine and ethanol/water were used respectively as a model drug and crystallization system. Eight solvents as binder liquid including chloroform, dichloromethane, isopropyl acetate, ethyl acetate, n-hexane, dimethyl aniline, benzene and toluene were examined to better understand the relationship between the physical properties of the binder liquid and its ability to bring about the formation of the agglomerates. Moreover, the agglomerates obtained from effective solvents as binder liquid were evaluated in term of size, apparent particle density and compressive strength. In this study the clear trend was observed experimentally in the agglomerate formation as a function of physical properties of the binder liquid such as miscibility with crystallization system. Furthermore, the properties of obtained agglomerates such as size, apparent particle density and compressive strength were directly related to physical properties of effective binder liquids. RESULTS of this study offer a useful starting point for a conceptual framework to guide the selection of solvent systems for spherical crystallization.
Low Mach number fluctuating hydrodynamics of multispecies liquid mixtures

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

Donev, Aleksandar, E-mail: donev@courant.nyu.edu; Bhattacharjee, Amit Kumar; Nonaka, Andy

We develop a low Mach number formulation of the hydrodynamic equations describing transport of mass and momentum in a multispecies mixture of incompressible miscible liquids at specified temperature and pressure, which generalizes our prior work on ideal mixtures of ideal gases [Balakrishnan et al., “Fluctuating hydrodynamics of multispecies nonreactive mixtures,” Phys. Rev. E 89 013017 (2014)] and binary liquid mixtures [Donev et al., “Low mach number fluctuating hydrodynamics of diffusively mixing fluids,” Commun. Appl. Math. Comput. Sci. 9(1), 47-105 (2014)]. In this formulation, we combine and extend a number of existing descriptions of multispecies transport available in the literature. Themore » formulation applies to non-ideal mixtures of arbitrary number of species, without the need to single out a “solvent” species, and includes contributions to the diffusive mass flux due to gradients of composition, temperature, and pressure. Momentum transport and advective mass transport are handled using a low Mach number approach that eliminates fast sound waves (pressure fluctuations) from the full compressible system of equations and leads to a quasi-incompressible formulation. Thermal fluctuations are included in our fluctuating hydrodynamics description following the principles of nonequilibrium thermodynamics. We extend the semi-implicit staggered-grid finite-volume numerical method developed in our prior work on binary liquid mixtures [Nonaka et al., “Low mach number fluctuating hydrodynamics of binary liquid mixtures,” http://arxiv.org/abs/1410.2300 (2015)] and use it to study the development of giant nonequilibrium concentration fluctuations in a ternary mixture subjected to a steady concentration gradient. We also numerically study the development of diffusion-driven gravitational instabilities in a ternary mixture and compare our numerical results to recent experimental measurements [Carballido-Landeira et al., “Mixed-mode instability of a miscible interface due to coupling between Rayleigh–Taylor and double-diffusive convective modes,” Phys. Fluids 25, 024107 (2013)] in a Hele-Shaw cell. We find that giant nonequilibrium fluctuations can trigger the instability but are eventually dominated by the deterministic growth of the unstable mode, in both quasi-two-dimensional (Hele-Shaw) and fully three-dimensional geometries used in typical shadowgraph experiments.« less
Fluid helium at conditions of giant planetary interiors

PubMed Central

Stixrude, Lars; Jeanloz, Raymond

2008-01-01

As the second most-abundant chemical element in the universe, helium makes up a large fraction of giant gaseous planets, including Jupiter, Saturn, and most extrasolar planets discovered to date. Using first-principles molecular dynamics simulations, we find that fluid helium undergoes temperature-induced metallization at high pressures. The electronic energy gap (band gap) closes at 20,000 K at a density half that of zero-temperature metallization, resulting in electrical conductivities greater than the minimum metallic value. Gap closure is achieved by a broadening of the valence band via increased s–p hydridization with increasing temperature, and this influences the equation of state: The Grüneisen parameter, which determines the adiabatic temperature–depth gradient inside a planet, changes only modestly, decreasing with compression up to the high-temperature metallization and then increasing upon further compression. The change in electronic structure of He at elevated pressures and temperatures has important implications for the miscibility of helium in hydrogen and for understanding the thermal histories of giant planets.
An experimental study of miscible viscous fingering of annular ring

NASA Astrophysics Data System (ADS)

Nagatsu, Yuichiro; Othman, Hamirul Bin; Mishra, Manoranjan

2017-11-01

Understanding the viscous fingering (VF) dynamics of finite width sample is important in the fields especially such as liquid chromatography and groundwater contamination and mixing in microfluidics. In this paper, we experimentally investigate such hydrodynamical morphology of VF using a Hele-Shaw flow system in which a miscible annular ring of fluid is displaced radially. Experiments are performed to investigate the effects of the sample volume, the effects of dispersion and log mobility ratio R on the dynamics of VF pattern and onset of such instability. Depending whether the finite width ring is more or less viscous than the carrier fluid, the log mobility ratio R becomes positive or negative respectively. The experiments are successfully conducted to obtain the VF patterns for R>0 and R<0, of the finite annular ring at the inner and outer radial interfaces, respectively. It is found that in the radial displacement, the inward finger moves slower than the outward finger. The experimental results are found to be qualitatively in good agreement with the corresponding linear stability analysis and non-linear simulations results available in the literature.
Prediction of solubility parameters and miscibility of pharmaceutical compounds by molecular dynamics simulations.

PubMed

Gupta, Jasmine; Nunes, Cletus; Vyas, Shyam; Jonnalagadda, Sriramakamal

2011-03-10

The objectives of this study were (i) to develop a computational model based on molecular dynamics technique to predict the miscibility of indomethacin in carriers (polyethylene oxide, glucose, and sucrose) and (ii) to experimentally verify the in silico predictions by characterizing the drug-carrier mixtures using thermoanalytical techniques. Molecular dynamics (MD) simulations were performed using the COMPASS force field, and the cohesive energy density and the solubility parameters were determined for the model compounds. The magnitude of difference in the solubility parameters of drug and carrier is indicative of their miscibility. The MD simulations predicted indomethacin to be miscible with polyethylene oxide and to be borderline miscible with sucrose and immiscible with glucose. The solubility parameter values obtained using the MD simulations values were in reasonable agreement with those calculated using group contribution methods. Differential scanning calorimetry showed melting point depression of polyethylene oxide with increasing levels of indomethacin accompanied by peak broadening, confirming miscibility. In contrast, thermal analysis of blends of indomethacin with sucrose and glucose verified general immiscibility. The findings demonstrate that molecular modeling is a powerful technique for determining the solubility parameters and predicting miscibility of pharmaceutical compounds. © 2011 American Chemical Society
Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

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

Dudowicz, Jacek, E-mail: dudowicz@jfi.uchicago.edu; Freed, Karl F.; Douglas, Jack F.

2015-10-07

Standard Flory-Huggins (FH) theory is utilized to describe the enigmatic cosolvency and cononsolvency phenomena for systems of polymers dissolved in mixed solvents. In particular, phase boundaries (specifically upper critical solution temperature spinodals) are calculated for solutions of homopolymers B in pure solvents and in binary mixtures of small molecule liquids A and C. The miscibility (or immiscibility) patterns for the ternary systems are classified in terms of the FH binary interaction parameters (χ{sub αβ}) and the ratio r = ϕ{sub A}/ϕ{sub C} of the concentrations ϕ{sub A} and ϕ{sub C} of the two solvents. The trends in miscibility are comparedmore » to those observed for blends of random copolymers (A{sub x}C{sub 1−x}) with homopolymers (B) and to those deduced for A/B/C solutions of polymers B in liquid mixtures of small molecules A and C that associate into polymeric clusters (A{sub p}C{sub q}){sub i}, (i = 1, 2, …, ∞). Although the classic FH theory is able to explain cosolvency and cononsolvency phenomena, the theory does not include a consideration of the mutual association of the solvent molecules and the competitive association between the solvent molecules and the polymer. These interactions can be incorporated in refinements of the FH theory, and the present paper provides a foundation for such extensions for modeling the rich thermodynamics of polymers in mixed solvents.« less
Development of solvent systems with room temperature ionic liquids for the countercurrent chromatographic separation of very nonpolar lipid compounds.

PubMed

Müller, Marco; Englert, Michael; Earle, Martyn J; Vetter, Walter

2017-03-10

Solvent systems are not readily available for the separation of very nonpolar compounds by countercurrent chromatography (CCC). In this study we therefore evaluated the suitability of room temperature ionic liquids (IL) in organic solvents for the CCC separation of the extremely nonpolar lipid compounds tripalmitin (PPP) and cholesteryl stearate (CS). The four IL tested were [C 10 mim][OTf], [C 2 mim][NTf 2 ], [P66614][NTf 2 ], and [P66614][Cl]. Search for a CCC-suited solvent system started with solubility studies with fourteen organic solvents. Following this, combinations were made with one organic solvent miscible and one organic solvent immiscible with IL (147 combinations). Twenty-four initially monophasic mixtures of two organic solvents became biphasic by adding IL. Several unexpected results could be observed. For instance, n-hexane and n-heptane became biphasic with [P66614][Cl]. Further nine systems became biphasic although the IL was not miscible in any of the two components. These 33 solvent systems were investigated with regard to phase ratio, settling time, share of IL in the upper phase and last not least the K U/L values of PPP and CS, which were 8.1 and 7.7 respectively. The most promising system, n-heptane/chloroform/[C 10 mim][OTf] (3:3:1, v/v/v) allowed a partial separation of PPP and CS by CCC which was not achieved beforehand. Copyright © 2017 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.

Vapor-liquid equilibria for R-22, R-134a, R-125, and R-32/125 with a polyol ester lubricant: Measurements and departure from ideality

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

Martz, W.L.; Burton, C.M.; Jacobi, A.M.

1996-11-01

The effect of a polyol ester lubricant on equilibrium pressure, liquid density, and viscosity is presented for R-22, R-125, and R-134a at varying temperatures and concentrations. Preliminary vapor-liquid equilibrium (VLE) data and miscibility observations are also presented for an R-32/R-125 blend (50%/50%) with the ISO 68 polyol ester (POE). Real-gas behavior is modeled using the vapor-phase fugacity, and vapor pressure effects on liquid fugacities are taken into account with the Poynting effect. Positive, negative, and mixed deviations form the Lewis-Randall rule are observed in the activity coefficient behavior. Departures from ideality are related to molecular size differences, intermolecular forces inmore » the mixture, and other factors. The data are discussed in the context of previous results for other refrigerants and thermodynamic modeling of refrigerant and oil mixtures.« less
Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.
MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.
Synthesis and evaluation of novel siloxane-methacrylate monomers used as dentin adhesives

PubMed Central

Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette

2014-01-01

Objectives The objectives of this study were to synthesize two new siloxane-methacrylate (SM) monomers for application in dentin adhesives and to investigate the influence of different functionality of the siloxane-containing monomers on the adhesive photopolymerization, water sorption, and mechanical properties. Materials and method Two siloxane-methacrylate monomers (SM1 and SM2) with four and eight methacrylate groups were synthesized. Dentin adhesives containing BisGMA, HEMA and the siloxane-methacrylate monomers were photo-polymerized. The experimental adhesives were compared with the control adhesive (HEMA/BisGMA 45/55 w/w) and characterized with regard to degree of conversion (DC), water miscibility of the liquid resin, water sorption and dynamic mechanical analysis (DMA). Results The experimental adhesives exhibited improved water miscibility as compared to the control. When cured in the presence of 12 wt % water to simulate the wet environment of the mouth, the SM-containing adhesives showed DC comparable to the control. The experimental adhesives showed higher rubbery modulus than the control under dry conditions. Under wet conditions, the mechanical properties of the formulations containing SM monomer with increased functionality were comparable with the control, even with more water sorption. Significance The concentration and functionality of the newly synthesized siloxane-methacrylate monomers affected the water miscibility, water sorption and mechanical properties of the adhesives. The experimental adhesives show improved water compatibility compared with the control. The mechanical properties were enhanced with an increase of the functionality of the siloxane-containing monomers. The results provide critical structure/property relationships and important information for future development of durable, versatile siloxane-containing dentin adhesives. PMID:24993811
Synthesis and evaluation of novel siloxane-methacrylate monomers used as dentin adhesives.

PubMed

Ge, Xueping; Ye, Qiang; Song, Linyong; Misra, Anil; Spencer, Paulette

2014-09-01

The objectives of this study were to synthesize two new siloxane-methacrylate (SM) monomers for application in dentin adhesives and to investigate the influence of different functionality of the siloxane-containing monomers on the adhesive photopolymerization, water sorption, and mechanical properties. Two siloxane-methacrylate monomers (SM1 and SM2) with four and eight methacrylate groups were synthesized. Dentin adhesives containing BisGMA, HEMA and the siloxane-methacrylate monomers were photo-polymerized. The experimental adhesives were compared with the control adhesive (HEMA/BisGMA, 45/55, w/w) and characterized with regard to degree of conversion (DC), water miscibility of the liquid resin, water sorption and dynamic mechanical analysis (DMA). The experimental adhesives exhibited improved water miscibility as compared to the control. When cured in the presence of 12 wt% water to simulate the wet environment of the mouth, the SM-containing adhesives showed DC comparable to the control. The experimental adhesives showed higher rubbery modulus than the control under dry conditions. Under wet conditions, the mechanical properties of the formulations containing SM monomer with increased functionality were comparable with the control, even with more water sorption. The concentration and functionality of the newly synthesized siloxane-methacrylate monomers affected the water miscibility, water sorption and mechanical properties of the adhesives. The experimental adhesives show improved water compatibility compared with the control. The mechanical properties were enhanced with an increase of the functionality of the siloxane-containing monomers. The results provide critical structure/property relationships and important information for future development of durable, versatile siloxane-containing dentin adhesives. Published by Elsevier Ltd.
Physicochemical properties of film-coated melt-extruded pellets.

PubMed

Young, Chistopher R; Crowley, Michael; Dietzsch, Caroline; McGinity, James W

2007-02-01

The purpose of this study was to investigate the physicochemical properties of poly(ethylene oxide) (PEO) and guaifenesin containing beads prepared by a melt-extrusion process and film-coated with a methacrylic acid copolymer. Solubility parameter calculations, thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), modulated differential scanning calorimetry (MDSC), X-ray powder diffraction (XRPD) and high performance liquid chromatography (HPLC) were used to determine drug/polymer miscibility and/or the thermal processibility of the systems. Powder blends of guaifenesin, PEO and functional excipients were processed using a melt-extrusion and spheronization technique and then film-coated in a fluidized bed apparatus. Solubility parameter calculations were used to predict miscibility between PEO and guaifenesin, and miscibility was confirmed by SEM and observation of a single melting point for extruded drug/polymer blends during MDSC investigations. The drug was stable following melt-extrusion as determined by TGA and HPLC; however, drug release rate from pellets decreased upon storage in sealed HDPE containers with silica desiccants at 40 degrees C/75% RH. The weight loss on drying, porosity and tortuosity determinations were not influenced by storage. Recrystallization of guaifenesin and PEO was confirmed by SEM and XRPD. Additionally, the pellets exhibited a change in adhesion behaviour during dissolution testing. The addition of ethylcellulose to the extruded powder blend decreased and stabilized the drug release rate from the thermally processed pellets. The current study also demonstrated film-coating to be an efficient process for providing melt-extruded beads with pH-dependent drug release properties that were stable upon storage at accelerated conditions.
Entropic depletion in colloidal suspensions and polymer liquids: Role of nanoparticle surface topography

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

Banerjee, Debapriya; Yang, Jian; Schweizer, Kenneth S.

2015-01-01

Here, we employ a hybrid Monte Carlo plus integral equation theory approach to study how dense fluids of small nanoparticles or polymer chains mediate entropic depletion interactions between topographically rough particles where all interaction potentials are hard core repulsion. The corrugated particle surfaces are composed of densely packed beads which present variable degrees of controlled topographic roughness and free volume associated with their geometric crevices. This pure entropy problem is characterized by competing ideal translational and (favorable and unfavorable) excess entropic contributions. Surface roughness generically reduces particle depletion aggregation relative to the smooth hard sphere case. However, the competition betweenmore » ideal and excess packing entropy effects in the bulk, near the particle surface and in the crevices, results in a non-monotonic variation of the particle-monomer packing correlation function as a function of the two dimensionless length scale ratios that quantify the effective surface roughness. As a result, the inter-particle potential of mean force (PMF), second virial coefficient, and spinodal miscibility volume fraction vary non-monotonically with the surface bead to monomer diameter and particle core to surface bead diameter ratios. A miscibility window is predicted corresponding to an optimum degree of surface roughness that completely destroys depletion attraction resulting in a repulsive PMF. Variation of the (dense) matrix packing fraction can enhance or suppress particle miscibility depending upon the amount of surface roughness. Connecting the monomers into polymer chains destabilizes the system via enhanced contact depletion attraction, but the non-monotonic variations with surface roughness metrics persist.« less
Application of film-casting technique to investigate drug-polymer miscibility in solid dispersion and hot-melt extrudate.

PubMed

Parikh, Tapan; Gupta, Simerdeep Singh; Meena, Anuprabha K; Vitez, Imre; Mahajan, Nidhi; Serajuddin, Abu T M

2015-07-01

Determination of drug-polymer miscibility is critical for successful development of solid dispersions. This report details a practical method to predict miscibility and physical stability of drug with various polymers in solid dispersion and, especially, in melt extrudates by applying a film-casting technique. Mixtures of itraconazole (ITZ) with hydroxypropylmethylcellulose phthalate (HPMCP), Kollidon(®) VA 64, Eudragit(®) E PO, and Soluplus(®) were film-casted, exposed to 40°C/75% RH for 1 month and then analyzed using differential scanning calorimetry (DSC), powder X-ray diffractometry, and polarized light microscopy (PLM). ITZ had the highest miscibility with HPMCP, being miscible at drug to polymer ratio of 6:4 (w/w). There was a downward trend of lower miscibility with Soluplus(®) (miscible at 3:7, w/w, and a few microcrystals present at 4:6, w/w), Kollidon(®) VA 64 (2:8, w/w) and Eudragit(®) E PO (<1:9, w/w). PLM was found more sensitive to detect drug crystallization than DSC and powder X-ray diffractometry. There was general correlation between results of film casting and hot-melt extrusion (HME) using a twin screw extruder. For ITZ-Soluplus(®) mixtures, HME at 4:6 (w/w) resulted in a single phase, whereas drug crystallization was observed at higher drug load. HME of ITZ-Kollidon(®) VA 64 mixtures also correlated well with the miscibility predicted by film casting. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.
Thermo-Rheometric Studies of New Class Ionic Liquid Lubricants

NASA Astrophysics Data System (ADS)

Bakhtiyarov, Sayavur; Street, Kenneth; Scheiman, Daniel; van Dyke, Alan

2010-11-01

Due to their specific properties, such as small volatility, nonflammability, extreme thermal stability, low melting point, wide liquid range, and good miscibility with organic materials, ionic liquids attracted particular interest in various industrial processes. Recently, the unique properties of ionic liquids caught the attention of space tribologists. The traditional lubricating materials used in space have limited lifetimes in vacuum due to the catalytic degradation on metal surfaces, high vaporization at high temperatures, dewetting, and other disadvantages. The lubricants for the space applications must have vacuum stability, high viscosity index, low creep tendency, good elastohydrodynamic and boundary lubrication properties, radiation atomic oxygen resistance, optical or infrared transparency. Unfortunately, the properties such as heat flow, heat capacity, thermogravimetric weight loss, and non-linearity in the rheological behavior of the lubricants are not studied well for newly developed systems. These properties are crucial to analyzing thermodynamic and energy dissipative aspects of the lubrication process. In this paper we will present the rheological and heat and mass transfer measurements for the ionic liquid lubricants, their mixtures with and without additive.
A non-ideal model for predicting the effect of dissolved salt on the flash point of solvent mixtures.

PubMed

Liaw, Horng-Jang; Wang, Tzu-Ai

2007-03-06

Flash point is one of the major quantities used to characterize the fire and explosion hazard of liquids. Herein, a liquid with dissolved salt is presented in a salt-distillation process for separating close-boiling or azeotropic systems. The addition of salts to a liquid may reduce fire and explosion hazard. In this study, we have modified a previously proposed model for predicting the flash point of miscible mixtures to extend its application to solvent/salt mixtures. This modified model was verified by comparison with the experimental data for organic solvent/salt and aqueous-organic solvent/salt mixtures to confirm its efficacy in terms of prediction of the flash points of these mixtures. The experimental results confirm marked increases in liquid flash point increment with addition of inorganic salts relative to supplementation with equivalent quantities of water. Based on this evidence, it appears reasonable to suggest potential application for the model in assessment of the fire and explosion hazard for solvent/salt mixtures and, further, that addition of inorganic salts may prove useful for hazard reduction in flammable liquids.
Atomistic Modeling of RuAl and (RuNi) Al Alloys

NASA Technical Reports Server (NTRS)

Gargano, Pablo; Mosca, Hugo; Bozzolo, Guillermo; Noebe, Ronald D.; Gray, Hugh R. (Technical Monitor)

2002-01-01

Atomistic modeling of RuAl and RuAlNi alloys, using the BFS (Bozzolo-Ferrante-Smith) method for alloys is performed. The lattice parameter and energy of formation of B2 RuAl as a function of stoichiometry and the lattice parameter of (Ru(sub 50-x)Ni(sub x)Al(sub 50)) alloys as a function of Ni concentration are computed. BFS based Monte Carlo simulations indicate that compositions close to Ru25Ni25Al50 are single phase with no obvious evidence of a miscibility gap and separation of the individual B2 phases.
A Study of Production of Miscibility Gap Alloys with Controlled Structures

NASA Technical Reports Server (NTRS)

Parr, R. A.; Johnston, M. H.; Burka, J. A.; Davis, J. H.; Lee, J. A.

1983-01-01

Composite materials were directionally solidified using a new technique to align the constituents longitudinally along the length of the specimen. In some instances a tin coating was applied and diffused into the sample to form a high transition temperature superconducting phase. The superconducting properties were measured and compared with the properties obtained for powder composites and re-directionally solidified powder compacts. The samples which were compacted and redirectionally solidified showed the highest transition temperature and wildest transition range. This indicates that both steps, powder compaction and resolidification, determine the final superconducting properties of the material.
Pseudomorphic Semiconducting Heterostructures from Combinations of AlN, GaN and Selected SiC Polytypes: Theoretical Advancement and its Coordination with Experimental Studies of Nucleation, Growth, Characterization and Device Development

DTIC Science & Technology

1994-06-01

simultaneously expluiting the favorable characteristics of these materials include the thin film deposition of both pseudomorphic beterostructure and alloys ...diagram proposed by Zangvil and Ruh [10] shows a flat miscibility gap at =1900*C between -20 and 80 wt % AIN. Above this temperature, a 2H solid solution...was reported from >20 wt % AIN. For .20 wt % AIN, 8 I I solutions and two phase mixtures of 6H, 4H, and 2H were observed. Thin film solid solutions
The preparation and characterization of silk fibroin blended with low molecular weight hydroxypropyl methylcellulose (HPMC)

NASA Astrophysics Data System (ADS)

Shetty, G. Rajesha; Rao, B. Lakshmeesha; Gowda, Mahadeva; Shivananda, C. S.; Asha, S.; Sangappa, Y.

2018-04-01

In this work, the structure and optical properties of Silk Fibroin (SF), lower molecular weight Hydroxypropyl Methylcellulose (HPMC(L)) and its blend film of SF-HPMC(L) were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron Microscope (SEM) and UV-Visible spectroscopy (UV-Vis). The results indicates that the homogeneous miscible blend of SF-HPMC(L) has lower crystallite size and lower optical band gap compared to virgin SF and HPMC(L). FTIR study confirms the presence of both SF and HPMC(L) molecules in the prepared blend films.
Monte Carlo simulation of star/linear and star/star blends with chemically identical monomers

NASA Astrophysics Data System (ADS)

Theodorakis, P. E.; Avgeropoulos, A.; Freire, J. J.; Kosmas, M.; Vlahos, C.

2007-11-01

The effects of chain size and architectural asymmetry on the miscibility of blends with chemically identical monomers, differing only in their molecular weight and architecture, are studied via Monte Carlo simulation by using the bond fluctuation model. Namely, we consider blends composed of linear/linear, star/linear and star/star chains. We found that linear/linear blends are more miscible than the corresponding star/star mixtures. In star/linear blends, the increase in the volume fraction of the star chains increases the miscibility. For both star/linear and star/star blends, the miscibility decreases with the increase in star functionality. When we increase the molecular weight of linear chains of star/linear mixtures the miscibility decreases. Our findings are compared with recent analytical and experimental results.
Transient Interfacial Phenomena in Miscible Polymer Systems (TIPMPS)

NASA Technical Reports Server (NTRS)

Pojman, John A.; Bessonov, Nicholas; Volpert, Vitaly; Wilke, Hermann

2003-01-01

Almost one hundred years ago Korteweg published a theory of how stresses could be induced in miscible fluids by concentration gradients, causing phenomena that would appear to be the same as with immiscible fluids. Miscible fluids could manifest a transient or effective interfacial tension (EIT). To this day, there has been no definitive experiment to confirm Korteweg's model but numerous fascinating and suggestive experiments have been reported. The goal of TIPMPS is to answer the question: Can concentration and temperature gradients in miscible materials induce stresses that cause convection? Many polymer processes involving miscible monomer and polymer systems could be affected by fluid flow and so this work could help understand miscible polymer processing, not only in microgravity, but also on earth. Demonstrating the existence of this phenomenon in miscible fluids will open up a new area of study for materials science. The science objectives of TIPMPS are: (1) Determine if convection can be induced by variation of the width of a miscible interface; (2) Determine if convection can be induced by variation of temperature along a miscible interface; (3) Determine if convection can be induced by variation of conversion along a miscible interface An interface between two miscible fluids can best be created via a spatially-selective photopolymerization of dodecyl acrylate with a photoinitiator, which allows the creation of precise and accurate concentration gradients between polymer and monomer. Optical techniques will be used to measure the refractive index variation caused by the resultant temperature and concentration fields. The viscosity of the polymer will be measured from the increase in the fluorescence of pyrene. Because the large concentration and temperature gradients cause buoyancy-driven convection that prevents the observation of the predicted flows, the experiment must be done in microgravity. In this report, we will consider our efforts to estimate the square gradient parameter, k, and our use of the estimates in modeling of the planned TIPMPS experiments. We developed a model consisting of the heat and diffusion equations with convective terms and of the Navier-Stokes equations with an additional volume force written in the form of the Korteweg stresses arising from nonlocal interaction in the fluid. The fluid's viscosity dependence on polymer conversion and temperature was taken from measurements of poly(dodecyl acrylate). Numerical modeling demonstrated that significant flows would arise for conditions corresponding to the planned experiments.
Atomistic modeling of the solid-state chemistry of actinide materials

NASA Astrophysics Data System (ADS)

Shuller, Lindsay C.

Materials that incorporate actinides are critical to the nuclear fuel cycle, either as nuclear fuels or nuclear waste forms. In this thesis, I examine four materials: i) ThO2-UO2 solid solutions, ii) binary ThO2-CeO2-ZrO2 solid solutions, iii) Np-doped studtite, iv) Np-doped boltwoodite. Computational methods, particularly density functional theory (DFT) calculations and Monte-Carlo (MC) simulations, are used to determine the energetics and structures of these actinide-bearing materials. The solid-solution behavior of nuclear fuels and nuclear waste forms indicate the thermodynamic stability of the material, which is important for understanding the in-reactor fuel properties and long-term stability of used fuel. The ThxU1-xO2 and ThxCe 1-xO2 binaries are almost completely miscible; however, DeltaGmix reveals a small tendency for the systems to exsolve (e.g., DeltaEexsoln(Th xU1-xO2) = 0.13 kJ/(mol cations) at 750 K). Kinetic hindrances (e.g., interfacial energy) may inhibit exsolution, especially at the low temperatures necessary to stabilize the nanoscale exsolution lamellae observed in the ThxU1-xO2 and Ce xZr1-xO2 binaries. Miscibility in the Zr-bearing binaries is limited. At 1400 °C, only 3.6 and 0.09 mol% ZrO2 is miscible in CeO2 and ThO2, respectively. The incorporation of minor amounts of Np5+,6+ into uranium alteration phases, e.g., studtite [UO2O2 (H2O)4] or boltwoodite [K(UO2)(SiO 3OH)(H2O)1.5] , may limit the mobility of aqueous neptunyl complexes released from oxidized nuclear fuels. Np6+-incorporation into studtite requires less energy than Np5+-incorporation (e.g., with source/sink = Np2O5/UO 3 DeltaEincorp(Np6+) = 0.42 eV and DeltaEincorp(Np5+) = 1.12 eV). In addition, Np6+ is completely miscible in studtite at room temperature with respect to a hypothetical Np6+-studtite. Electronic structure calculations provide insight into Np-bonding in studtite. The Np 5f orbitals are within the band gap of studtite, resulting in the narrowing of the band gap from 2.29 eV for studtite to 1.09 eV for Np-incorporated studtite. Three charge-balancing mechanisms for the substitution of Np5+ for U6+ were compared: i) addition of H+ [DeltaEincorp(bolt) = 0.79 eV; DeltaEincorp(stud) = 1.12 eV], ii) interlayer coupled substitution [DeltaEincorp (bolt) = 1.40 eV], iii) intra-layer coupled-substitution [DeltaEincorp(bolt) = 0.86 eV]. Solid-solution calculations of the intra-layer coupled-substitution mechanism, where Np 5+ and P5+ substitute for U6+ and Si 4+, predict an incorporation limit of 585 ppm at 300 °C.
Experimental Investigation and Thermodynamic Assessment of Phase Equilibria in the PLLA/Dioxane/Water Ternary System for Applications in the Biomedical Field.

PubMed

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

2015-12-01

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

NASA Astrophysics Data System (ADS)

Schamp, Crispin T.

When evaluating the path of phase transformations in systems with nanoscopic dimensions one often relies on bulk phase diagrams for guidance because of the lack of phase diagrams that show the effect of particle size. The GaAs-GaSb pseudo-binary alloy is chosen for study to gain insight into the size dependence of solid-solubility in a two-phase system. To this end, a study is performed using independent laser ablation of high purity targets of GaAs and GaSb. The resultant samples are analyzed by transmission electron microscopy. Experimental results indicate that GaAs-GaSb nanoparticles have been formed with compositions that lie within the miscibility gap of bulk GaAs-GaSb. An unusual nanoparticle morpohology resembling the appearance of ice cream cones has been observed in single component experiments. These particles are composed of a spherical cap of Ga in contact with a crystalline cone of either GaAs or GaSb. The cones take the projected 2-D shape of a triangle or a faceted gem. The liquid Ga is found to consistently be of spherical shape and wets to the widest corners of the cone, suggesting an energy minimum exists at that wetting condition. To explore this observation a liquid sphere is modeled as being penetrated by a solid gem. The surface energies of the solid and liquid, and interfacial energy are summed as a function of penetration depth, with the sum showing a cusped minimum at the penetration depth corresponding to the waist of the gem. The angle of contact of the liquid wetting the cone is also calculated, and Young's contact angle is found to occur when the derivative of the total energy with respect to penetration depth is zero, which can be a maximum or a minimum depending on the geometrical details. The spill-over of the meniscus across the gem corners is found to be energetically favorable when the contact angle achieves the value of the equilibrium angle; otherwise the meniscus is pinned at the corners.
DEVELOPMENT AND OPTIMIZATION OF GAS-ASSISTED GRAVITY DRAINAGE (GAGD) PROCESS FOR IMPROVED LIGHT OIL RECOVERY

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

Dandina N. Rao; Subhash C. Ayirala; Madhav M. Kulkarni

This report describes the progress of the project ''Development and Optimization of Gas-Assisted Gravity Drainage (GAGD) Process for Improved Light Oil Recovery'' for the duration of the second project year (October 1, 2003--September 30, 2004). There are three main tasks in this research project. Task 1 is scaled physical model study of GAGD process. Task 2 is further development of vanishing interfacial tension (VIT) technique for miscibility determination. Task 3 is determination of multiphase displacement characteristics in reservoir rocks. In Section I, preliminary design of the scaled physical model using the dimensional similarity approach has been presented. Scaled experiments onmore » the current physical model have been designed to investigate the effect of Bond and capillary numbers on GAGD oil recovery. Experimental plan to study the effect of spreading coefficient and reservoir heterogeneity has been presented. Results from the GAGD experiments to study the effect of operating mode, Bond number and capillary number on GAGD oil recovery have been reported. These experiments suggest that the type of the gas does not affect the performance of GAGD in immiscible mode. The cumulative oil recovery has been observed to vary exponentially with Bond and capillary numbers, for the experiments presented in this report. A predictive model using the bundle of capillary tube approach has been developed to predict the performance of free gravity drainage process. In Section II, a mechanistic Parachor model has been proposed for improved prediction of IFT as well as to characterize the mass transfer effects for miscibility development in reservoir crude oil-solvent systems. Sensitivity studies on model results indicate that provision of a single IFT measurement in the proposed model is sufficient for reasonable IFT predictions. An attempt has been made to correlate the exponent (n) in the mechanistic model with normalized solute compositions present in both fluid phases. IFT measurements were carried out in a standard ternary liquid system of benzene, ethanol and water using drop shape analysis and capillary rise techniques. The experimental results indicate strong correlation among the three thermodynamic properties solubility, miscibility and IFT. The miscibility determined from IFT measurements for this ternary liquid system is in good agreement with phase diagram and solubility data, which clearly indicates the sound conceptual basis of VIT technique to determine fluid-fluid miscibility. Model fluid systems have been identified for VIT experimentation at elevated pressures and temperatures. Section III comprises of the experimental study aimed at evaluating the multiphase displacement characteristics of the various gas injection EOR process performances using Berea sandstone cores. During this reporting period, extensive literature review was completed to: (1) study the gravity drainage concepts, (2) identify the various factors influencing gravity stable gas injection processes, (3) identify various multiphase mechanisms and fluid dynamics operative during the GAGD process, and (4) identify important dimensionless groups governing the GAGD process performance. Furthermore, the dimensional analysis of the GAGD process, using Buckingham-Pi theorem to isolate the various dimensionless groups, as well as experimental design based on these dimensionless quantities have been completed in this reporting period. On the experimental front, recommendations from previous WAG and CGI have been used to modify the experimental protocol. This report also includes results from scaled preliminary GAGD displacements as well as the details of the planned GAGD corefloods for the next quarter. The technology transfer activities have mainly consisted of preparing technical papers, progress reports and discussions with industry personnel for possible GAGD field tests.« less

Growth of lattice-matched GaInAsP grown on vicinal GaAs(001) substrates within the miscibility gap for solar cells

DOE PAGES

Oshima, Ryuji; France, Ryan M.; Geisz, John F.; ...

2016-10-13

The growth of quaternary Ga 0.68In 0.32As 0.35P 0.65 by metal-organic vapor phase epitaxy is very sensitive to growth conditions because the composition is within a miscibility gap. In this investigation, we fabricated 1 um-thick lattice-matched GaInAsP films grown on GaAs(001) for application to solar cells. In order to characterize the effect of the surface diffusion of adatoms on the material quality of alloys, the growth temperature and substrate miscut are varied. Transmission electron microscopy and two-dimensional in-situ multi-beam optical stress determine that growth temperatures of 650 degrees C and below enhance the formation of the CuPtB atomic ordering andmore » suppress material decomposition, which is found to occur at the growth surface. The root-mean-square (RMS) roughness is reduced from 33.6 nm for 750 degrees C to 1.62 nm for 650 degrees C, determined by atomic force microscopy. Our initial investigations show that the RMS roughness can be further reduced using increased miscut angle, and substrates miscut toward (111)A, leading to an RMS roughness of 0.56 nm for the sample grown at 600 degrees C on GaAs miscut 6 degrees toward (111)A. Using these conditions, we fabricate an inverted hetero-junction 1.62 eV Ga 0.68In 0.32As 0.35P 0.65 solar cell without an anti-reflection coating with a short-circuit current density, open-circuit voltage, fill factor, and efficiency of 12.23 mA/cm2, 1.12 V, 86.18%, and 11.80%, respectively.« less
Measuring Diffusion of Liquids by Common-Path Interferometry

NASA Technical Reports Server (NTRS)

Rashidnia, Nasser

2003-01-01

A method of observing the interdiffusion of a pair of miscible liquids is based on the use of a common-path interferometer (CPI) to measure the spatially varying gradient of the index refraction in the interfacial region in which the interdiffusion takes place. Assuming that the indices of refraction of the two liquids are different and that the gradient of the index of refraction of the liquid is proportional to the gradient in the relative concentrations of either liquid, the diffusivity of the pair of liquids can be calculated from the temporal variation of the spatial variation of the index of refraction. This method yields robust measurements and does not require precise knowledge of the indices of refraction of the pure liquids. Moreover, the CPI instrumentation is compact and is optomechanically robust by virtue of its common- path design. The two liquids are placed in a transparent rectangular parallelepiped test cell. Initially, the interface between the liquids is a horizontal plane, above which lies pure liquid 2 (the less-dense liquid) and below which lies pure liquid 1 (the denser liquid). The subsequent interdiffusion of the liquids gives rise to a gradient of concentration and a corresponding gradient of the index of refraction in a mixing layer. For the purpose of observing the interdiffusion, the test cell is placed in the test section of the CPI, in which a collimated, polarized beam of light from a low-power laser is projected horizontally through a region that contains the mixing layer.
Effect of PEO molecular weight on the miscibility and dynamics in epoxy/PEO blends.

PubMed

Lu, Shoudong; Zhang, Rongchun; Wang, Xiaoliang; Sun, Pingchuan; Lv, Weifeng; Liu, Qingjie; Jia, Ninghong

2015-11-01

In this work, the effect of poly(ethylene oxide) (PEO) molecular weight in blends of epoxy (ER) and PEO on the miscibility, inter-chain weak interactions and local dynamics were systematically investigated by multi-frequency temperature modulation DSC and solid-state NMR techniques. We found that the molecular weight (M(w)) of PEO was a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interactions between PEO and ER. A critical PEO molecular weight (M(crit)) around 4.5k was found. PEO was well miscible with ER when the molecular weight was below M(crit), where the chain motion of PEO was restricted due to strong inter-chain hydrogen bonding interactions. However, for the blends with high molecular weight PEO (M(w) > M(crit)), the miscibility between PEO and ER was poor, and most of PEO chains were considerably mobile. Finally, polarization inversion spin exchange at magic angle (PISEMA) solid-state NMR experiment further revealed the different mobility of the PEO in ER/PEO blends with different molecular weight of PEO at molecular level. Based on the DSC and NMR results, a tentative model was proposed to illustrate the miscibility in ER/PEO blends.
Microtubules as platforms for probing liquid-liquid phase separation in cells: application to RNA-binding proteins.

PubMed

Maucuer, Alexandre; Desforges, Bénédicte; Joshi, Vandana; Boca, Mirela; Kretov, Dmitry; Hamon, Loic; Bouhss, Ahmed; Curmi, Patrick A; Pastré, David

2018-05-04

Liquid-liquid phase separation enables compartmentalization of biomolecules in cells, notably RNA and associated proteins in the nucleus. Besides critical functions in RNA processing, there is a major interest in deciphering the molecular mechanisms of compartmentalization orchestrated by RNA-binding proteins such as TDP-43 and FUS due to their link to neuron diseases. However, tools for probing compartmentalization in cells are lacking. Here we developed a method to analyze the mixing:demixing of two different phases in a cellular context. The principle is the following: mRNA-binding proteins are confined on microtubules and quantitative parameters defining their spatial segregation are measured along the microtubule network. Through this approach, we found that four mRNA binding proteins, HuR, G3BP1, TDP-43 and FUS form mRNA-rich liquid-like compartments on microtubules. TDP-43 is partly miscible with FUS but immiscible with either HuR or G3BP1. We also demonstrate that mRNA is essential to capture the mixing:demixing behavior of RNA-binding proteins in cells. Altogether we show that microtubules can be used as platforms to understand the mechanisms underlying liquid-liquid phase separation and their deregulation in human diseases. © 2018. Published by The Company of Biologists Ltd.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnhill, William C.; Qu, Jun; Luo, Huimin

In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less
Characteristics of proportionate growth observed in instability patterns of miscible fluids

NASA Astrophysics Data System (ADS)

Bischofberger, Irmgard; Ramachandran, Radha; Nagel, Sidney R.; Nagel lab Team

2014-11-01

As a baby mammal grows, different parts of its body develop at the nearly the same rate and thus to a good approximation in direct proportion to one another. This type of growth is called proportionate growth. As familiar as it appears to us, it is very rarely found in physical systems outside of the biological world. We here show an example of proportionate growth that occurs in the instability formed when a less viscous liquid, of viscosity ηin displaces a more viscous miscible one, of viscosity ηout. We investigate the growth of these patterns in a quasi-two-dimensional geometry. Within a range of viscosity ratios 0.1 <ηin /ηout <0.3, we observe the formation of small blunt structures that form at the edges of an inner circular region devoid of fingers. As the pattern grows, the size of these structures increases in proportion to the size of the inner circle, such that even small details in the shape of the pattern remain essentially unchanged during growth. These characteristics of proportionate growth are reflected in the shape of the interface in the third dimension as well.
High throughput screening: an in silico solubility parameter approach for lipids and solvents in SLN preparations.

PubMed

Shah, Malay; Agrawal, Yadvendra

2013-01-01

The present paper describes an in silico solubility behavior of drug and lipids, an essential screening study in preparation of solid lipid nanoparticles (SLN). Ciprofloxacin HCl was selected as a model drug along with 11 lipids and 5 organic solvents. In silico miscibility study of drug/lipid/solvent was performed using Hansen solubility parameter approach calculated by group contribution method of Van Krevelen and Hoftyzer. Predicted solubility was validated by determining solubility of lipids in various solvent at different temperature range, while miscibility of drug in lipids was determined by apparent solubility study and partition experiment. The presence of oxygen and OH functionality increases the polarity and hydrogen bonding possibilities of the compound which has reflected the highest solubility parameter values for Geleol and Capmul MCM C8. Ethyl acetate, Geleol and Capmul MCM C8 was identified as suitable organic solvent, solid lipid and liquid lipid respectively based on a solubility parameter approach which was in agreement with the result of an apparent solubility study and partition coefficient. These works demonstrate the validity of solubility parameter approach and provide a feasible predictor to the rational selection of excipients in designing SLN formulation.
Initial Observations on the Burning of an Ethanol Droplet in Microgravity

NASA Technical Reports Server (NTRS)

Kazakov, Andrei; Urban, Bradley; Conley, Jordan; Dryer, Frederick L.; Ferkul, Paul (Technical Monitor)

1999-01-01

Combustion of liquid ethanol represents an important system both from fundamental and practical points of view, Ethanol is currently being used as an additive to gasoline in order to reduce carbon monoxide and particulate emissions as well as to improve the fuel octane rating. A detailed physical understanding of liquid ethanol combustion is therefore necessary to achieve an optimal performance of such fuel blends in practical conditions. Ethanol is also a relatively simple model compound suitable for investigation of important combustion characteristics typical of more complex fuels. In particular, ethanol has been proposed for studies of sooting behavior during droplet burning. The sooting nature of ethanol has pressure sensitivities similar to that of n-heptane, but shifted to a higher range of pressures (1-3 atm). Additionally, liquid ethanol is miscible with water produced during its combustion forming mixtures with azeotropic behavior, a phenomenon important for understanding multi-component, liquid fuel combustion. In this work, we present initial results obtained in a series of recent space-based experiments and develop a detailed model describing the burning of ethanol droplet in microgravity.
Silicate and Carbonatite Melts in the Mantle: Adding CO2 to the pMELTS Thermodynamic Model of Silicate Phase Equilibria

NASA Astrophysics Data System (ADS)

Antoshechkina, P. M.; Shorttle, O.

2016-12-01

The current rhyolite-MELTS algorithm includes a mixed H2O-CO2 vapor phase, and a self-consistent speciation model for CO2 and CaCO3 in the silicate liquid (Ghiorso & Gualda 2012; 2015). Although intended primarily to model crustal differentiation and degassing, GG15 captures much of the experimentally-observed melting behavior of CO2-rich mafic lithologies, including generation of small-degree carbonatite melts, a miscibility gap between carbonatite and silicate liquids at low P and a smooth transition to a single carbonated-silicate melt at high P (e.g. Dasgupta et al. 2007). However, solid and liquid carbonate phases were not used in calibration of GG15, and it is suitable only for P < 3 GPa. We present a preliminary model, based on pMELTS (Ghiorso et al. 2002), for melting of nominally-anhydrous carbonated peridotite and pyroxenite. In Antoshechkina et al. (2015; and references therein) we developed a scheme for calibration of molar volumes that directly interfaces with a MySQL database, adapted from LEPR (Hirschmann et al. 2008). Here, we further extend our database, e.g. to include multiple carbonate phases, and combine the calibration scheme with the libalphaMELTS interface to the rhyolite-MELTS, pMELTS, and H2O-CO2 fluid thermodynamic models (see magmasource.caltech.edu/alphamelts). We use a Monte-Carlo type calibration approach to fit the observed phases and compositions, though stop short of a fully Bayesian formulation. The CO2-fluid experimental database has been updated to include more recent and higher P studies, adding approximately 40 pure fluid plus liquid constraints that conform to the selection criteria used in GG15. To further expand the database, we plan to use some or all of: solid carbonate-bearing experiments; coexisting silicate and carbonatite liquids; phase-present, and phase-absent constraints. As a first approximation, we include four carbonate phases: pure calcite and aragonite, and binary solutions for dolomite-ankerite and magnesite-siderite. Following GG15, we have adopted the CO2 fluid model of Duan & Zhang (2006) and added CO2 and CaCO3 species to the pMELTS liquid model. A key question that we hope to address during calibration is whether a Na2CO3 liquid species is justified instead of, or in addition to, CaCO3 for the range over which pMELTS is calibrated (1 < P < 4 GPa).
Liquid-liquid phase separation in atmospheric aerosol particles: dependence on organic functionalities and mixture complexity

NASA Astrophysics Data System (ADS)

Song, M.; Marcolli, C.; Krieger, U. K.; Zuend, A.; Peter, T.

2012-04-01

In the troposphere, aerosol particles undergo phase transitions such as deliquescence and efflorescence during humidity cycles (Marcolli and Krieger, 2006). In addition, interactions between organic and inorganic compounds lead to liquid-liquid phase separation (LLPS) (Ciobanu et al., 2009). Recent studies on a limited number of model systems have shown that oxygen-to-carbon ratios (O:C) of the organic aerosol fraction might be a good predictor for LLPS in mixed organic/ammonium sulfate (AS) particles (Bertram et al., 2011; Song et al., 2011). However, in order to corroborate this hypothesis experiments with an organic fraction that consists of a higher number of components with different O:C ratios and functional groups are needed. In order to determine the influence of O:C ratio, the specific organic functionalities and the mixture complexity on LLPS, we subjected organic/AS particles deposited on a hydrophobically coated substrate to relative humidity (RH) cycles and observed phase changes using optical microscopy and micro-Raman spectroscopy. To determine the influence of mixture complexity, we mixed together up to 10 organic compounds. We also prepared mixtures that were rich in different types of functional groups like polyols, aromatics and dicarboxylic acids which were identified from field measurements. We screened for a miscibility gap by varying the organic-to-inorganic ratio from 2:1 to 1:6. AS in the investigated single particles effloresced at 27 - 50 %RH and deliquesced at 72 - 79 %RH during humidity cycles. The occurrence of LLPS is determined to a high degree by the O:C of the organics: there was no LLPS for mixtures with O:C > 0.8 and there was always LLPS for mixtures with O:C < 0.57. In the range in between, we observed a dependence on the specific functional groups: a high share of aromatic functionalities shifts the range of O:C for which LLPS occurs to lower values. A correlation was also found for the onset RH of LLPS as a function of O:C. We did not find any dependence of LLPS on the complexity of the mixture. Overall, the RH range of coexistence of two liquid phases depends in first place on the O:C ratio of the particles and in second place also on the specific organic functionalities.
Two-liquid-phase bioreactors.

PubMed

Van Sonsbeek, H M; Beeftink, H H; Tramper, J

1993-09-01

The application of two liquid phases that are poorly miscible is a fascinating research topic for biocatalytical conversions because of the promising results. Motives for application include an increase of productivity and achievement of continuous processing, but new limitations arise, e.g., interfacial effects such as biocatalyst accumulation and loss of activity, medium component accumulation, and slow coalescence. Centrifuges, membranes, and immobilization are tools that can overcome part of the problems, but more fundamental knowledge about interfaces and coalescence is still necessary for successful application. For scaleup and further development of processes based on the obtained results, a choice must be made for the configuration of the experimental setup of a bioreactor. Aspects like aeration, shear stress, batch or continuous processing, and immobilization can play an important role. This review article describes these aspects and the proposals that have been made in recent years concerning two-liquid-phase bioreactors. It shows some adaptations to existing bioreactors, such as loop reactors and stirred-tank reactors.
Efficient capture of SO2 by a binary mixture of caprolactam tetrabutyl ammonium bromide ionic liquid and water.

PubMed

Duan, Erhong; Guo, Bin; Zhang, Miaomiao; Guan, Yanan; Sun, Hua; Han, Jing

2011-10-30

The solubility of SO(2) in a binary mixture of water and caprolactam tetrabutyl ammonium bromide ionic liquid (CPL-TBAB IL) was investigated. Though the ionic liquid and water were fully miscible, a phase separation occurred when SO(2) was introduced into the mixture. The SO(2) concentrated in the lower layer, and it could be released by heating the solution under reduced pressure (382.2K, 10.1 kPa). After desorption, the mixture could be reused to absorb SO(2). It was found that SO(2) acts as a switch to cause the water and CPL-TBAB IL to phase separate, and the mechanics of this phase separation process was studied by gas chromatography-mass spectrometry, fourier transform-infrared spectroscopy and Karl-Fisher titration. The absorption and desorption of SO(2) in the CPL-TBAB/water mixtures were reversible. Copyright © 2011 Elsevier B.V. All rights reserved.
Description of Adsorption in Liquid Chromatography under Nonideal Conditions.

PubMed

Ortner, Franziska; Ruppli, Chantal; Mazzotti, Marco

2018-05-15

A thermodynamically consistent description of binary adsorption in reversed-phase chromatography is presented, accounting for thermodynamic nonidealities in the liquid and adsorbed phases. The investigated system involves the adsorbent Zorbax 300SB-C18, as well as phenetole and 4- tert-butylphenol as solutes and methanol and water as inert components forming the eluent. The description is based on adsorption isotherms, which are a function of the liquid-phase activities, to account for nonidealities in the liquid phase. Liquid-phase activities are calculated with a UNIQUAC model established in this work, based on experimental phase equilibrium data. The binary interaction in the adsorbed phase is described by the adsorbed solution theory, assuming an ideal (ideal adsorbed solution theory) or real (real adsorbed solution theory) adsorbed phase. Implementation of the established adsorption model in a chromatographic code achieves a quantitative description of experimental elution profiles, with feed compositions exploiting the entire miscible region, and involving a broad range of different eluent compositions (methanol/water). The quantitative agreement of the model and experimental data serves as a confirmation of the underlying physical (thermodynamic) concepts and of their applicability to a broad range of operating conditions.
Sensitivity of a Wave Structure to Initial Conditions

NASA Technical Reports Server (NTRS)

Duval, Walter M. B.; Duval, Walter M. B. (Technical Monitor)

2000-01-01

Microgravity experiments aimed at quantifying effects of gentler via controlled sinusoidal forcing transmitted on the interface between two miscible liquids have shown the evolution of a quasi -stationary four-mode wave structure oriented vertically. The sensitivity of the wave structure to phase angle variation is investigated computationally. We show that a slight variation of the phase angle is sufficient to cause a bifurcation to a two-mode structure. The dependence of phase angle on wave structure is attributed to sensitivity on initial conditions due to the strong nonlinearity of the coupled field equations for the parametric space of interest.
Magnetic cellulose-derivative structures

DOEpatents

Walsh, M.A.; Morris, R.S.

1986-09-16

Structures to serve as selective magnetic sorbents are formed by dissolving a cellulose derivative such as cellulose triacetate in a solvent containing magnetic particles. The resulting solution is sprayed as a fine mist into a chamber containing a liquid coagulant such as n-hexane in which the cellulose derivative is insoluble but in which the coagulant is soluble or miscible. On contact with the coagulant, the mist forms free-flowing porous magnetic microspheric structures. These structures act as containers for the ion-selective or organic-selective sorption agent of choice. Some sorption agents can be incorporated during the manufacture of the structure. 3 figs.
Magnetic cellulose-derivative structures

DOEpatents

Walsh, Myles A.; Morris, Robert S.

1986-09-16

Structures to serve as selective magnetic sorbents are formed by dissolving a cellulose derivative such as cellulose triacetate in a solvent containing magnetic particles. The resulting solution is sprayed as a fine mist into a chamber containing a liquid coagulant such as n-hexane in which the cellulose derivative is insoluble but in which the coagulant is soluble or miscible. On contact with the coagulant, the mist forms free-flowing porous magnetic microspheric structures. These structures act as containers for the ion-selective or organic-selective sorption agent of choice. Some sorbtion agents can be incorporated during the manufacture of the structure.
Thermochemical generation of hydrogen

NASA Technical Reports Server (NTRS)

Lawson, D. D.; Petersen, G. R. (Inventor)

1982-01-01

The direct fluid contact heat exchange with H2SO4 at about 330 C prior to high temperature decomposition at about 830 C in the oxygen release step of several thermochemical cycles for splitting water into hydrogen and oxygen provides higher heat transfer rates, savings in energy and permits use of cast vessels rather than expensive forged alloy indirect heat exchangers. Among several candidate perfluorocarbon liquids tested, only perfluoropropylene oxide polymers having a degree of polymerization from about 10 to 60 were chemically stable, had low miscibility and vapor pressure when tested with sulfuric acid at temperatures from 300 C to 400 C.
Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties.

PubMed

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-03-16

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.
Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties

PubMed Central

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-01-01

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs. PMID:26999112
Deformation of interface in a partially miscible system during favorable displacement

NASA Astrophysics Data System (ADS)

Suzuki, Ryuta; Nagatsu, Yuichiro; Mishra, Manoranjan; Ban, Takahiko

2017-11-01

The Saffman-Taylor instability triggers a well-known viscous fingering (VF, called unfavorable displacement), occurring when a less viscous fluid displaces a more viscous one in porous media or in a Hele-Shaw cell because the boundary of the two fluids becomes hydrodynamically unstable. In the reverse situation (called favorable displacement) in which a more viscous fluid displaces a less viscous one, no instabilities occur due to hydrodynamically stable system. It has been reported that the favorable displacements become unstable by several physicochemical effects. So far, studies of both displacements have focused on fluids that are either fully miscible or immiscible. However, little attention has been paid to displacements in partially miscible system. Here, we have discovered that a partial miscibility triggers fingering instability in a favorable displacement without any chemical reactions. The occurrence of this new instability is induced by not hydrodynamic effects but a thermodynamic effect that is so-called Korteweg effect in which convection is induced during phase separation process in a partially miscible system.

Hydrodynamic instabilities in miscible fluids

NASA Astrophysics Data System (ADS)

Truzzolillo, Domenico; Cipelletti, Luca

2018-01-01

Hydrodynamic instabilities in miscible fluids are ubiquitous, from natural phenomena up to geological scales, to industrial and technological applications, where they represent the only way to control and promote mixing at low Reynolds numbers, well below the transition from laminar to turbulent flow. As for immiscible fluids, the onset of hydrodynamic instabilities in miscible fluids is directly related to the physics of their interfaces. The focus of this review is therefore on the general mechanisms driving the growth of disturbances at the boundary between miscible fluids, under a variety of forcing conditions. In the absence of a regularizing mechanism, these disturbances would grow indefinitely. For immiscible fluids, interfacial tension provides such a regularizing mechanism, because of the energy cost associated to the creation of new interface by a growing disturbance. For miscible fluids, however, the very existence of interfacial stresses that mimic an effective surface tension is debated. Other mechanisms, however, may also be relevant, such as viscous dissipation. We shall review the stabilizing mechanisms that control the most common hydrodynamic instabilities, highlighting those cases for which the lack of an effective interfacial tension poses deep conceptual problems in the mathematical formulation of a linear stability analysis. Finally, we provide a short overview on the ongoing research on the effective, out of equilibrium interfacial tension between miscible fluids.
Characterization of interfaces in Binary and Ternary Polymer Blends by Positron Lifetime Spectroscopy

NASA Astrophysics Data System (ADS)

Ranganathaiah, C.

2015-06-01

A miscible blend is a single-phase system with compact packing of the polymeric chains/segments due configuration/conformational changes upon blending. Differential Scanning Calorimetry (DSC) is the most employed method to ascertain whether the blend is miscible or immiscible. Positron Lifetime Spectroscopy (PLS) has been employed in recent times to study miscibility properties of polymer blends by monitoring the ortho-Positronium annihilation lifetimes as function of composition. However, just free volume monitoring and the DSC methods fail to provide the composition dependent miscibility of blends. To overcome this limitation, an alternative approach based on hydrodynamic interactions has been developed to derive this information using the same o-Ps lifetime measurements. This has led to the development of a new method of measuring composition dependent miscibility level in binary and ternary polymer blends. Further, the new method also provides interface characteristics for immiscible blends. The interactions between the blend components has a direct bearing on the strength of adhesion at the interface and hence the hydrodynamic interaction. Understanding the characteristic of interfaces which decides the miscibility level of the blend and their end applications is made easy by the present method. The efficacy of the present method is demonstrated for few binary and ternary blends.
Metastable liquid lamellar structures in binary and ternary mixtures of Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Díaz-Herrera, Enrique; Ramírez-Santiago, Guillermo; Moreno Razo, José A.

2004-03-01

We have carried out extensive equilibrium MD simulations to investigate the Liquid-Vapor coexistence in partially miscible binary and ternary mixtures LJ fluids. We have studied in detail the time evolution of the density profiles and the interfacial properties in a temperature region of the phase diagram where the condensed phase is demixed. The composition of the mixtures are fixed, 50% for the binary mixture and 33.33% for the ternary mixture. The results of the simulations clearly indicate that in the range of temperatures 78 < T < 102 ^oK,--in the scale of argon-- the system evolves towards a metastable alternated liquid-liquid lamellar state in coexistence with its vapor phase. These states can be achieved if the initial configuration is fully disordered, that is, when the particles of the fluids are randomly placed on the sites of an FCC crystal or the system is completely mixed. As temperature decreases these states become very well defined and more stable in time. We find that below 90 ^oK, the alternated liquid-liquid lamellar state remains alive for 80 ns, in the scale of argon, the longest simulation we have carried out. Nonetheless, we believe that in this temperature region these states will be alive for even much longer times.
Sheath liquid interface for the coupling of normal-phase liquid chromatography with electrospray mass spectrometry and its application to the analysis of neoflavonoids.

PubMed

Charles, Laurence; Laure, Frédéric; Raharivelomanana, Phila; Bianchini, Jean-Pierre

2005-01-01

A novel interface that allows normal-phase liquid chromatography to be coupled with electrospray ionization (ESI) is reported. A make-up solution of 60 mM ammonium acetate in methanol, infused at a 5 microl min(-1) flow-rate at the tip of the electrospray probe, provides a sheath liquid which is poorly miscible with the chromatographic effluent, but promotes efficient ionization of the targeted analytes. Protonated molecules generated in the ESI source were subjected to tandem mass spectrometric experiments in a triple-quadrupole mass spectrometer. The main fragmentation reactions were characterized for each analyte and specific mass spectral transitions were used to acquire chromatographic data in the multiple reaction monitoring detection mode. Results obtained during optimization of the sheath liquid composition and flow-rate suggest that the electrospray process was mainly under the control of the make-up solution, and that it forms an external charged layer around a neutral chromatographic mobile phase core. This sheath liquid interface was implemented for the analysis of some neoflavonoid compounds and its performance was evaluated. Limits of detection were established for calophillolide, inophyllum B, inophyllum P and inophyllum C at 100, 25, 15 and 100 ng ml(-1), respectively.
Liquid ``Coffee Rings'' and the Spreading of Volatile Liquid Mixtures

NASA Astrophysics Data System (ADS)

Wood, Clay; Pye, Justin; Burton, Justin

When a volatile liquid drop is placed on a wetting surface, it rapidly spreads and evaporates. The spreading dynamics and drop geometry are determined by a balance between thermal and interfacial forces, including Marangoni effects. However, this spreading behavior is drastically altered when drops contain a miniscule amount of a less-volatile miscible liquid (solute) in the bulk (solvent); contact line instabilities in the form of ``fingers'' develop. Characteristic finger size increases with increasing solute concentration and is apparent for concentrations as small as 0.1% by volume. Also, the spreading rate depends sensitively on the solute concentration, especially if the solute preferentially wets the substrate. At higher solute concentrations, the spreading droplet will form ``beads'' at the contact line, rather than fingers, and are deposited as the solvent recedes and evaporates, leaving behind a complex pattern of solute micro-droplets. Liquid ``coffee rings'' are often left behind after evaporation because there is a high evaporation rate of the solvent at the contact line, which increases the concentration of the solute, and the longevity of the rings depends on the solute vapor pressure. These results highlight the unusual sensitivity to contamination of volatile spreading, and the complex patterns of liquid contamination deposited following evaporation from a wetted surface. NSF 1455086.
Liquid level detector

DOEpatents

Tokarz, Richard D.

1982-01-01

A liquid level sensor having a pair of upright conductors spaced by an insulator defining a first high resistance path between the conductors. An electrically conductive path is interposed between the upright conductors at a discrete location at which liquid level is to be measured. It includes a liquid accessible gap of a dimension such that the electrical resistance across the conductor when the gap is filled with the liquid is detectably less than when the gap is emptied. The conductor might also be physically altered by temperature changes to serve also as an indicator of elevated temperature.
Characterization and cytotoxicity evaluation of biocompatible amino acid esters used to convert salicylic acid into ionic liquids.

PubMed

Moshikur, Rahman Md; Chowdhury, Md Raihan; Wakabayashi, Rie; Tahara, Yoshiro; Moniruzzaman, Muhammad; Goto, Masahiro

2018-07-30

The technological utility of active pharmaceutical ingredients (APIs) is greatly enhanced when they are transformed into ionic liquids (ILs). API-ILs have better solubility, thermal stability, and the efficacy in topical delivery than solid or crystalline drugs. However, toxicological issue of API-ILs is the main challenge for their application in drug delivery. To address this issue, 11 amino acid esters (AAEs) were synthesized and investigated as biocompatible counter cations for the poorly water-soluble drug salicylic acid (Sal) to form Sal-ILs. The AAEs were characterized using 1 H and 13 C NMR, FTIR, elemental, and thermogravimetric analyses. The cytotoxicities of the AAE cations, Sal-ILs, and free Sal were investigated using mammalian cell lines (L929 and HeLa). The toxicities of the AAE cations greatly increased with inclusion of long alkyl chains, sulfur, and aromatic rings in the side groups of the cations. Ethyl esters of alanine, aspartic acid, and proline were selected as a low cytotoxic AAE. The cytotoxicities of the Sal-ILs drastically increased compared with the AAEs on incorporation of Sal into the cations, and were comparable to that of free Sal. Interestingly, the water miscibilities of the Sal-ILs were higher than that of free Sal, and the Sal-ILs were miscible with water at any ratio. A skin permeation study showed that the Sal-ILs penetrated through skin faster than the Sal sodium salt. These results suggest that AAEs could be used in biomedical applications to eliminate the use of traditional toxic solvents for transdermal delivery of poorly water-soluble drugs. Copyright © 2018 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferrell, Jack R; Ware, Anne E

Two catalytic fast pyrolysis (CFP) oils (bottom/heavy fraction) were analyzed in various solvents that are used in common analytical methods (nuclear magnetic resonance - NMR, gas chromatography - GC, gel permeation chromatography - GPC, thermogravimetric analysis - TGA) for oil characterization and speciation. A more accurate analysis of the CFP oils can be obtained by identification and exploitation of solvent miscibility characteristics. Acetone and tetrahydrofuran can be used to completely solubilize CFP oils for analysis by GC and tetrahydrofuran can be used for traditional organic GPC analysis of the oils. DMSO-d6 can be used to solubilize CFP oils for analysismore » by 13C NMR. The fractionation of oils into solvents that did not completely solubilize the whole oils showed that miscibility can be related to the oil properties. This allows for solvent selection based on physico-chemical properties of the oils. However, based on semi-quantitative comparisons of the GC chromatograms, the organic solvent fractionation schemes did not speciate the oils based on specific analyte type. On the other hand, chlorinated solvents did fractionate the oils based on analyte size to a certain degree. Unfortunately, like raw pyrolysis oil, the matrix of the CFP oils is complicated and is not amenable to simple liquid-liquid extraction (LLE) or solvent fractionation to separate the oils based on the chemical and/or physical properties of individual components. For reliable analyses, for each analytical method used, it is critical that the bio-oil sample is both completely soluble and also not likely to react with the chosen solvent. The adoption of the standardized solvent selection protocols presented here will allow for greater reproducibility of analysis across different users and facilities.« less
Large-volume injection of sample diluents not miscible with the mobile phase as an alternative approach in sample preparation for bioanalysis: an application for fenspiride bioequivalence.

PubMed

Medvedovici, Andrei; Udrescu, Stefan; Albu, Florin; Tache, Florentin; David, Victor

2011-09-01

Liquid-liquid extraction of target compounds from biological matrices followed by the injection of a large volume from the organic layer into the chromatographic column operated under reversed-phase (RP) conditions would successfully combine the selectivity and the straightforward character of the procedure in order to enhance sensitivity, compared with the usual approach of involving solvent evaporation and residue re-dissolution. Large-volume injection of samples in diluents that are not miscible with the mobile phase was recently introduced in chromatographic practice. The risk of random errors produced during the manipulation of samples is also substantially reduced. A bioanalytical method designed for the bioequivalence of fenspiride containing pharmaceutical formulations was based on a sample preparation procedure involving extraction of the target analyte and the internal standard (trimetazidine) from alkalinized plasma samples in 1-octanol. A volume of 75 µl from the octanol layer was directly injected on a Zorbax SB C18 Rapid Resolution, 50 mm length × 4.6 mm internal diameter × 1.8 µm particle size column, with the RP separation being carried out under gradient elution conditions. Detection was made through positive ESI and MS/MS. Aspects related to method development and validation are discussed. The bioanalytical method was successfully applied to assess bioequivalence of a modified release pharmaceutical formulation containing 80 mg fenspiride hydrochloride during two different studies carried out as single-dose administration under fasting and fed conditions (four arms), and multiple doses administration, respectively. The quality attributes assigned to the bioanalytical method, as resulting from its application to the bioequivalence studies, are highlighted and fully demonstrate that sample preparation based on large-volume injection of immiscible diluents has an increased potential for application in bioanalysis.
Optimising Drug Solubilisation in Amorphous Polymer Dispersions: Rational Selection of Hot-melt Extrusion Processing Parameters.

PubMed

Li, Shu; Tian, Yiwei; Jones, David S; Andrews, Gavin P

2016-02-01

The aim of this article was to construct a T-ϕ phase diagram for a model drug (FD) and amorphous polymer (Eudragit® EPO) and to use this information to understand the impact of how temperature-composition coordinates influenced the final properties of the extrudate. Defining process boundaries and understanding drug solubility in polymeric carriers is of utmost importance and will help in the successful manufacture of new delivery platforms for BCS class II drugs. Physically mixed felodipine (FD)-Eudragit(®) EPO (EPO) binary mixtures with pre-determined weight fractions were analysed using DSC to measure the endset of melting and glass transition temperature. Extrudates of 10 wt% FD-EPO were processed using temperatures (110°C, 126°C, 140°C and 150°C) selected from the temperature-composition (T-ϕ) phase diagrams and processing screw speed of 20, 100 and 200rpm. Extrudates were characterised using powder X-ray diffraction (PXRD), optical, polarised light and Raman microscopy. To ensure formation of a binary amorphous drug dispersion (ADD) at a specific composition, HME processing temperatures should at least be equal to, or exceed, the corresponding temperature value on the liquid-solid curve in a F-H T-ϕ phase diagram. If extruded between the spinodal and liquid-solid curve, the lack of thermodynamic forces to attain complete drug amorphisation may be compensated for through the use of an increased screw speed. Constructing F-H T-ϕ phase diagrams are valuable not only in the understanding drug-polymer miscibility behaviour but also in rationalising the selection of important processing parameters for HME to ensure miscibility of drug and polymer.
Quantification of amino acids and peptides in an ionic liquid based aqueous two-phase system by LC-MS analysis.

PubMed

Oppermann, Sebastian; Oppermann, Christina; Böhm, Miriam; Kühl, Toni; Imhof, Diana; Kragl, Udo

2018-04-25

Aqueous two-phase systems (ATPS) occur by the mixture of two polymers or a polymer and an inorganic salt in water. It was shown that not only polymers but also ionic liquids in combination with inorganic cosmotrophic salts are able to build ATPS. Suitable for the formation of ionic liquid-based ATPS systems are hydrophilic water miscible ionic liquids. To understand the driving force for amino acid and peptide distribution in IL-ATPS at different pH values, the ionic liquid Ammoeng 110™ and K 2 HPO 4 have been chosen as a test system. To quantify the concentration of amino acids and peptides in the different phases, liquid chromatography and mass spectrometry (LC-MS) technologies were used. Therefore the peptides and amino acids have been processed with EZ:faast™-Kit from Phenomenex for an easy and reliable quantification method even in complex sample matrices. Partitioning is a surface-dependent phenomenon, investigations were focused on surface-related amino acid respectively peptide properties such as charge and hydrophobicity. Only a very low dependence between the amino acids or peptides hydrophobicity and the partition coefficient was found. Nevertheless, the presented results show that electrostatic respectively ionic interactions between the ionic liquid and the amino acids or peptides have a strong impact on their partitioning behavior.
Influence of miscibility phenomenon on crystalline polymorph transition in poly(vinylidene fluoride)/acrylic rubber/clay nanocomposite hybrid.

PubMed

Abolhasani, Mohammad Mahdi; Naebe, Minoo; Jalali-Arani, Azam; Guo, Qipeng

2014-01-01

In this paper, intercalation of nanoclay in the miscible polymer blend of poly(vinylidene fluoride) (PVDF) and acrylic rubber(ACM) was studied. X-ray diffraction was used to investigate the formation of nanoscale polymer blend/clay hybrid. Infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF/Clay nanocomposite while α crystalline form was found to be dominant in PVDF/ACM/Clay miscible hybrids. Flory-Huggins interaction parameter (B) was used to further explain the miscibility phenomenon observed. The B parameter was determined by combining the melting point depression and the binary interaction model. The estimated B values for the ternary PVDF/ACM/Clay and PVDF/ACM pairs were all negative, showing both proper intercalation of the polymer melt into the nanoclay galleries and the good miscibility of PVDF and ACM blend. The B value for the PVDF/ACM blend was almost the same as that measured for the PVDF/ACM/Clay hybrid, suggesting that PVDF chains in nanocomposite hybrids interact with ACM chains and that nanoclay in hybrid systems is wrapped by ACM molecules.
Miscibility, Crystallization, and Rheological Behavior of Solution Casting Poly(3-hydroxybutyrate)/poly(ethylene succinate) Blends Probed by Differential Scanning Calorimetry, Rheology, and Optical Microscope Techniques

NASA Astrophysics Data System (ADS)

Sun, Wei-hua; Qiao, Xiao-ping; Cao, Qi-kun; Liu, Jie-ping

2010-02-01

The miscibility and crystallization of solution casting biodegradable poly(3-hydroxybutyrate)/poly(ethylene succinate) (PHB/PES) blends was investigated by differential scanning calorimetry, rheology, and optical microscopy. The blends showed two glass transition temperatures and a depression of melting temperature of PHB with compositions in phase diagram, which indicated that the blend was partially miscible. The morphology observation supported this result. It was found that the PHB and PES can crystallize simultaneously or upon stepwise depending on the crystallization temperatures and compositions. The spherulite growth rate of PHB increased with increasing of PES content. The influence of compositions on the spherulitic growth rate for the partially miscible polymer blends was discussed.
1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide as a co-solvent in Li-ion batteries

NASA Astrophysics Data System (ADS)

Kim, Ketack; Cho, Young-Hyun; Shin, Heon-Cheol

2013-03-01

1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide (EMP-TFSI) is an ionic liquid with a melting temperature of 85 °C. Although it is a solid salt, it shows good miscibility with carbonate solvents, which allows EMP-TFSI to be used as a co-solvent in these systems. Ethylene carbonate is another solid co-solvent used in Li-ion batteries. Due to its smaller cationic size, EMP-TFSI provides better conductivity as a co-solvent than 1-methyl-1-propyl piperidinium bis(trifluoromethanesulfonyl)imide (MPP-TFSI), which is the smallest room-temperature piperidinium liquid salt known. In cells with 50 wt% IL and 50 wt% carbonate electrolyte, an EMP-TFSI mixed electrolyte performs better than an MPP-TFSI mixed electrolyte. Additionally, the discharge capacity values obtained from rate capability tests carried out with mixed EMP-TFSI are as good as those conducted with a pure carbonate electrolyte.
Gold Raspberry-Like Colloidosomes Prepared at the Water-Nitromethane Interface.

PubMed

Smirnov, Evgeny; Peljo, Pekka; Girault, Hubert H

2018-02-27

In this study, we propose a simple shake-flask method to produce micron-size colloidosomes from a liquid-liquid interface functionalized with a gold nanoparticle (AuNP) film. A step-by-step extraction process of an organic phase partially miscible with water led to the formation of raspberry-like structures covered and protected by a gold nanofilm. The distinctive feature of the prepared colloidosomes is a very thin shell consisting of small AuNPs of 12 or 38 nm in diameter instead of several hundred nanometers reported previously. The interesting and remarkable property of the proposed approach is their reversibility: the colloidosomes may be easily transformed back to a nanofilm state simply by adding pure organic solvent. The obtained colloidosomes have a broadband absorbance spectrum, which makes them of great interest in applications such as photothermal therapy, surface-enhanced Raman spectroscopy studies, and microreactor vesicles for interfacial electrocatalysis.
Liquid-state nuclear spin comagnetometers.

PubMed

Ledbetter, M P; Pustelny, S; Budker, D; Romalis, M V; Blanchard, J W; Pines, A

2012-06-15

We discuss nuclear spin comagnetometers based on ultralow-field nuclear magnetic resonance in mixtures of miscible solvents, each rich in a different nuclear spin. In one version thereof, Larmor precession of protons and 19F nuclei in a mixture of thermally polarized pentane and hexafluorobenzene is monitored via a sensitive alkali-vapor magnetometer. We realize transverse relaxation times in excess of 20 s and suppression of magnetic field fluctuations by a factor of 3400. We estimate it should be possible to achieve single-shot sensitivity of about 5×10(-9) Hz, or about 5×10(-11) Hz in ≈1 day of integration. In a second version, spin precession of protons and 129Xe nuclei in a mixture of pentane and hyperpolarized liquid xenon is monitored using superconducting quantum interference devices. Application to spin-gravity experiments, electric dipole moment experiments, and sensitive gyroscopes is discussed.
Evidence of Superstoichiometric H/d Lenr Active Sites and High-Temperature Superconductivity in a Hydrogen-Cycled Pd/PdO

NASA Astrophysics Data System (ADS)

Lipson, A. G.; Castano, C. H.; Miley, G. H.; Lyakhov, B. F.; Tsivadze, A. Yu.; Mitin, A. V.

Electron transport and magnetic properties have been studied in a 12.5 μm thick Pd foil with a thermally grown oxide and a low-residual concentration of hydrogen. This foil was deformed by cycling across the Pd hydride miscibility gap and the residual hydrogen was trapped at dislocation cores. Anomalies of both resistance and magnetic susceptibility have been observed below 70 K, indicating the appearance of excess conductivity and a diamagnetic response that we interpret in terms of filamentary superconductivity. These anomalies are attributed to a condensed hydrogen-rich phase at dislocation cores. The role of deuterium rich dislocation cores as LENR active sites is discussed.
Laboratory Layered Latte

NASA Astrophysics Data System (ADS)

Xue, Nan; Khodaparast, Sepideh; Zhu, Lailai; Nunes, Janine; Kim, Hyoungsoo; Stone, Howard

2017-11-01

Layered composite fluids are sometimes observed in confined systems of rather chaotic initial states, for example, layered lattes formed by pouring espresso into a glass of warm milk. In such configurations, pouring forces a lower density liquid (espresso) into a higher density ambient, which is similar to the fountain effects that characterize a wide range of flows driven by injecting a fluid into a second miscible phase. Although the initial state of the mixture is complex and chaotic, there are conditions where the mixture cools at room temperature and exhibits an organized layered pattern. Here we report controlled experiments injecting a fluid into a miscible phase and show that, above a critical injection velocity, layering naturally emerges over the time scale of minutes. We perform experimental and numerical analyses of the time-dependent flows to observe and understand the convective circulation in the layers. We identify critical conditions to produce the layering and relate the results quantitatively to the critical Rayleigh number in double-diffusive convection, which indicates the competition between the horizontal thermal gradient and the vertical density gradient generated by the fluid injection. Based on this understanding, we show how to employ this single-step process to produce layered structures in soft materials, where the local elastic properties as well as the local material concentration vary step-wise along the length of the material.
Electro-driven extraction of inorganic anions from water samples and water miscible organic solvents and analysis by ion chromatography.

PubMed

Nojavan, Saeed; Bidarmanesh, Tina; Memarzadeh, Farkhondeh; Chalavi, Soheila

2014-09-01

A simple electromembrane extraction (EME) procedure combined with ion chromatography (IC) was developed to quantify inorganic anions in different pure water samples and water miscible organic solvents. The parameters affecting extraction performance, such as supported liquid membrane (SLM) solvent, extraction time, pH of donor and acceptor solutions, and extraction voltage were optimized. The optimized EME conditions were as follows: 1-heptanol was used as the SLM solvent, the extraction time was 10 min, pHs of the acceptor and donor solutions were 10 and 7, respectively, and the extraction voltage was 15 V. The mobile phase used for IC was a combination of 1.8 mM sodium carbonate and 1.7 mM sodium bicarbonate. Under these optimized conditions, all anions had enrichment factors ranging from 67 to 117 with RSDs between 7.3 and 13.5% (n = 5). Good linearity values ranging from 2 to 1200 ng/mL with coefficients of determination (R(2) ) between 0.987 and 0.999 were obtained. The LODs of the EME-IC method ranged from 0.6 to 7.5 ng/mL. The developed method was applied to different samples to evaluate the feasibility of the method for real applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

Raju, Muralikrishna; Banuti, Daniel T; Ma, Peter C; Ihme, Matthias

2017-06-08

Recent experiments on pure fluids have identified distinct liquid-like and gas-like regimes even under supercritical conditions. The supercritical liquid-gas transition is marked by maxima in response functions that define a line emanating from the critical point, referred to as Widom line. However, the structure of analogous state transitions in mixtures of supercritical fluids has not been determined, and it is not clear whether a Widom line can be identified for binary mixtures. Here, we present first evidence for the existence of multiple Widom lines in binary mixtures from molecular dynamics simulations. By considering mixtures of noble gases, we show that, depending on the phase behavior, mixtures transition from a liquid-like to a gas-like regime via distinctly different pathways, leading to phase relationships of surprising complexity and variety. Specifically, we show that miscible binary mixtures have behavior analogous to a pure fluid and the supercritical state space is characterized by a single liquid-gas transition. In contrast, immiscible binary mixture undergo a phase separation in which the clusters transition separately at different temperatures, resulting in multiple distinct Widom lines. The presence of this unique transition behavior emphasizes the complexity of the supercritical state to be expected in high-order mixtures of practical relevance.

Nonlinear Dynamics of a Diffusing Interface

NASA Technical Reports Server (NTRS)

Duval, Walter M. B.

2001-01-01

Excitation of two miscible-viscous liquids inside a bounded enclosure in a microgravity environment has shown the evolution of quasi-stationary waves of various modes for a range of parameters. We examine computationally the nonlinear dynamics of the system as the interface breakup and bifurcates to resonance structures typified by the Rayleigh-Taylor instability mechanism. Results show that when the mean steady field is much smaller than the amplitude of the sinusoidal excitation, the system behaves linearly, and growth of quasi-stationary waves occurs through the Kelvin-Helmholtz instability mechanism. However, as the amplitude of excitation increases, nonlinearity occurs through subharmonic bifurcation prior to broadband chaos.
Effect of the universal acid-base indicator on the formation of the concentration-dependent diffusion instability

NASA Astrophysics Data System (ADS)

Mosheva, E. A.; Shmyrov, A. V.

2017-06-01

The effect of the universal acid-base indicator on the pattern formation and mass transfer in a two-layer system composed of two reactive miscible liquids in a vertical Hele-Shaw cell is studied experimentally. The reaction we study is a neutralization one. It turns out that the presence of the indicator leads to a change in the spatio-temporal characteristics of the system and even in the mass transfer mechanism near the reaction front—from diffusive to convective. The conditions, where the universal indicator does not affect the reaction and can be used as a visualizing mean, are reported.
Vapour-mediated sensing and motility in two-component droplets

NASA Astrophysics Data System (ADS)

Cira, N. J.; Benusiglio, A.; Prakash, M.

2015-03-01

Controlling the wetting behaviour of liquids on surfaces is important for a variety of industrial applications such as water-repellent coatings and lubrication. Liquid behaviour on a surface can range from complete spreading, as in the `tears of wine' effect, to minimal wetting as observed on a superhydrophobic lotus leaf. Controlling droplet movement is important in microfluidic liquid handling, on self-cleaning surfaces and in heat transfer. Droplet motion can be achieved by gradients of surface energy. However, existing techniques require either a large gradient or a carefully prepared surface to overcome the effects of contact line pinning, which usually limit droplet motion. Here we show that two-component droplets of well-chosen miscible liquids such as propylene glycol and water deposited on clean glass are not subject to pinning and cause the motion of neighbouring droplets over a distance. Unlike the canonical predictions for these liquids on a high-energy surface, these droplets do not spread completely but exhibit an apparent contact angle. We demonstrate experimentally and analytically that these droplets are stabilized by evaporation-induced surface tension gradients and that they move in response to the vapour emitted by neighbouring droplets. Our fundamental understanding of this robust system enabled us to construct a wide variety of autonomous fluidic machines out of everyday materials.
Interactions of ionic liquids and acetone: thermodynamic properties, quantum-chemical calculations, and NMR analysis.

PubMed

Ruiz, Elia; Ferro, Victor R; Palomar, Jose; Ortega, Juan; Rodriguez, Juan Jose

2013-06-20

The interactions between ionic liquids (ILs) and acetone have been studied to obtain a further understanding of the behavior of their mixtures, which generally give place to an exothermic process, mutual miscibility, and negative deviation of Raoult's law. COSMO-RS was used as a suitable computational method to systematically analyze the excess enthalpy of IL-acetone systems (>300), in terms of the intermolecular interactions contributing to the mixture behavior. Spectroscopic and COSMO-RS results indicated that acetone, as a polar compound with strong hydrogen bond acceptor character, in most cases, establishes favorable hydrogen bonding with ILs. This interaction is strengthened by the presence of an acidic cation and an anion with dispersed charge and non-HB acceptor character in the IL. COSMO-RS predictions indicated that gas-liquid and vapor-liquid equilibrium data for IL-acetone systems can be finely tuned by the IL selection, that is, acting on the intermolecular interactions between the molecular and ionic species in the liquid phase. NMR measurements for IL-acetone mixtures at different concentrations were also carried out. Quantum-chemical calculations by using molecular clusters of acetone and IL species were finally performed. These results provided additional evidence of the main role played by hydrogen bonding in the behavior of systems containing ILs and HB acceptor compounds, such as acetone.
Simulation studies of ionic liquids: Orientational correlations and static dielectric properties

NASA Astrophysics Data System (ADS)

Schröder, C.; Rudas, T.; Steinhauser, O.

2006-12-01

The ionic liquids BMIM+I-, BMIM+BF4-, and BMIM+PF6- were simulated by means of the molecular dynamics method over a time period of more than 100ns. Besides the common structural analysis, e.g., radial distribution functions and three dimensional occupancy plots, a more sophisticated orientational analysis was performed. The angular correlation functions g00110(r) and g00101(r) are the first distance dependent coefficients of the pairwise orientational distribution function g(rij,Ω1,Ω2,Ω12). These functions help to interpret the three dimensional plot and reveal interesting insights into the local structure of the analyzed ionic liquids. Furthermore, the collective network of ionic liquids can be characterized by the Kirkwood factor Gκ(r ) [J. Chem. Phys. 7, 911 (1939)]. The short-range behavior (r<10Å) of this factor may be suitable to predict the water miscibility of the ionic liquid. The long-range limit of Gk∞ is below 1 which demonstrates the strongly coupled nature of the ionic liquid networks. In addition, this factor relates the orientational structure and the dielectric properties of the ionic liquids. The static dielectric constant ɛ(ω =0) for the simulated system is 8.9-9.5. Since in ionic liquids the very same molecule contributes to the total dipole moment as well as carries a net charge, a small, but significant contribution of the cross term between the total dipole moment and the electric current to ɛ(ω =0) is observed.
Role of Thickness Confinement on Relaxations of the Fast Component in a Miscible A/B Blend

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

Green, Peter; Sharma, Ravi P.; Dong, Ban Xuan

Spatial compositional heterogeneity strongly influences the dynamics of the A and B components of bulk miscible blends. Its effects are especially apparent in mixtures, such as poly(vinyl methyl ether) (PVME)/polystyrene (PS), where there exist significant disparities between the component glass transition temperatures (Tgs) and relaxation times. The relaxation processes characterized by distinct temperature dependencies and relaxation rates manifest different local compositional environments for temperatures above and below the glass transition temperature of the miscible blend. This same behavior is shown to exist in miscible PS/PVME films as thin as 100 nm. Moreover, in thin films, the characteristic segmental relaxation timesmore » t of the PVME component of miscible PVME/PS blends confined between aluminum (Al) substrates decrease with increasing molecular weight M of the PS component. These relaxation rates are film thickness dependent, in films up to a few hundred nanometers in thickness. This is in remarkable contrast to homopolymer films, where thickness confinement effects are apparent only on length scales on the order of nanometers. These surprisingly large length scales and M dependence are associated with the preferential interfacial enrichment - wetting layer formation - of the PVME component at the external Al interfaces, which alters the local spatial blend composition within the interior of the film. The implications are that the dynamics of miscible thin film blends are dictated in part by component Tg differences, disparities in component relaxation rates, component-substrate interactions, and chain lengths (entropy of mixing).« less
A thermoplastic/thermoset blend exhibiting thermal mending and reversible adhesion.

PubMed

Luo, Xiaofan; Ou, Runqing; Eberly, Daniel E; Singhal, Amit; Viratyaporn, Wantinee; Mather, Patrick T

2009-03-01

In this paper, we report on the development of a new and broadly applicable strategy to produce thermally mendable polymeric materials, demonstrated with an epoxy/poly(-caprolactone) (PCL) phase-separated blend. The initially miscible blend composed of 15.5 wt % PCL undergoes polymerization-induced phase separation during cross-linking of the epoxy, yielding a "bricks and mortar" morphology wherein the epoxy phase exists as interconnected spheres (bricks) interpenetrated with a percolating PCL matrix (mortar). The fully cured material is stiff, strong, and durable. A heating-induced "bleeding" behavior was witnessed in the form of spontaneous wetting of all free surfaces by the molten PCL phase, and this bleeding is capable of repairing damage by crack-wicking and subsequent recrystallization with only minor concomitant softening during that process. The observed bleeding is attributed to volumetric thermal expansion of PCL above its melting point in excess of epoxy brick expansion, which we term differential expansive bleeding (DEB). In controlled thermal-mending experiments, heating of a cracked specimen led to PCL extrusion from the bulk to yield a liquid layer bridging the crack gap. Upon cooling, a "scar" composed of PCL crystals formed at the site of the crack, restoring a significant portion of the mechanical strength. When a moderate force was applied to assist crack closure, thermal-mending efficiencies exceeded 100%. We further observed that the DEB phenomenon enables strong and facile adhesion of the same material to itself and to a variety of materials, without any requirement for macroscopic softening or flow.
Apatite-hosted melt inclusions in Damiao massif anorthosite complex, North China

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

PubMed

Yang, Shuai; Liu, Ying

2018-08-01

Liquid crystal nematic elastomers are one kind of smart anisotropic and viscoelastic solids simultaneously combing the properties of rubber and liquid crystals, which is thermal sensitivity. In this paper, the wave dispersion in a liquid crystal nematic elastomer porous phononic crystal subjected to an external thermal stimulus is theoretically investigated. Firstly, an energy function is proposed to determine thermo-induced deformation in NE periodic structures. Based on this function, thermo-induced band variation in liquid crystal nematic elastomer porous phononic crystals is investigated in detail. The results show that when liquid crystal elastomer changes from nematic state to isotropic state due to the variation of the temperature, the absolute band gaps at different bands are opened or closed. There exists a threshold temperature above which the absolute band gaps are opened or closed. Larger porosity benefits the opening of the absolute band gaps. The deviation of director from the structural symmetry axis is advantageous for the absolute band gap opening in nematic state whist constrains the absolute band gap opening in isotropic state. The combination effect of temperature and director orientation provides an added degree of freedom in the intelligent tuning of the absolute band gaps in phononic crystals. Copyright © 2018 Elsevier B.V. All rights reserved.
Liquid-level detector

DOEpatents

Not Available

1981-01-29

Aliquid level sensor is described which has a pair of upright conductors spaced by an insulator defining a first high resistance path between the conductors. An electrically conductive path is interposed between the upright conductors at a discrete location at which liquid level is to be measured. It includes a liquid accessible gap of a dimension such that the electrical resistance across the conductor when the gap is filled with the liquid is detectably less than when the gap is emptied. The conductor might also be physically altered by temperature changes to serve also as an indicator of elevated temperature.
Neutrally Charged Gas/Liquid Interface by a Catanionic Langmuir Monolayer

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

Vaknin, David; Bu, Wei

Surface-sensitive synchrotron X-ray scattering and spectroscopic experiments were performed to explore the characteristics of Langmuir monolayers of oppositely charged mixed amphiphiles. A premixed (molar 1:1 stearic acid/stearylamine) solution was spread as a monolayer at the gas/liquid interface on pure water and on mono- and divalent salt solutions, revealing that the negatively charged carboxyl groups and positively charged amine groups are miscible into one another and tend to bond together to form a nearly neutral surface. Similar control experiments on pure stearic acid (SA) and stearylamine (ST) were also conducted for comparison. Due to the strong bonding, hexagonal structures in smallmore » domains with acyl-chains normal to the liquid surface are formed at zero surface pressures, that is, at molecular areas much larger than those of the densely packed acyl chains. In-plane X-ray diffraction indicates that the catanionic surface is highly ordered and modifies the structure of the water surface and thus can serve as a model system for interactions of an amino acid template with solutes.« less
Influence of Miscibility Phenomenon on Crystalline Polymorph Transition in Poly(Vinylidene Fluoride)/Acrylic Rubber/Clay Nanocomposite Hybrid

PubMed Central

Abolhasani, Mohammad Mahdi; Naebe, Minoo; Jalali-Arani, Azam; Guo, Qipeng

2014-01-01

In this paper, intercalation of nanoclay in the miscible polymer blend of poly(vinylidene fluoride) (PVDF) and acrylic rubber(ACM) was studied. X-ray diffraction was used to investigate the formation of nanoscale polymer blend/clay hybrid. Infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF/Clay nanocomposite while α crystalline form was found to be dominant in PVDF/ACM/Clay miscible hybrids. Flory-Huggins interaction parameter (B) was used to further explain the miscibility phenomenon observed. The B parameter was determined by combining the melting point depression and the binary interaction model. The estimated B values for the ternary PVDF/ACM/Clay and PVDF/ACM pairs were all negative, showing both proper intercalation of the polymer melt into the nanoclay galleries and the good miscibility of PVDF and ACM blend. The B value for the PVDF/ACM blend was almost the same as that measured for the PVDF/ACM/Clay hybrid, suggesting that PVDF chains in nanocomposite hybrids interact with ACM chains and that nanoclay in hybrid systems is wrapped by ACM molecules. PMID:24551141
Lagrangian formulation and symmetrical description of liquid dynamics.

PubMed

Trachenko, K

2017-12-01

Theoretical description of liquids has been primarily based on the hydrodynamic approach and its generalization to the solid-like regime. We show that the same liquid properties can be derived starting from solid-like equations and generalizing them to account for the hydrodynamic flow. Both approaches predict propagating shear waves with the notable gap in k-space. This gives an important symmetry of liquids regarding their description. We subsequently construct a two-field Lagrangian of liquid dynamics where the dissipative hydrodynamic and solid-like terms are treated on equal footing. The Lagrangian predicts two gapped waves propagating in opposite space-time directions. The dissipative and mass terms compete by promoting gaps in k-space and energy, respectively. When bare mass is close to the field hopping frequency, both gaps close and the dissipative term annihilates the bare mass.
Lagrangian formulation and symmetrical description of liquid dynamics

NASA Astrophysics Data System (ADS)

Trachenko, K.

2017-12-01

Theoretical description of liquids has been primarily based on the hydrodynamic approach and its generalization to the solid-like regime. We show that the same liquid properties can be derived starting from solid-like equations and generalizing them to account for the hydrodynamic flow. Both approaches predict propagating shear waves with the notable gap in k -space. This gives an important symmetry of liquids regarding their description. We subsequently construct a two-field Lagrangian of liquid dynamics where the dissipative hydrodynamic and solid-like terms are treated on equal footing. The Lagrangian predicts two gapped waves propagating in opposite space-time directions. The dissipative and mass terms compete by promoting gaps in k -space and energy, respectively. When bare mass is close to the field hopping frequency, both gaps close and the dissipative term annihilates the bare mass.
DEVELOPMENT AND OPTIMIZATION OF GAS-ASSISTED GRAVITY DRAINAGE (GAGD) PROCESS FOR IMPROVED LIGHT OIL RECOVERY

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

Dandina N. Rao

This is the first Annual Technical Progress Report being submitted to the U. S. Department of Energy on the work performed under the Cooperative Agreement DE-FC26-02NT15323. This report follows two other progress reports submitted to U.S. DOE during the first year of the project: The first in April 2003 for the project period from October 1, 2002 to March 31, 2003, and the second in July 2003 for the period April 1, 2003 to June 30, 2003. Although the present Annual Report covers the first year of the project from October 1, 2002 to September 30, 2003, its contents reflectmore » mainly the work performed in the last quarter (July-September, 2003) since the work performed during the first three quarters has been reported in detail in the two earlier reports. The main objective of the project is to develop a new gas-injection enhanced oil recovery process to recover the oil trapped in reservoirs subsequent to primary and/or secondary recovery operations. The project is divided into three main tasks. Task 1 involves the design and development of a scaled physical model. Task 2 consists of further development of the vanishing interfacial tension (VIT) technique for miscibility determination. Task 3 involves the determination of multiphase displacement characteristics in reservoir rocks. Each technical progress report, including this one, reports on the progress made in each of these tasks during the reporting period. Section I covers the scaled physical model study. A survey of literature in related areas has been conducted. Test apparatus has been under construction throughout the reporting period. A bead-pack visual model, liquid injection system, and an image analysis system have been completed and used for preliminary experiments. Experimental runs with decane and paraffin oil have been conducted in the bead pack model. The results indicate the need for modifications in the apparatus, which are currently underway. A bundle of capillary tube model has been considered and formulated aiming to reveal the interplay of the viscous, interfacial and gravity forces and to predict the gravity drainage performance. Scaling criteria for the scaled physical model design have been proposed based on an inspectional analysis. In Section II, equation of state (EOS) calculations were extended to study the effect of different tuning parameters on MMP for two reservoir crude oils of Rainbow Keg River and Terra Nova. This study indicates that tuning of EOS may not always be advisable for miscibility determination. Comparison of IFT measurements for benzene in water, ethanol mixtures with the solubility data from the literature showed that a strong mutual relationship between these two thermodynamic properties exists. These preliminary experiments indicate applicability of the new vanishing interfacial tension (VIT) technique to determine miscibility of ternary liquid systems. The VIT experimental apparatus is under construction with considerations of expanded capacity of using equilibrated fluids and a new provision for low IFT measurement in gas-oil systems. In Section III, recommendations in the previous progress reports have been investigated in this reporting period. WAG coreflood experiments suggest the use of ''Hybrid''-WAG type floods for improved CO{sub 2} utilization factors and recoveries. The effect of saturating the injection water with CO{sub 2} for core-floods has been investigated further in this quarter. Miscible WAG floods using CO{sub 2} saturated brine showed higher recoveries (89.2% ROIP) compared to miscible WAG floods using normal brine (72.5%). Higher tertiary recovery factors (TRF) were also observed for WAG floods using CO{sub 2} saturated brine due to improved mobility ratio and availability of CO{sub 2}. Continued experimentation for evaluation of both, ''Hybrid''-WAG and gravity stable type displacements, in Berea sandstone cores using synthetic as well as real reservoir fluids are planned for the next quarter.« less
Emulsification kinetics during quasi-miscible flow in dead-end pores

NASA Astrophysics Data System (ADS)

Broens, M.; Unsal, E.

2018-03-01

Microemulsions have found applications as carriers for the transport of solutes through various porous media. They are commonly pre-prepared in bulk form, and then injected into the medium. The preparation is done by actively mixing the surfactant, water and oil, and then allowing the mixture to stagnate until equilibrium is reached. The resulting microemulsion characteristics of the surfactant/oil/water system are studied at equilibrium conditions, and perfect mixing is assumed. But in applications like subsurface remediation and enhanced oil recovery, microemulsion formation may occur in the pore space. Surfactant solutions are injected into the ground to solubilize and/or mobilize the non-aqueous phase liquids (NAPLs) by in-situ emulsification. Flow dynamics and emulsification kinetics are coupled, which also contributes to in-situ mixing. In this study, we investigated the nature of such coupling for a quasi-miscible fluid system in a conductive channel with dead-end extensions. A microfluidic setup was used, where an aqueous solution of an anionic, internal olefin sulfonate 20-24 (IOS) surfactant was injected into n-decane saturated glass micromodel. The oil phase was coloured using a solvatochromatic dye allowing for direct visualization of the aqueous and oil phases as well as their microemulsions under fluorescent light. Presence of both conductive and stagnant dead-end channels in a single pore system made it possible to isolate different transport mechanisms from each other but also allowed to study the transitions from one to the other. In the conductive channel, the surfactant was carried with flow, and emulsification was controlled by the localized flow dynamics. In the stagnant zones, the driving force of the mass transfer was driven by the chemical concentration gradient. Some of the equilibrium phase behaviour characteristics of the surfactant/oil/water system were recognisable during the quasi-miscible displacement. However, the equilibrium tests alone were not sufficient to predict the emulsification process under dynamic conditions.
Miscibility of ethyl cellulose/copolyamide6/66/1010 blends by viscometry and refractive index method

NASA Astrophysics Data System (ADS)

Zhang, Xiuzhen; Shen, Yuhua; Xie, Anjian; Gao, Sulian; Xing, Zhiying

2011-04-01

The miscibility of ethyl cellulose (EC)/copolyamide6/66/1010 (PA-130) in formic acid is studied by viscometry and refractive index techniques at 25°C. Using viscosity data, the criteria Δ b, Δ b', Δ[η]m, interaction parameter μ, β and thermodynamic parameter α are calculated. These investigations indicate that blend of EC/PA-130 is miscible when the ethyl cellulose content is more than 50 wt % in the blend. Further the result was also confirmed by refractive index measurements.
Subsolidus and melting phase relations in the system CaCO3-MgCO3-FeCO3 at 35 kbar: from experiments to predictions based on a thermodynamic model

NASA Astrophysics Data System (ADS)

Franzolin, E.; Schmidt, M. W.; Poli, S.

2009-12-01

At convergent margins volatile components, most notably CO2 and H2O, stored in oceanic sediments and MORB are recycled into the mantle. Mafic protoliths become enriched in CO2 and H2O, stored in carbonates and hydrous phases, by hydrothermal alteration. As carbonates are more refractory than hydrous phases, CO2 is more likely to survive in the oceanic lithosphere beyond sub-arc depths [1,2]. Despite the main role of carbonates on cycling crustal and atmospheric CO2 into the mantle, experimental data within the system CaCO3-MgCO3-FeCO3 are scarce. To bridge this gap, piston-cylinder experiments have been performed at 35 kbar, 900-1100 °C to determine subsolidus relations, and up to 1300 °C to constrain melting relations. Pure synthetic calcite, natural magnesite and synthetic siderite have been mixed in different proportions in double Pt-C capsules, to avoid major siderite oxidation. Subsolidus experiments reveal the presence of two miscibility gaps at 900 °C: the solvus dolomite-calcite, which closes at XMgCO3 ~ 0.7, and the solvus dolomite-magnesite, which ranges to the Fe-side of the ternary. Increasing the temperature, the two miscibility gaps became narrower until complete solid solutions between CaCO3-Ca0.5Mg0.5CO3 at 1100 °C, and between CaCO3-FeCO3 at 1000 °C, are observed. The system is characterized by strong compositional asymmetry, thermodynamically described with a van Laar macroscopic formalism [3], and by R-3<=>R-3c phase transitions due to cation disordering, treated by redefining the compositional space with an independent set of end-members that describe both composition and states of ordering. The result is a solid solution model able to reproduce both the phase relations experimentally observed at 35 kbar and those experimentally determined and naturally observed at lower pressure [4-5]. Our model can be reliable extended to pressures of the breakdown of dolomite, e.g. 5-6 GPa, 600-1000 °C. Melting experiments carried out at 1250 °C along the join CaCO3-MgCO3, yield an eutectic at a slightly lower temperature at XCa ~ 0.7; the eutectic temperature decreases with the Fe content in the bulk. The 2-phase field calcite (XCa~0.75) + liquid, broadens with the increase of XFe in the system. Along the join CaMg(CO3)2-CaFe(CO3)2, melting takes place at XFe ~ 0.2, producing Ca enriched melt + Mg enriched dolomite. The new subsolidus and melting data and the ternary thermodynamic solid solution model, have been combined to predict the fate of FeO and CO2 rich systems (i.e. BIF associated with Fe-shale, high-Fe altered basalts and Fe-enriched carbonated metapelites), recycled back into the mantle during the history of the Earth. [1] Kerrick&Connolly, EPSL, 2001, 189, 19-29. [2] Poli et al., EPSL, 2009, 278, 350-360. [3] Holland&Powell, Contr. Min. Pet., 2003, 145, 492-501. [4] Goldsmith et al., Journ. of Geol., 1962, 70, 659-688. [5] Rosenberg, Am. Min., 1967, 52, 787-796.
Formation of silk fibroin nanoparticles in water-miscible organic solvent and their characterization

NASA Astrophysics Data System (ADS)

Zhang, Yu-Qing; Shen, Wei-De; Xiang, Ru-Li; Zhuge, Lan-Jian; Gao, Wei-Jian; Wang, Wen-Bao

2007-10-01

When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl2, the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35-125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the ɛ-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and α-helix form (Silk I) into anti-parallel β-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, 13C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain-chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with β-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular substructure of the degraded silk fibroin in aqueous solution. It is possible that the silk protein nanoparticles are potentially useful in biomaterials such as cosmetics, anti-UV skincare products, industrial materials and surface improving materials, especially in enzyme/drug delivery system as vehicle.
Viscous fingering with partially miscible fluids

NASA Astrophysics Data System (ADS)

Fu, Xiaojing; Cueto-Felgueroso, Luis; Juanes, Ruben

2017-10-01

Viscous fingering—the fluid-mechanical instability that takes place when a low-viscosity fluid displaces a high-viscosity fluid—has traditionally been studied under either fully miscible or fully immiscible fluid systems. Here we study the impact of partial miscibility (a common occurrence in practice) on the fingering dynamics. Through a careful design of the thermodynamic free energy of a binary mixture, we develop a phase-field model of fluid-fluid displacements in a Hele-Shaw cell for the general case in which the two fluids have limited (but nonzero) solubility into one another. We show, by means of high-resolution numerical simulations, that partial miscibility exerts a powerful control on the degree of fingering: fluid dissolution hinders fingering while fluid exsolution enhances fingering. We also show that, as a result of the interplay between compositional exchange and the hydrodynamic pattern-forming process, stronger fingering promotes the system to approach thermodynamic equilibrium more quickly.

Influence of water-miscible cutting fluid on tool wear behavior of various coated high-speed steel tools in hobbing

NASA Astrophysics Data System (ADS)

Sato, Yuta; Matsuoka, Hironori; Kubo, Akio; Ono, Hajime; Ryu, Takahiro; Qiu, Hua; Nakae, Takashi; Shuto, Shuichi; Watanabe, Suguru; Anan, Ruito

2017-04-01

This paper deals with the influence of water-miscible cutting fluid on tool life (flank wear) compared with that with dry cutting and water-insoluble cutting oil in hobbing. Experiments were conducted by simulating hobbing by fly tool cutting on a milling machine. The following results were clarified. (1) The water-miscible cutting fluid used in the test prolongs the tool life for TiN-, TiAlN-, TiSiN- and AlCrSiN-coated tools in comparison with that obtained by dry cutting and water-insoluble cutting oil. (2) It was presumed that the tool wear decreases and the tool life is improved by the lubrication effect of the synthetic lubrication additive, mineral oil and sulfuric EP additive contained in the water-miscible cutting fluid, and also by the cooling effect.
Tunable two-dimensional photonic crystals using liquid crystal infiltration

NASA Astrophysics Data System (ADS)

Leonard, S. W.; Mondia, J. P.; van Driel, H. M.; Toader, O.; John, S.; Busch, K.; Birner, A.; Gösele, U.; Lehmann, V.

2000-01-01

The photonic band gap of a two-dimensional photonic crystal is continuously tuned using the temperature dependent refractive index of a liquid crystal. Liquid crystal E7 was infiltrated into the air pores of a macroporous silicon photonic crystal with a triangular lattice pitch of 1.58 μm and a band gap wavelength range of 3.3-5.7 μm. After infiltration, the band gap for the H polarized field shifted dramatically to 4.4-6.0 μm while that of the E-polarized field collapsed. As the sample was heated to the nematic-isotropic phase transition temperature of the liquid crystal (59 °C), the short-wavelength band edge of the H gap shifted by as much as 70 nm while the long-wavelength edge was constant within experimental error. Band structure calculations incorporating the temperature dependence of the liquid crystal birefringence can account for our results and also point to an escaped-radial alignment of the liquid crystal in the nematic phase.
Mechanism of magnetic liquid flowing in the magnetic liquid seal gap of reciprocating shaft

NASA Astrophysics Data System (ADS)

Li, Decai; Chui, Haichun; Yang, Qingxin

2003-04-01

In order to solve the problems that exist in the magnetic liquid seal of reciprocating shaft, we have set up an experimental facility, which composes a camera, a microscope, a step-by-step motor, a pin roller screw, a reciprocating motion shaft, pole pieces, a permanent magnet and the magnetic liquid in the seal gap. Through the optical technology and image process of the experimental facility, we have studied the magnetic liquid flow in the seal gap when the reciprocating shaft moves with different velocities and strokes, this study especially concentrates on 1) the regular pattern of such flow; 2) the loss quantity of magnetic liquid caused by the reciprocating motion shaft; 3) the failure reasons of this magnetic liquid seal and 4) the design of a new structure for the magnetic liquid seal of reciprocating shaft. The application indicates that the new structure is very effective in some occasions.
COSOLVENCY AND SOPRTION OF HYDROPHOBIC ORGANIC CHEMICALS

EPA Science Inventory

Sorption of hydrophobic organic chemicals (HOCs) by two soils was measured from mixed solvents containing water plus completely miscible organic solvents (CMOSs) and partially miscible organic solvents (PMOSs). The utility of the log-linear cosolvency model for predicting HOC sor...
Miscibility and Thermodynamics of Mixing of Different Models of Formamide and Water in Computer Simulation.

PubMed

Kiss, Bálint; Fábián, Balázs; Idrissi, Abdenacer; Szőri, Milán; Jedlovszky, Pál

2017-07-27

The thermodynamic changes that occur upon mixing five models of formamide and three models of water, including the miscibility of these model combinations itself, is studied by performing Monte Carlo computer simulations using an appropriately chosen thermodynamic cycle and the method of thermodynamic integration. The results show that the mixing of these two components is close to the ideal mixing, as both the energy and entropy of mixing turn out to be rather close to the ideal term in the entire composition range. Concerning the energy of mixing, the OPLS/AA_mod model of formamide behaves in a qualitatively different way than the other models considered. Thus, this model results in negative, while the other ones in positive energy of mixing values in combination with all three water models considered. Experimental data supports this latter behavior. Although the Helmholtz free energy of mixing always turns out to be negative in the entire composition range, the majority of the model combinations tested either show limited miscibility, or, at least, approach the miscibility limit very closely in certain compositions. Concerning both the miscibility and the energy of mixing of these model combinations, we recommend the use of the combination of the CHARMM formamide and TIP4P water models in simulations of water-formamide mixtures.
Polymer-fullerene miscibility: a metric for screening new materials for high-performance organic solar cells.

PubMed

Treat, Neil D; Varotto, Alessandro; Takacs, Christopher J; Batara, Nicolas; Al-Hashimi, Mohammed; Heeney, Martin J; Heeger, Alan J; Wudl, Fred; Hawker, Craig J; Chabinyc, Michael L

2012-09-26

The improvement of the power conversion efficiency (PCE) of polymer bulk heterojunction (BHJ) solar cells has generally been achieved through synthetic design to control frontier molecular orbital energies and molecular ordering of the electron-donating polymer. An alternate approach to control the PCE of a BHJ is to tune the miscibility of the fullerene and a semiconducting polymer by varying the structure of the fullerene. The miscibility of a series of 1,4-fullerene adducts in the semiconducting polymer, poly(3-hexylselenophene), P3HS, was measured by dynamic secondary ion mass spectrometry using a model bilayer structure. The microstructure of the bilayer was investigated using high-angle annular dark-field scanning transmission microscopy and linked to the polymer-fullerene miscibility. Finally, P3HS:fullerene BHJ solar cells were fabricated from each fullerene derivative, enabling the correlation of the active layer microstructure to the charge collection efficiency and resulting PCE of each system. The volume fraction of polymer-rich, fullerene-rich, and polymer-fullerene mixed domains can be tuned using the miscibility leading to improvement in the charge collection efficiency and PCE in P3HS:fullerene BHJ solar cells. These results suggest a rational approach to the design of fullerenes for improved BHJ solar cells.
Miscibility comparison for three refrigerant mixtures and four component refrigerants

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

Kang, H.M.; Pate, M.B.

1999-07-01

Miscibility data were taken and compared for seven different refrigerants when mixed with the same polyol ester (POE) lubricant. Four of the seven refrigerants were single-component refrigerants while three of the refrigerants were mixtures composed of various combinations of the pure refrigerants. The purpose of this research was to investigate the difference in miscibility characteristics between refrigerant mixtures and their respective component refrigerants. The POE lubricant was a penta erythritol mixed-acid type POE which has a viscosity ISO32. The four pure refrigerants were R-32, R-125, R-134a, and R-143a and the three refrigerant mixtures were R-404A, R407C, and R-410A. The miscibilitymore » tests were performed in a test facility consisting of a series of miniature test cells submerged in a constant temperature bath. The test cells were constructed to allow for complete visibility of the refrigerant/lubricant mixtures under all test conditions. The tests were performed over a concentration range of 0 to 100% and a temperature range of {minus}40 to 194 F. The miscibility test results for refrigerant mixtures are compared to component refrigerants. In all cases, the refrigerant mixtures appear to have better miscibility than their most immiscible pure component.« less
Dancing droplets: Chemical space, substrates, and control

NASA Astrophysics Data System (ADS)

Cira, Nate; Benusiglio, Adrien; Prakash, Manu

2015-11-01

Previously we showed that droplets of propylene glycol and water display remarkable properties when placed on clean glass due to an interplay between surface tension and evaporation. (Cira, Benusiglio, Prakash: Nature, 2015). We showed that these mechanisms apply to a range of two-component mixtures of miscible liquids where one component has both higher surface tension and higher vapor pressure on a variety of high energy surfaces. We now show how this rule can be cheated using a simple trick. We go on to demonstrate applications for cleaning, and show how this system works on substrates prepared only with sunlight. We finish by demonstrating active control of droplets, allowing access to a host of new possibilities.
MISCIBILITY, SOLUBILITY, AND VISCOSITY MEASUREMENTS FOR R-236EA WITH POTENTIAL LUBRICANTS

EPA Science Inventory

The report gives results of miscibility, solubility, and viscosity measurements of refrigerant R-236ea with three potential lubricants. (NOTE: The data were needed to determine the suitability of refrigerant/lubricant combinations for use in refrigeration systems.) The lubricants...
Rotating electric machine with fluid supported parts

DOEpatents

Smith, Jr., Joseph L.; Kirtley, Jr., James L.

1981-01-01

A rotating electric machine in which the armature winding thereof and other parts are supported by a liquid to withstand the mechanical stresses applied during transient overloads and the like. In particular, a narrow gap is provided between the armature winding and the stator which supports it and this gap is filled with an externally pressurized viscous liquid. The liquid is externally pressurized sufficiently to balance the static loads on the armature winding. Transient mechanical loads which deform the armature winding alter the gap dimensions and thereby additionally pressurize the viscous liquid to oppose the armature winding deformation and more nearly uniformly to distribute the resulting mechanical stresses.
A strategy for low cost development of incremental oil in legacy reservoirs

USGS Publications Warehouse

Attanasi, E.D.

2016-01-01

The precipitous decline in oil prices during 2015 has forced operators to search for ways to develop low-cost and low-risk oil reserves. This study examines strategies to low cost development of legacy reservoirs, particularly those which have already implemented a carbon dioxide enhanced oil recovery (CO2 EOR) program. Initially the study examines the occurrence and nature of the distribution of the oil resources that are targets for miscible and near-miscible CO2 EOR programs. The analysis then examines determinants of technical recovery through the analysis of representative clastic and carbonate reservoirs. The economic analysis focusses on delineating the dominant components of investment and operational costs. The concluding sections describe options to maximize the value of assets that the operator of such a legacy reservoir may have that include incremental expansion within the same producing zone and to producing zones that are laterally or stratigraphically near main producing zones. The analysis identified the CO2 recycle plant as the dominant investment cost item and purchased CO2 and liquids management as a dominant operational cost items. Strategies to utilize recycle plants for processing CO2 from multiple producing zones and multiple reservoir units can significantly reduce costs. Industrial sources for CO2 should be investigated as a possibly less costly way of meeting EOR requirements. Implementation of tapered water alternating gas injection schemes can partially mitigate increases in fluid lifting costs.
Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

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

Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J., E-mail: saykally@berkeley.edu

While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure.more » The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.« less
Mechanism of magnetic liquid flowing in the magnetic liquid seal gap of reciprocating shaft

NASA Astrophysics Data System (ADS)

Li, Decai; Xu, Haiping; He, Xinzhi; Lan, Huiqing

2005-03-01

In order to solve the problems that exist in the magnetic liquid seal of reciprocating shaft, we have set up an experimental facility, which composes a camera, microscope, step-by-step motor, pin roller screw, reciprocating motion shaft, pole pieces, permanent magnet and the magnetic liquid in the seal gap. Through the optical technology and image process of the experimental facility, we have studied the magnetic liquid flow in the seal gap when the reciprocating shaft moves with different velocities and strokes. This study specially concentrates on: (1) the regular pattern of such flow; (2) the loss quantity of magnetic liquid caused by the reciprocating motion shaft; (3) the failure reasons of this magnetic liquid seal; and (4) the design of a new structure for the magnetic liquid seal of reciprocating shaft. The application indicates that the new structure is very effective in some occasions. The new structure was accepted as the state patent in 2001 and authenticated as the achievement in the scientific research in 2002.
MISCIBILITY, SOLUBILITY, VISCOSITY, AND DENSITY MEASUREMENTS FOR R-236FA WITH POTENTIAL LUBRICANTS

EPA Science Inventory

The report gives results of miscibility, solubility, viscosity, and density measurements for refrigerant R-236fa and two potential lubricants . (The data are needed to determine the suitability of refrigerant/lubricant combinations for use in refrigeration systems.) The tested oi...
Miscibility, solubility, viscosity, and density measurements for R-236ea with four different Exxon lubricants. Final report, March 1995-March 1997

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

Kang, H.M.; Pate, M.B.

1999-06-15

The report discusses miscibility, solubility, viscosity, and density data for the refrigerant hydrofluorocarbon (HFC)-236ea (or R-236ea) and four lubricants supplied by Exxon Corporation. The miscibility tests were performed in a test facility consisting of a series of miniature test cells submerged in a constant temperature bath, precisely controlled over a range of {minus}50 to 90 C. Critical solution temperatures obtained from the miscibility data are presented for each refrigerant/lubricant combination. Data for the R-236ea in each of the test lubricants have been collected for refrigerant concentrations of 10--90%. The raw data have been presented, and the results have been summarized.more » Solubility, viscosity, and density data were also obtained for R-236ea mixed with the same four oils for a refrigerant concentration range of 0--40 wt% refrigerant over a temperature range of 30--100 C.« less
Physico-Chemical Properties and Phase Behaviour of Pyrrolidinium-Based Ionic Liquids

PubMed Central

Domańska, Urszula

2010-01-01

A review of the relevant literature on 1-alkyl-1-methylpyrrolidinium-based ionic liquids has been presented. The phase diagrams for the binary systems of {1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [EMPYR][CF3SO3] + water, or + 1-butanol} and for the binary systems of {1-propyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [PMPYR][CF3SO3] + water, or + an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol)} have been determined at atmospheric pressure using a dynamic method. The influence of alcohol chain length was discussed for the [PMPYR][CF3SO3]. A systematic decrease in the solubility was observed with an increase of the alkyl chain length of an alcohol. (Solid + liquid) phase equilibria with complete miscibility in the liquid phase region were observed for the systems involving water and alcohols. The solubility of the ionic liquid increases as the alkyl chain length on the pyrrolidinium cation increases. The correlation of the experimental data has been carried out using the Wilson, UNIQUAC and the NRTL equations. The phase diagrams reported here have been compared to the systems published earlier with the 1-alkyl-1-methylpyrrolidinium-based ionic liquids. The influence of the cation and anion on the phase behaviour has been discussed. The basic thermal properties of pure ILs, i.e., melting temperature and the enthalpy of fusion, the solid-solid phase transition temperature and enthalpy have been measured using a differential scanning microcalorimetry technique. PMID:20480044
A method for matching the refractive index and kinematic viscosity of a blood analog for flow visualization in hydraulic cardiovascular models.

PubMed

Nguyen, T T; Biadillah, Y; Mongrain, R; Brunette, J; Tardif, J C; Bertrand, O F

2004-08-01

In this work, we propose a simple method to simultaneously match the refractive index and kinematic viscosity of a circulating blood analog in hydraulic models for optical flow measurement techniques (PIV, PMFV, LDA, and LIF). The method is based on the determination of the volumetric proportions and temperature at which two transparent miscible liquids should be mixed to reproduce the targeted fluid characteristics. The temperature dependence models are a linear relation for the refractive index and an Arrhenius relation for the dynamic viscosity of each liquid. Then the dynamic viscosity of the mixture is represented with a Grunberg-Nissan model of type 1. Experimental tests for acrylic and blood viscosity were found to be in very good agreement with the targeted values (measured refractive index of 1.486 and kinematic viscosity of 3.454 milli-m2/s with targeted values of 1.47 and 3.300 milli-m2/s).
MISCIBILITY, SOLUBILITY, VISCOSITY, AND DENSITY MEASUREMENTS FOR R-236EA WITH FOUR DIFFERENT EXXON LUBRICANTS

EPA Science Inventory

The report discusses miscibility, solubility, viscosity, and density data for the refrigerant hydrofluorocarbon (HFC)-236ea (or R-236ea) and four lubricants supplied by Exxon Corporation. Such data are needed to determine the suitability of refrigerant/lubricant combinations for ...
Steric Pressure among Membrane-Bound Polymers Opposes Lipid Phase Separation.

PubMed

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

2016-04-19

Lipid rafts are thought to be key organizers of membrane-protein complexes in cells. Many proteins that interact with rafts have bulky polymeric components such as intrinsically disordered protein domains and polysaccharide chains. Therefore, understanding the interaction between membrane domains and membrane-bound polymers provides insights into the roles rafts play in cells. Multiple studies have demonstrated that high concentrations of membrane-bound polymeric domains create significant lateral steric pressure at membrane surfaces. Furthermore, our recent work has shown that lateral steric pressure at membrane surfaces opposes the assembly of membrane domains. Building on these findings, here we report that membrane-bound polymers are potent suppressors of membrane phase separation, which can destabilize lipid domains with substantially greater efficiency than globular domains such as membrane-bound proteins. Specifically, we created giant vesicles with a ternary lipid composition, which separated into coexisting liquid ordered and disordered phases. Lipids with saturated tails and poly(ethylene glycol) (PEG) chains conjugated to their head groups were included at increasing molar concentrations. When these lipids were sparse on the membrane surface they partitioned to the liquid ordered phase. However, as they became more concentrated, the fraction of GUVs that were phase-separated decreased dramatically, ultimately yielding a population of homogeneous membrane vesicles. Experiments and physical modeling using compositions of increasing PEG molecular weight and lipid miscibility phase transition temperature demonstrate that longer polymers are the most efficient suppressors of membrane phase separation when the energetic barrier to lipid mixing is low. In contrast, as the miscibility transition temperature increases, longer polymers are more readily driven out of domains by the increased steric pressure. Therefore, the concentration of shorter polymers required to suppress phase separation decreases relative to longer polymers. Collectively, our results demonstrate that crowded, membrane-bound polymers are highly efficient suppressors of phase separation and suggest that the ability of lipid domains to resist steric pressure depends on both their lipid composition and the size and concentration of the membrane-bound polymers they incorporate.
Effects of Tetrafluoroborate and Bis(trifluoromethylsulfonyl)amide Anions on the Microscopic Structures of 1-Methyl-3-octylimidazolium-Based Ionic Liquids and Benzene Mixtures: A Multiple Approach by ATR-IR, NMR, and Femtosecond Raman-Induced Kerr Effect Spectroscopy.

PubMed

Shirota, Hideaki; Kakinuma, Shohei; Itoyama, Yu; Umecky, Tatsuya; Takamuku, Toshiyuki

2016-01-28

The microscopic aspects of the two series of mixtures of 1-methyl-3-octylimidazolium tetrafluoroborate ([MOIm][BF4])-benzene and 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)amide ([MOIm][NTf2])-benzene were investigated by several spectroscopic techniques such as attenuated total reflectance IR (ATR-IR), NMR, and fs-Raman-induced Kerr effect spectroscopy (fs-RIKES). All three different spectroscopic results indicate that the anions more strongly interact with the cations in the [MOIm][BF4]-benzene mixtures than in the [MOIm][NTf2]-benzene mixtures. This also explains the different miscibility features between the two mixture systems well. The xC6H6 dependences of the chemical shifts and the C-H out-of-plane bending mode of benzene are similar: the changes are large in the high benzene concentration (xC6H6 > ∼ 0.6) compared to the low benzene concentration. In contrast, the linear xC6H6 dependences of the first moments of the low-frequency spectra less than 200 cm(-1) were observed in both the [MOIm][BF4]-benzene and [MOIm][NTf2]-benzene systems. The difference in the xC6H6 dependent features between the chemical shifts and intramolecular vibrational mode and the intermolecular/interionic vibrational bands might come from the different probing space scales. The traces of the parallel aromatic ring structure and the T-shape structure were found in the ATR-IR and NMR experiments, but fs-RIKES did not observe a clear trace of the local structure. This might imply that the interactions between the imidazolium and benzene rings are not strong enough to librate the imidazolium and benzene rings together. The bulk properties, such as miscibility, density, viscosity, and surface tension, of the two ionic liquid-benzene mixture series were also compared to the microscopic aspects.

Solvent/Non-Solvent Sintering To Make Microsphere Scaffolds

NASA Technical Reports Server (NTRS)

Laurencin, Cato T.; Brown, Justin L.; Nair, Lakshmi

2011-01-01

A solvent/non-solvent sintering technique has been devised for joining polymeric microspheres to make porous matrices for use as drug-delivery devices or scaffolds that could be seeded with cells for growing tissues. Unlike traditional sintering at elevated temperature and pressure, this technique is practiced at room temperature and pressure and, therefore, does not cause thermal degradation of any drug, protein, or other biochemical with which the microspheres might be loaded to impart properties desired in a specific application. Also, properties of scaffolds made by this technique are more reproducible than are properties of comparable scaffolds made by traditional sintering. The technique involves the use of two miscible organic liquids: one that is and one that is not a solvent for the affected polymer. The polymeric microspheres are placed in a mold having the size and shape of the desired scaffold, then the solvent/non-solvent mixture is poured into the mold to fill the void volume between the microspheres, then the liquid mixture is allowed to evaporate. Some of the properties of the resulting scaffold can be tailored through choice of the proportions of the liquids and the diameter of the microspheres.
Symmetry-protected gapless Z2 spin liquids

NASA Astrophysics Data System (ADS)

Lu, Yuan-Ming

2018-03-01

Despite rapid progress in understanding gapped topological states, much less is known about gapless topological phases of matter, especially in strongly correlated electrons. In this work, we discuss a large class of robust gapless quantum spin liquids in frustrated magnets made of half-integer spins, which are described by gapless fermionic spinons coupled to dynamical Z2 gauge fields. Requiring U(1 ) spin conservation, time-reversal, and certain space-group symmetries, we show that certain spinon symmetry fractionalization class necessarily leads to a gapless spectrum. These gapless excitations are stable against any perturbations, as long as the required symmetries are preserved. Applying these gapless criteria to spin-1/2 systems on square, triangular, and kagome lattices, we show that all gapped symmetric Z2 spin liquids in Abrikosov-fermion representation can also be realized in Schwinger-boson representation. This leads to 64 gapped Z2 spin liquids on square lattice, and 8 gapped states on both kagome and triangular lattices.
Thermodynamics of phase-separating nanoalloys: Single particles and particle assemblies

NASA Astrophysics Data System (ADS)

Fèvre, Mathieu; Le Bouar, Yann; Finel, Alphonse

2018-05-01

The aim of this paper is to investigate the consequences of finite-size effects on the thermodynamics of nanoparticle assemblies and isolated particles. We consider a binary phase-separating alloy with a negligible atomic size mismatch, and equilibrium states are computed using off-lattice Monte Carlo simulations in several thermodynamic ensembles. First, a semi-grand-canonical ensemble is used to describe infinite assemblies of particles with the same size. When decreasing the particle size, we obtain a significant decrease of the solid/liquid transition temperatures as well as a growing asymmetry of the solid-state miscibility gap related to surface segregation effects. Second, a canonical ensemble is used to analyze the thermodynamic equilibrium of finite monodisperse particle assemblies. Using a general thermodynamic formulation, we show that a particle assembly may split into two subassemblies of identical particles. Moreover, if the overall average canonical concentration belongs to a discrete spectrum, the subassembly concentrations are equal to the semi-grand-canonical equilibrium ones. We also show that the equilibrium of a particle assembly with a prescribed size distribution combines a size effect and the fact that a given particle size assembly can adopt two configurations. Finally, we have considered the thermodynamics of an isolated particle to analyze whether a phase separation can be defined within a particle. When studying rather large nanoparticles, we found that the region in which a two-phase domain can be identified inside a particle is well below the bulk phase diagram, but the concentration of the homogeneous core remains very close to the bulk solubility limit.
Axially grooved heat pipe study

NASA Technical Reports Server (NTRS)

1977-01-01

A technology evaluation study on axially grooved heat pipes is presented. The state-of-the-art is reviewed and present and future requirements are identified. Analytical models, the Groove Analysis Program (GAP) and a closed form solution, were developed to facilitate parametric performance evaluations. GAP provides a numerical solution of the differential equations which govern the hydrodynamic flow. The model accounts for liquid recession, liquid/vapor shear interaction, puddle flow as well as laminar and turbulent vapor flow conditions. The closed form solution was developed to reduce computation time and complexity in parametric evaluations. It is applicable to laminar and ideal charge conditions, liquid/vapor shear interaction, and an empirical liquid flow factor which accounts for groove geometry and liquid recession effects. The validity of the closed form solution is verified by comparison with GAP predictions and measured data.
Combining liquid inertia with pressure recovery from bubble expansion for enhanced flow boiling

NASA Astrophysics Data System (ADS)

Kalani, A.; Kandlikar, S. G.

2015-11-01

In this paper, we demonstrate using liquid inertia force in a taper gap microchannel geometry to provide a high level of heat dissipation capacity accompanied by a high heat transfer coefficient and low pressure drop during flow boiling. The high mass flux increases liquid inertia force and promotes vapor removal from the manifold, thereby increasing critical heat flux (CHF) and heat transfer coefficient. The tapered gap above the microchannels provides an increasing cross-sectional area in the flow direction. This gap allows bubbles to emerge from microchannels and expand within the gap along the flow direction. The bubble evaporation and expansion in tapered gap causes pressure recovery and reduces the total pressure drop. The pressure recovery increases with the increased evaporation rate at higher heat fluxes. Using a 6% taper and a moderately high inlet liquid flow Reynolds number of 1095, we have reached a CHF of 1.07 kW/cm2 with a heat transfer coefficient of 295 kW/m2 °C and a pressure drop of 30 kPa.
Displacement front behavior of near miscible CO2 flooding in decane saturated synthetic sandstone cores revealed by magnetic resonance imaging.

PubMed

Liu, Yu; Teng, Ying; Jiang, Lanlan; Zhao, Jiafei; Zhang, Yi; Wang, Dayong; Song, Yongchen

2017-04-01

It is of great importance to study the CO 2 -oil two-phase flow characteristic and displacement front behavior in porous media, for understanding the mechanisms of CO 2 enhanced oil recovery. In this work, we carried out near miscible CO 2 flooding experiments in decane saturated synthetic sandstone cores to investigate the displacement front characteristic by using magnetic resonance imaging technique. Experiments were done in three consolidated sandstone cores with the permeabilities ranging from 80 to 450mD. The oil saturation maps and the overall oil saturation during CO 2 injections were obtained from the intensity of magnetic resonance imaging. Finally the parameters of the piston-like displacement fronts, including the front velocity and the front geometry factor (the length to width ratio) were analyzed. Experimental results showed that the near miscible vertical upward displacement is instable above the minimum miscible pressure in the synthetic sandstone cores. However, low permeability can restrain the instability to some extent. Copyright Â© 2016 Elsevier Inc. All rights reserved.
Fabrication of thermoplastic ductile films of chitin butyrate/poly(ɛ-caprolactone) blends and their cytocompatibility.

PubMed

Hashiwaki, Hiroki; Teramoto, Yoshikuni; Nishio, Yoshiyuki

2014-12-19

We fabricate thermoplastic films of chitin burtyrate (ChB)/poly(ɛ-caprolactone) (PCL) blends with different degree of miscibility (miscible (M), partially miscible (PM), and immiscible (IM)), and examined the feasibility as a cell scaffold system through evaluating mechanical properties and cytocompatibility. We found a remediation of the brittleness and an increase in ductility of ChB by blending PCL for the M and PM blends. The blend films were subjected to alkaline hydrolysis (2-M NaOH/37°C/48 h) with expectation of the improvement of the surface hydrophilicity and cell accessibility. ATR-FTIR spectroscopy of the alkaline-treated PM and IM films revealed that PCL component and ester side-chains of acyl chitin were selectively removed from the surface domain. L929 fibroblast cells well adhered and proliferated on these films. Therefore, the materials possess a great potential for the utilization as a thermoplastic cell scaffold in tissue engineering by adequate selection of the degree of miscibility and post treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.
Preparation and Analysis of Co-precipitated, Biodegradable Poly-(Lactide-co-Glycolide) and Polyethylene Glycol Microspheres Prepared by Spray Drying

NASA Astrophysics Data System (ADS)

Javiya, Curie

Biodegradable poly-(d,l-lactide-co-glycolide) (PLGA) based microspheres are commonly used for numerous clinical applications. PEG is a widely used polymer due to its hydrophilic, biocompatible, and nontoxic nature. In this study, different blends of PLGA/PEG microspheres were prepared using a spray drying technique. The microspheres were spherical with maximum yield found to be 60.3% and average particle size in the range of 2.4 to 3.1 microm. Under the spray drying processing conditions, the polymers showed full miscibility slightly below 15% w/w and partial miscibility up to 20% w/w of PEG in the blended microspheres. At higher temperatures, PLGA and PEG were miscible in all proportions used for the blended microspheres. Blending 10% w/w PEG in PLGA membranes showed significant reduction in attachment of macrophages compared to PLGA membranes. The in-vitro response of macrophage towards the miscible blends of PLGA/PEG microspheres was further characterized. Results showed some reduction in macrophage viability and activation, however, significant effects with PLGA/PEG microspheres were not observed.
Stress-tuned conductor-polymer composite for use in sensors

DOEpatents

Martin, James E; Read, Douglas H

2013-10-22

A method for making a composite polymeric material with electrical conductivity determined by stress-tuning of the conductor-polymer composite, and sensors made with the stress-tuned conductor-polymer composite made by this method. Stress tuning is achieved by mixing a miscible liquid into the polymer precursor solution or by absorbing into the precursor solution a soluble compound from vapor in contact with the polymer precursor solution. The conductor may or may not be ordered by application of a magnetic field. The composite is formed by polymerization with the stress-tuning agent in the polymer matrix. The stress-tuning agent is removed following polymerization to produce a conductor-polymer composite with a stress field that depends on the amount of stress-tuning agent employed.
Melt Miscibility in Block Copolymers Containing Polyethylene and Substituted Polynorbornenes

NASA Astrophysics Data System (ADS)

Mulhearn, William; Register, Richard

Very few polymer species exist with a sufficiently weak repulsive interaction against polyethylene (PE), characterized by a low Flory parameter χ or interaction energy density X, to be useful for preparing PE-containing block copolymers with disordered melts at high molecular weights. Most suitably miscible polymers are chemically similar to PE, such as copolymers of ethylene with a minority content of an α-olefin, and so are only marginally useful for property modification due to similar physical properties like the glass transition temperature (Tg) . However, the family of polymers consisting of substituted norbornenes prepared via ring-opening metathesis polymerization (ROMP) and subsequent hydrogenation is unique in that many of its members exhibit very low X against PE (comparable with the interaction energy between poly(ethylene-alt-propylene) and PE), and some of these also exhibit high Tg. The miscibility between PE and a substituted, hydrogenated ROMP polynobornene, or between two dissimilar hydrogenated polynorbornenes, is a strong function of the substituent appended to the norbornene monomer. The mixing thermodynamics of this polymer series are irregular, in that the interaction energies do not follow X = (δ1 - δ2)2 where δ is the solubility parameter. However, other systematic trends do apply and we develop a set of mixing rules to quantitatively describe the experimental miscibility behavior. We also investigate statistical copolymerization of two norbornene monomers as a means to continuously tune miscibility with a homopolymer of a third monomer.
Miscibility and in vitro osteocompatibility of biodegradable blends of poly[(ethyl alanato) (p-phenyl phenoxy) phosphazene] and poly(lactic acid-glycolic acid).

PubMed

Deng, Meng; Nair, Lakshmi S; Nukavarapu, Syam P; Kumbar, Sangamesh G; Jiang, Tao; Krogman, Nicholas R; Singh, Anurima; Allcock, Harry R; Laurencin, Cato T

2008-01-01

Previously we demonstrated the ability of ethyl glycinato substituted polyphosphazenes to neutralize the acidic degradation products and control the degradation rate of poly(lactic acid-glycolic acid) (PLAGA) by blending. In this study, blends of high strength poly[(50% ethyl alanato) (50% p-phenyl phenoxy) phosphazene] (PNEA(50)PhPh(50)) and 85:15 PLAGA were prepared using a mutual solvent approach. Three different solvents, methylene chloride (MC), chloroform (CF) and tetrahydrofuran (THF) were studied to investigate solvent effects on blend miscibility. Three different blends were then fabricated at various weight ratios namely 25:75 (BLEND25), 50:50 (BLEND50), and 75:25 (BLEND75) using THF as the mutual solvent. The miscibility of the blends was evaluated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). Among these, BLEND25 was miscible while BLEND50 and BLEND75 were partially miscible. Furthermore, BLEND25 formed apatite layers on its surface as evidenced in a biomimetic study performed. These novel blends showed cell adhesion and proliferation comparable to PLAGA. However, the PNEA(50)PhPh(50) component in the blends was able to increase the phenotypic expression and mineralized matrix synthesis of the primary rat osteoblasts (PRO) in vitro. Blends of high strength PNEA(50)PhPh(50) and 85:15 PLAGA are promising biomaterials for a variety of musculoskeletal applications.
Magnetic resonance imaging study on near miscible supercritical CO2 flooding in porous media

NASA Astrophysics Data System (ADS)

Song, Yongchen; Zhu, Ningjun; Zhao, Yuechao; Liu, Yu; Jiang, Lanlan; Wang, Tonglei

2013-05-01

CO2 flooding is one of the most popular secondary or tertiary recoveries for oil production. It is also significant for studying the mechanisms of the two-phase and multiphase flow in porous media. In this study, an experimental study was carried out by using magnetic resonance imaging technique to examine the detailed effects of pressure and rates on CO2/decane flow in a bead-pack porous media. The displacing processes were conducted under various pressures in a region near the minimum miscibility pressure (the system tuned from immiscible to miscible as pressure is increasing in this region) and the temperature of 37.8 °C at several CO2 injection volumetric rates of 0.05, 0.10, and 0.15 ml/min (or linear rates of 3.77, 7.54, and 11.3 ft/day). The evolution of the distribution of decane and the characteristics of the two phase flow were investigated and analyzed by considering the pressure and rate. The area and velocity of the transition zone between the two phases were calculated and analyzed to quantify mixing. The area of transition zone decreased with pressure at near miscible region and a certain injection rate and the velocity of the transition zone was always less than the "volumetric velocity" due to mutual solution and diffusion of the two phases. Therefore, these experimental results give the fundamental understanding of tertiary recovery processes at near miscible condition.
The Dynamics of Miscible Interfaces: Simulations

NASA Technical Reports Server (NTRS)

Meiburg, Eckart

2002-01-01

The goal of this experimental/computational investigation (joint with Prof Maxworthy at USC) has been to study the dynamics of miscible interfaces, both from a scientific and a practical point of view, and to prepare a related experiment to be flown on the International Space Station. In order to address these effects, we have focused experimental and computational investigations on miscible displacements in cylindrical capillary tubes, as well as in Hele-Shaw cells. Regarding the flow in a capillary tube, the question was addressed as to whether Korteweg stresses and/or divergence effects can potentially account for discrepancies observed between conventional Stokes flow simulations and experiments for miscible flows in capillary tubes. An estimate of the vorticity and streamfunction fields induced by the Kortewegs stresses was derived, which shows these stresses to result in the formation of a vortex ring structure near the tip of the concentration front. Through this mechanism the propagation velocity of the concentration front is reduced, in agreement with the experimental observations. Divergence effects, on the other hand, were seen to be very small, and they have a negligible influence on the tip velocity. As a result, it can be concluded that they are not responsible for the discrepancies between experiments and conventional Stokes simulations. A further part of our investigation focussed on the development of high-accuracy three-dimensional spectral element simulation techniques for miscible flows in capillary tubes, including the effects of variable density and viscosity. Towards this end, the conservation equations are treated in cylindrical coordinates.
Mixing in three-phase systems: Implications for enhanced oil recovery and unconventional gas extraction

NASA Astrophysics Data System (ADS)

Jimenez-Martinez, J.; Porter, M. L.; Hyman, J.; Carey, J. W.; Viswanathan, H. S.

2015-12-01

Although the mixing of fluids within a porous media is a common process in natural and industrial systems, how the degree of mixing depends on the miscibility of multiple phases is poorly characterized. Often, the direct consequence of miscible mixing is the modification of the resident fluid (brine and hydrocarbons) rheological properties. We investigate supercritical (sc)CO2 displacement and mixing processes in a three-phase system (scCO2, oil, and H2O) using a microfluidics experimental system that accommodates the high pressures and temperatures encountered in fossil fuel extraction operations. The miscibility of scCO2 with the resident fluids, low with aqueous solutions and high with hydrocarbons, impacts the mixing processes that control sweep efficiency in enhanced oil recovery (EOR) and the unlocking of the system in unconventional oil and gas extraction. Using standard volume-averaging techniques we upscale the aqueous phase saturation to the field-scale (i.e., Darcy scale) and interpret the results as a simpler two-phase system. This process allows us to perform a statistical analysis to quantify i) the degree of heterogeneity in the system resulting from the immiscible H2O and ii) how that heterogeneity impacts mixing between scCO2 and oil and their displacement. Our results show that when scCO2 is used for miscible displacement, the presence of an aqueous solution, which is common in secondary and tertiary EOR and unconventional oil and gas extraction, strongly impacts the mixing of scCO2 with the hydrocarbons due to low scCO2-H2O miscibility. H2O, which must be displaced advectively by the injected scCO2, introduces spatio-temporal variability into the system that acts as a barrier between the two miscibile fluids. This coupled with the effect of viscosity contrast, i.e., viscous fingering, has an impact on the mixing of the more miscible pair.
Hydrogen-bonded side chain liquid crystalline block copolymer: Molecular design, synthesis, characterization and applications

NASA Astrophysics Data System (ADS)

Chao, Chi-Yang

Block copolymers can self-assemble into highly regular, microphase-separated morphologies with dimensions at nanometer length scales. Potential applications such as optical wavelength photonic crystals, templates for nanolithographic patterning, or nanochannels for biomacromolecular separation take advantage of the well-ordered, controlled size microdomains of block copolymers. Side-chain liquid crystalline block copolymers (SCLCBCPs) are drawing increasing attention since the incorporation of liquid crystallinity turns their well-organized microstructures into dynamic functional materials. As a special type of block copolymer, hydrogen-bonded SCLCBCPs are unique, compositionally tunable materials with multiple dynamic functionalities that can readily respond to thermal, electrical and mechanical fields. Hydrogen-bonded SCLCBCPs were synthesized and assembled from host poly(styrene- b-acrylic acid) diblock copolymers with narrow molecular weight distributions as proton donors and guest imidazole functionalized mesogenic moieties as proton acceptors. In these studies non-covalent hydrogen bonding is employed to connect mesogenic side groups to a block copolymer backbone, both for its dynamic character as well as for facile materials preparation. The homogeneity and configuration of the hydrogen-bonded complexes were determined by both the molecular architecture of imidazolyl side groups and the process conditions. A one-dimensional photonic crystal composed of high molecular weight hydrogen-bonded SCLCBCP, with temperature dependent optical wavelength stop bands was successfully produced. The microstructures of hydrogen-bonded complexes could be rapidly aligned in an AC electric field at temperatures below the order-disorder transition but above their glass transitions. Remarkable dipolar properties of the mesogenic groups and thermal dissociation of hydrogen bonds are key elements to fast orientation switching. Studies of a wide range of mesogen and polymer combinations were carried out to investigate the interplay between morphology, mesophase behavior and blend composition (molar ratios of proton acceptors to proton donors). A critical composition for mesophase formation was identified and the characteristics of the H-bonded complexes below the critical blend ratios were very different than those above. Hydrogen bonding was also used to direct microphase separation of miscible poly(hydroxystyrene-b-methyl methacrylate) diblock copolymer by adopting imidazolyl additives able to hydrogen bond with poly(hydroxystyrene). The miscibility between PHS and PMMA segments was diminished significantly by introducing small quantities of H-binding additives. The critical blend ratio for microphase separation was determined more by the molecular structure of the additives than the number of hydrogen bonds formed between PHS and additives.
First-principles prediction of stabilities and instabilities of compounds and alloys in the ternary B-As-P system

NASA Astrophysics Data System (ADS)

Ektarawong, A.; Simak, S. I.; Alling, B.

2017-07-01

We examine the thermodynamic stability of compounds and alloys in the ternary B-As-P system theoretically using first-principles calculations. We demonstrate that the icosahedral B12As2 is the only stable compound in the binary B-As system, while the zinc-blende BAs is thermodynamically unstable with respect to B12As2 and the pure arsenic phase at 0 K, and increasingly so at higher temperature, suggesting that BAs may merely exist as a metastable phase. On the contrary, in the binary B-P system, both zinc-blende BP and icosahedral B12P2 are predicted to be stable. As for the binary As-P system, As1 -xPx disordered alloys are predicted at elevated temperature—for example, a disordered solid solution of up to ˜75 at.% As in black phosphorus as well as a small solubility of ˜1 at.% P in gray arsenic at T =750 K, together with the presence of miscibility gaps. The calculated large solubility of As in black phosphorus explains the experimental syntheses of black-phosphorus-type As1 -xPx alloys with tunable compositions, recently reported in the literature. We investigate the phase stabilities in the ternary B-As-P system and demonstrate a high tendency for a formation of alloys in the icosahedral B12(As1 -xPx )2 structure by intermixing of As and P atoms at the diatomic chain sites. The phase diagram displays noticeable mutual solubility of the icosahedral subpnictides in each other even at room temperature as well as a closure of a pseudobinary miscibility gap around 900 K. As for pseudobinary BAs1 -xPx alloys, only a tiny amount of BAs is predicted to be able to dissolve in BP to form the BAs1 -xPx disordered alloys at elevated temperature. For example, less than 5% of BAs can dissolve in BP at T =1000 K. The small solubility limit of BAs in BP is attributed to the thermodynamic instability of BAs with respect to B12As2 and As.
Liquid-liquid phase separation and core-shell structure of ternary Al-In-Sn immiscible alloys

NASA Astrophysics Data System (ADS)

Zhao, Degang; Bo, Lin; Wang, Lin; Li, Shanshan

2018-04-01

In this study, the liquid-liquid phase separation of four kinds of ternary immiscible Al-In-Sn melts was investigated with resistivity and thermodynamics method. The nonlinear changes in ρ-T and DSC curves of Al-In-Sn immiscible alloys above monotectic reaction temperature revealed the occurrence of liquid-liquid phase separation of Al-In-Sn melts. The monotectic temperature, liquid phase separation temperature and immiscible gap of ternary Al-In-Sn alloys were lower than those of binary Al-In alloy. With the Al content decreasing, the immiscible gap of Al-In-Sn alloy decreased. The composition of Al80In10Sn10, Al70In15Sn15, Al60In20Sn20 and Al50In25Sn25 was located in the immiscible zone of Al-In-Sn system. Due to the differences of Stokes effect, Marangoni convection and immiscible gap, the solidification morphology of four kinds of Al-In-Sn monotectic alloy was different. The core–shell structure of Al-In-Sn monotectic alloy can form within a certain range of composition.
Mechanical and electro-optical properties of unconventional liquid crystal systems

NASA Astrophysics Data System (ADS)

Liao, Guangxun

Four types of unconventional liquid crystal systems - amphotropic glycolipids; novel bent-core liquid crystals, bent-core liquid crystal and glycolipid mixtures, and colloidal crystal-liquid crystal systems - were studied and characterized by polarizing microscopy, electrical current, digital scanning calorimetry, and dielectric spectroscopy. Thermotropic properties of glycolipids show a number of unusual properties, most notably high (60-120) relative dielectric constants mainly proportional to the number of polar sugar heads. The relaxation of this dielectric mode is found to be governed by the hydrogen bonding between sugar heads. Studies on novel bent-core liquid crystals reveal a new optically isotropic ferroelectric phase, molecular chirality-induced polarity, and transitions between molecular chirality and polarity driven phases. Mixtures of several bent-core substances with nematic, polar SmA and SmC phases, and a simple amphiphilic sugar lipid with SmA mesophase found to obey the well known miscibility rules, i.e. the sugar lipid mixes best with the polar SmA bent-core material. In addition, the chiral sugar lipid was found to induce tilt to the non-tilted polar SmA phase, which represents a new direction among the chirality--polarity--tilt relations. The effects of the surface properties and electric fields were studied on various colloid particles--and liquid crystal systems. It is found that the surface properties (hydrophobicity, roughness, rubbing) of the substrates are important in determining the size and symmetry of colloidal crystals. The director field of the liquid crystal infiltrated in the colloid crystals can be rendered both random and uniform along one of the crystallographic axis. We present the first observations of DC electric-field-induced rotational and translational motion of finite particles in liquid crystals. The electrorotation is essentially identical to the well - known Quincke rotation, which in liquid crystals triggers an additional translational motion at higher fields. Analysis of the electro-rotation and translations provides new ways to probe local rheological properties of liquid crystals.
NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.
Persistence of the gapless spin liquid in the breathing kagome Heisenberg antiferromagnet

NASA Astrophysics Data System (ADS)

Iqbal, Yasir; Poilblanc, Didier; Thomale, Ronny; Becca, Federico

2018-03-01

The nature of the ground state of the spin S =1 /2 Heisenberg antiferromagnet on the kagome lattice with breathing anisotropy (i.e., with different superexchange couplings J▵ and J▿ within elementary up- and down-pointing triangles) is investigated within the framework of Gutzwiller projected fermionic wave functions and Monte Carlo methods. We analyze the stability of the U(1 ) Dirac spin liquid with respect to the presence of fermionic pairing that leads to a gapped Z2 spin liquid. For several values of the ratio J▿/J▵ , the size scaling of the energy gain due to the pairing fields and the variational parameters are reported. Our results show that the energy gain of the gapped spin liquid with respect to the gapless state either vanishes for large enough system size or scales to zero in the thermodynamic limit. Similarly, the optimized pairing amplitudes (responsible for opening the spin gap) are shown to vanish in the thermodynamic limit. Our outcome is corroborated by the application of one and two Lanczos steps to the gapless and gapped wave functions, for which no energy gain of the gapped state is detected when improving the quality of the variational states. Finally, we discuss the competition with the "simplex" Z2 resonating-valence-bond spin liquid, valence-bond crystal, and nematic states in the strongly anisotropic regime, i.e., J▿≪J▵ .

Miscibility and in vitro osteocompatibility of biodegradable blends of poly[(ethyl alanato) (p-phenyl phenoxy) phosphazene] and poly(lactic acid-glycolic acid)

PubMed Central

Deng, Meng; Nair, Lakshmi S.; Nukavarapu, Syam P.; Kumbar, Sangamesh G.; Jiang, Tao; Krogman, Nicholas R.; Singh, Anurima; Allcock, Harry R.; Laurencin, Cato T.

2007-01-01

Previously we demonstrated the ability of ethyl glycinato substituted polyphosphazenes to neutralize the acidic degradation products and control the degradation rate of poly(lactic acid-glycolic acid) by blending. In this study, blends of high strength poly[(50% ethyl alanato) (50% p-phenyl phenoxy) phosphazene] (PNEA50PhPh50) and 85:15 poly(lactic acid-glycolic acid) (PLAGA) were prepared using a mutual solvent approach. Three different solvents, methylene chloride (MC), chloroform (CF) and tetrahydrofuran (THF) were studied to investigate solvent effects on blend miscibility. Three different blends were then fabricated at various weight ratios namely 25:75 (BLEND25), 50:50 (BLEND50), and 75:25 (BLEND75) using THF as the mutual solvent. The miscibility of the blends was evaluated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). Among these, BLEND25 was miscible while BLEND50 and BLEND75 were partially miscible. Furthermore, BLEND25 formed apatite layers on its surface as evidenced in a biomimetic study performed. These novel blends showed cell adhesion and proliferation comparable to PLAGA. However, the PNEA50PhPh50 component in the blends was able to increase the phenotypic expression and mineralized matrix synthesis of the primary rat osteoblasts (PRO) in vitro. Blends of high strength poly[(50% ethyl alanato) (50% p-phenyl phenoxy) phosphazene] (PNEA50PhPh50) and 85:15 poly(lactic acid-glycolic acid) (PLAGA) are promising biomaterials for a variety of musculoskeletal applications. PMID:17942150
Buoyant miscible displacement flows in a nonuniform Hele-Shaw cell

NASA Astrophysics Data System (ADS)

Walling, E.; Mollaabbasi, R.; Taghavi, S. M.

2018-03-01

Miscible displacement flows within the gap of a nonuniform Hele-Shaw cell are considered, theoretically and experimentally. The cell is vertical and it can be diverging or converging. A light fluid displaces a heavy fluid downwards. The displacement imposed velocity is sufficiently large so that diffusive effects are negligible within our time scale of interest. For certain flow parameters, the displacement flow is characterized by a symmetric, two-dimensional penetration of the light fluid into the heavy one, for which a lubrication approximation approach is developed to simplify the governing equations and find a semianalytical solution for the flux functions. The solutions reveal how the cell nonuniformity may affect the propagation of the interface between the two fluids, versus the other flow parameters, i.e., the viscosity ratio (m ) and a buoyancy number (χ ), for which a detailed flow regime classification is presented. Our results demonstrate that the presence of nonuniformity adds a unique spatiotemporal nature to these displacements which is not the case for uniform cell flows. The combination of the model and experiments reveals the existence of self-spreading, spike, and unstable (viscous fingering) flow regimes, which may occur at various spatial positions within the cell. A converging cell may allow a transition from spike to self-spreading or unstable regime, whereas a diverging cell may offer a transition from self-spreading or unstable to spike regime. Our work demonstrates that the novel spatiotemporal nature of nonuniform cell flows must be considered through the numerical solution of the interface propagation equation, to yield accurate predictions about the flow behaviors at various spatial positions.
Dynamical electron-phonon coupling, G W self-consistency, and vertex effect on the electronic band gap of ice and liquid water

NASA Astrophysics Data System (ADS)

Ziaei, Vafa; Bredow, Thomas

2017-06-01

We study the impact of dynamical electron-phonon (el-ph) effects on the electronic band gap of ice and liquid water by accounting for frequency-dependent Fan contributions in the el-ph mediated self-energy within the many-body perturbation theory (MBPT). We find that the dynamical el-ph coupling effects greatly reduce the static el-ph band-gap correction of the hydrogen-rich molecular ice crystal from-2.46 to -0.23 eV in great contrast to the result of Monserrat et al. [Phys. Rev. B 92, 140302 (2015), 10.1103/PhysRevB.92.140302]. This is of particular importance as otherwise the static el-ph gap correction would considerably reduce the electronic band gap, leading to considerable underestimation of the intense peaks of optical absorption spectra of ice which would be in great disagreement to experimental references. By contrast, the static el-ph gap correction of liquid water is very moderate (-0.32 eV), and inclusion of dynamical effects slightly reduces the gap correction to -0.19 eV. Further, we determine the diverse sensitivity of ice and liquid water to the G W self-consistency and show that the energy-only self-consistent approach (GnWn ) exhibits large implicit vertex character in comparison to the quasiparticle self-consistent approach, for which an explicit calculation of vertex corrections is necessary for good agreement with experiment.
Miscibility of poly(lactic acid) and poly(ethylene oxide) solvent polymer blends and nanofibers made by solution blow spinning

USDA-ARS?s Scientific Manuscript database

The miscibility of blends of poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO) was studied in polymer solutions by dilute solution viscometry and in solution blow spun nanofibers by microscopy (SEM, TEM) and by thermal and spectral analysis. Three blends of PLA and PEO were solution blended in...
A smoothed particle hydrodynamics model for miscible flow in three-dimensional fractures and the two-dimensional Rayleigh–Taylor instability

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

Tartakovsky, Alexandre M.; Meakin, Paul

2005-08-10

A numerical model based on smoothed particle hydrodynamics (SPH) has been developed and used to simulate the classical two-dimensional Rayleigh–Taylor instability and three-dimensional miscible flow in fracture apertures with complex geometries. To model miscible flow fluid particles with variable, composition dependent, masses were used. By basing the SPH equations on the particle number density artificial surface tension effects were avoided. The simulation results for the growth of a single perturbation driven by the Rayleigh – Taylor instability compare well with numerical results obtained by Fournier et al., and the growth of a perturbation with time can be represented quite wellmore » by a second-degree polynomial, in accord with the linear stability analysis of Duff et al. The dispersion coefficient found from SPH simulation of flow and diffusion in an ideal fracture was in excellent agreement with the value predicted by the theory of Taylor and Aris. The simulations of miscible flow in fracture apertures can be used to determination dispersion coefficients for transport in fractured media - a parameter used in large-scale simulations of contaminant transport.« less
Onset of space charge effects in liquid argon ionization chambers

NASA Astrophysics Data System (ADS)

Toggerson, B.; Newcomer, A.; Rutherfoord, J.; Walker, R. B.

2009-09-01

Using a thin-gap liquid argon ionization chamber and Strontium-90 beta sources we have measured ionization currents over a wide range of gap potentials. These precision "HV plateau curves" advance the understanding of liquid argon sampling calorimeter signals, particularly at high ionization rates. The order of magnitude differences in the activities of the beta sources allow us to estimate where the ionization chamber is driven into the space-charge dominated regime.
Experimentally Determined Phase Diagram for the Barium Sulfide-Copper(I) Sulfide System Above 873 K (600 °C)

NASA Astrophysics Data System (ADS)

Stinn, Caspar; Nose, Katsuhiro; Okabe, Toru; Allanore, Antoine

2017-12-01

The phase diagram of the barium sulfide-copper(I) sulfide system was investigated above 873 K (600 °C) using a custom-built differential thermal analysis (DTA) apparatus. The melting point of barium sulfide was determined utilizing a floating zone furnace. Four new compounds, Ba2Cu14S9, Ba2Cu2S3, Ba5Cu4S7, and Ba9Cu2S10, were identified through quench experiments analyzed with wavelength dispersive X-ray spectroscopy (WDS) and energy dispersive X-ray analysis (EDS). A miscibility gap was observed between 72 and 92 mol pct BaS using both DTA experiments and in situ melts observation in a floating zone furnace. A monotectic was observed at 94.5 mol pct BaS and 1288 K (1015 °C).
Compositional partitioning during the spinodal decomposition in Cu-Ni-Sn alloy

NASA Astrophysics Data System (ADS)

Basak, C. B.; Poswal, A. K.

2018-05-01

Spinodal decomposition in Cu-9.4at%Ni-3.1at%Sn alloy was elucidated with the new insight from the experimental EXAFS analysis supported by ab initio total energy calculations suggesting the strong influence of the first near-neighbour atoms. Enthalpy of mixing was calculated for all crystallographically unique first near-neighbour configurations and finally an average positive enthalpy of mixing of 1604 J/mol was obtained. Combination of ab initio results, XRD and EXAFS analysis indicate that one of the daughter phase becomes rich in Ni and Sn than the other phase; in contrary to the earlier proposition that Cu/Ni ratio remains constant in both daughter phases. It is also shown that the present thermodynamic description requires further refinement to extend the miscibility gap towards lower Ni content in Cu-Ni-Sn system.
Scaled equation of state parameters for gases in the critical region

NASA Technical Reports Server (NTRS)

Sengers, J. M. H. L.; Greer, W. L.; Sengers, J. V.

1976-01-01

In the light of recent theoretical developments, the paper presents an accurate characterization of anomalous thermodynamic behavior of xenon, helium 4, helium 3, carbon dioxide, steam and oxygen in the critical region. This behavior is associated with long range fluctuations in the system and the physical properties depend primarily on a single variable, namely, the correlation length. A description of the thermodynamic behavior of fluids in terms of scaling laws is formulated, and the two successfully used scaled equations of state (NBS equation and Linear Model parametric equation) are compared. Methods for fitting both equations to experimental equation of state data are developed and formulated, and the optimum fit for each of the two scaled equations of the above gases are presented and the results are compared. By extending the experimental data for the above one-component fluids to partially miscible binary liquids, superfluid liquid helium, ferromagnets and solids exhibiting order-disorder transitions, the principle of universality is concluded. Finally by using this principle, the critical regions for nine additional fluids are described.
Phase Equilibria and Transport Properties in the Systems AgNO3/RCN/H2O. R = CH3, C2H5, C3H7, C4H,, C6H5, and C6H5CH2

NASA Astrophysics Data System (ADS)

Das, Surjya P.; Wittekopf, Burghard; Weil, Konrad G.

1988-11-01

Silver nitrate can form homogeneous liquid phases with some organic nitriles and water, even when there is no miscibility between the pure liquid components. We determined the shapes of the single phase regions in the ternary phase diagram for the following systems: silver nitrate /RCN /H2O with R =CH3, C3H7, C6H5, and C6H5CH2 at room temperature and for R =C6H5 also at 60 °C and O °C. Furthermore we studied kinematic viscosities, electrical conductivities, and densities of mixtures containing silver nitrate, RCN, and water with the mole ratios X /4 /1 (0.2≦ X ≦S 3.4). In these cases also R = C2H5 and C4H9 were studied. The organic nitriles show different dependences of viscosity and conductivity on the silver nitrate content from the aliphatic ones.
Controlling the Formation of Ionic-Liquid-based Aqueous Biphasic Systems by Changing the Hydrogen-Bonding Ability of Polyethylene Glycol End Groups.

PubMed

Pereira, Jorge F B; Kurnia, Kiki A; Freire, Mara G; Coutinho, João A P; Rogers, Robin D

2015-07-20

The formation of aqueous biphasic systems (ABS) when mixing aqueous solutions of polyethylene glycol (PEG) and an ionic liquid (IL) can be controlled by modifying the hydrogen-bond-donating/-accepting ability of the polymer end groups. It is shown that the miscibility/immiscibility in these systems stems from both the solvation of the ether groups in the oxygen chain and the ability of the PEG terminal groups to preferably hydrogen bond with water or the anion of the salt. The removal of even one hydrogen bond in PEG can noticeably affect the phase behavior, especially in the region of the phase diagram in which all the ethylene oxide (EO) units of the polymeric chain are completely solvated. In this region, removing or weakening the hydrogen-bond-donating ability of PEG results in greater immiscibility, and thus, in a higher ability to form ABS, as a result of the much weaker interactions between the IL anion and the PEG end groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Lyotropic liquid crystal engineering moving beyond binary compositional space - ordered nanostructured amphiphile self-assembly materials by design.

PubMed

van 't Hag, Leonie; Gras, Sally L; Conn, Charlotte E; Drummond, Calum J

2017-05-22

Ordered amphiphile self-assembly materials with a tunable three-dimensional (3D) nanostructure are of fundamental interest, and crucial for progressing several biological and biomedical applications, including in meso membrane protein crystallization, as drug and medical contrast agent delivery vehicles, and as biosensors and biofuel cells. In binary systems consisting of an amphiphile and a solvent, the ability to tune the 3D cubic phase nanostructure, lipid bilayer properties and the lipid mesophase is limited. A move beyond the binary compositional space is therefore required for efficient engineering of the required material properties. In this critical review, the phase transitions upon encapsulation of more than 130 amphiphilic and soluble additives into the bicontinuous lipidic cubic phase under excess hydration are summarized. The data are interpreted using geometric considerations, interfacial curvature, electrostatic interactions, partition coefficients and miscibility of the alkyl chains. The obtained lyotropic liquid crystal engineering design rules can be used to enhance the formulation of self-assembly materials and provides a large library of these materials for use in biomedical applications (242 references).
Transport properties at fluids interfaces: a molecular study for a macroscopic modelling

NASA Astrophysics Data System (ADS)

Russo, Antonio; Morciano, Matteo; Sibley, David N.; Nold, Andreas; Goddard, Benjamin D.; Asinari, Pietro; Kalliadasis, Serafim

2017-11-01

Rapid developments in the field of micro- and nano-fluidics require detailed analysis of the properties of matter at the molecular level. But despite numerous works in the literature, appropriate macroscopic relations able to integrate a microscopic description of fluid and soft matter properties at liquid-vapour and multi-fluid interfaces are missing. As a consequence, studies on interfacial phenomena and micro-device designs often rely on oversimplified assumptions, e.g. that the viscosities can be considered constant across interfaces. In our work, we present non-equilibrium MD simulations to scrutinise efficiently and systematically, through the tools of statistical mechanics, the anisotropic properties of fluids, namely density variations, stress tensor, and shear viscosity, at the fluid interfaces between liquid and vapour and between two partially miscible fluids. Our analysis has led to the formulation of a general relation between shear viscosity and density variations validated for a wide spectrum of interfacial fluid problems. In addition, it provides a rational description of other interfacial quantities of interest, including surface tension and its origins, and more generally, it offers valuable insight of molecular transport phenomena at interfaces.
Thermodiffusion as a means to manipulate liquid film dynamics on chemically patterned surfaces

PubMed Central

Kalpathy, Sreeram K.; Shreyes, Amrita Ravi

2017-01-01

The model problem examined here is the stability of a thin liquid film consisting of two miscible components, resting on a chemically patterned solid substrate and heated from below. In addition to surface tension gradients, the temperature variations also induce gradients in the concentration of the film by virtue of thermodiffusion/Soret effects. We study the stability and dewetting behaviour due to the coupled interplay between thermal gradients, Soret effects, long-range van der Waals forces, and wettability gradient-driven flows. Linear stability analysis is first employed to predict growth rates and the critical Marangoni number for chemically homogeneous surfaces. Then, nonlinear simulations are performed to unravel the interfacial dynamics and possible locations of the film rupture on chemically patterned substrates. Results suggest that appropriate tuning of the Soret parameter and its direction, in conjunction with either heating or cooling, can help manipulate the location and time scales of the film rupture. The Soret effect can either potentially aid or oppose film instability depending on whether the thermal and solutal contributions to flow are cooperative or opposed to each other. PMID:28595391
Statistical Mechanical Theory of Coupled Slow Dynamics in Glassy Polymer-Molecule Mixtures

NASA Astrophysics Data System (ADS)

Zhang, Rui; Schweizer, Kenneth

The microscopic Elastically Collective Nonlinear Langevin Equation theory of activated relaxation in one-component supercooled liquids and glasses is generalized to polymer-molecule mixtures. The key idea is to account for dynamic coupling between molecule and polymer segment motion. For describing the molecule hopping event, a temporal casuality condition is formulated to self-consistently determine a dimensionless degree of matrix distortion relative to the molecule jump distance based on the concept of coupled dynamic free energies. Implementation for real materials employs an established Kuhn sphere model of the polymer liquid and a quantitative mapping to a hard particle reference system guided by the experimental equation-of-state. The theory makes predictions for the mixture dynamic shear modulus, activated relaxation time and diffusivity of both species, and mixture glass transition temperature as a function of molecule-Kuhn segment size ratio and attraction strength, composition and temperature. Model calculations illustrate the dynamical behavior in three distinct mixture regimes (fully miscible, bridging, clustering) controlled by the molecule-polymer interaction or chi-parameter. Applications to specific experimental systems will be discussed.
Ionic liquids as lubricant additives: A review

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

Zhou, Yan; Qu, Jun

In pursuit of energy efficiency and durability throughout human history, advances in lubricants have always played important roles. Ionic liquids (ILs) are room-temperature molten salts that possess unique physicochemical properties and have shown great potential in many applications with lubrication as one of the latest. While earlier work (2001–2011) primarily explored the feasibility of using ILs as neat or base lubricants, using ILs as lubricant additives has become the new focal research topic since the breakthrough in ILs’ miscibility in nonpolar hydrocarbon oils in early 2012. This work reviews the recent advances in developing ILs as additives for lubrication withmore » an attempt to correlate among the cationic and anionic structures, oil-solubility, and other relevant physicochemical properties, and lubricating behavior. Effects of the concentration of ILs in lubricants and the compatibility between ILs and other additives in the lubricant formulation on the tribological performance are described followed by a discussion of wear protection mechanism based on tribofilm characterization. As a result, future research directions are suggested at the end.« less
Ionic liquids as lubricant additives: A review

DOE PAGES

Zhou, Yan; Qu, Jun

2016-12-28

In pursuit of energy efficiency and durability throughout human history, advances in lubricants have always played important roles. Ionic liquids (ILs) are room-temperature molten salts that possess unique physicochemical properties and have shown great potential in many applications with lubrication as one of the latest. While earlier work (2001–2011) primarily explored the feasibility of using ILs as neat or base lubricants, using ILs as lubricant additives has become the new focal research topic since the breakthrough in ILs’ miscibility in nonpolar hydrocarbon oils in early 2012. This work reviews the recent advances in developing ILs as additives for lubrication withmore » an attempt to correlate among the cationic and anionic structures, oil-solubility, and other relevant physicochemical properties, and lubricating behavior. Effects of the concentration of ILs in lubricants and the compatibility between ILs and other additives in the lubricant formulation on the tribological performance are described followed by a discussion of wear protection mechanism based on tribofilm characterization. As a result, future research directions are suggested at the end.« less
Structural Evolution Following Spinodal Decomposition of the Pseudoternary Compound (Pb0.3Sn0.1Ge0.6)Te

NASA Astrophysics Data System (ADS)

Dado, Boaz; Gelbstein, Yaniv; Mogilansky, Dimitri; Ezersky, Vladimir; Dariel, Moshe P.

2010-09-01

Pseudoternary (Ge,Sn,Pb)Te compounds display favorable thermoelectric properties. Spinodal decomposition in the quasiternary (Ge,Sn,Pb)Te system is at the origin of a wide solubility gap at low Sn concentrations. The structural evolution of the spinodal decomposition was investigated as a function of aging time at 500°C, using x-ray diffraction, electron microscopy, and scanning electron microscopy. The evolution of the structure at 500°C consists initially of a short diffusion-controlled demixing stage into Pb- and Ge-rich coherent areas, with compositions corresponding to the inflection points of the free-energy curve. The Pb-rich areas adopt configurations associated with the directions of the soft elastic moduli of the cubic compound. Both the Pb- and Ge-rich areas are supersaturated and undergo in a second stage a nucleation and growth process and give rise to a biphased structure with equilibrium compositions corresponding to the boundaries of the miscibility gap. The resulting Pb-rich areas display a relatively stable microstructure suggesting the presence of long-range interactions between the Pb-rich precipitates in the Ge-rich matrix.
Evaporation-Triggered Segregation of Sessile Binary Droplets.

PubMed

Li, Yaxing; Lv, Pengyu; Diddens, Christian; Tan, Huanshu; Wijshoff, Herman; Versluis, Michel; Lohse, Detlef

2018-06-01

Droplet evaporation of multicomponent droplets is essential for various physiochemical applications, e.g., in inkjet printing, spray cooling, and microfabrication. In this work, we observe and study the phase segregation of an evaporating sessile binary droplet, consisting of a miscible mixture of water and a surfactantlike liquid (1,2-hexanediol). The phase segregation (i.e., demixing) leads to a reduced water evaporation rate of the droplet, and eventually the evaporation process ceases due to shielding of the water by the nonvolatile 1,2-hexanediol. Visualizations of the flow field by particle image velocimetry and numerical simulations reveal that the timescale of water evaporation at the droplet rim is faster than that of the Marangoni flow, which originates from the surface tension difference between water and 1,2-hexanediol, eventually leading to segregation.
Phases and structures of sunset yellow and disodium cromoglycate mixtures in water.

PubMed

Yamaguchi, Akihiro; Smith, Gregory P; Yi, Youngwoo; Xu, Charles; Biffi, Silvia; Serra, Francesca; Bellini, Tommaso; Zhu, Chenhui; Clark, Noel A

2016-01-01

We study phases and structures of mixtures of two representative chromonic liquid crystal materials, sunset yellow FCF (SSY) and disodium cromoglycate (DSCG), in water. A variety of combinations of isotropic, nematic (N), and columnar (also called M) phases are observed depending on their concentrations, and a phase diagram is made. We find a tendency for DSCG-rich regions to show higher-order phases while SSY-rich regions show lower-order ones. We observe uniform mesophases only when one of the materials is sparse in the N phases. Their miscibility in M phases is so low that essentially complete phase separation occurs. X-ray scattering and spectroscopy studies confirm that SSY and DSCG molecules do not mix when they form chromonic aggregates and neither do their aggregates when they form M phases.

Modeling the Impact of Deformation on Unstable Miscible Displacements in Porous Media

NASA Astrophysics Data System (ADS)

Santillán, D.; Cueto-Felgueroso, L.

2014-12-01

Coupled flow and geomechanics is a critical research challenge in engineering and the geosciences. The simultaneous flow of two or more fluids with different densities or viscosities through deformable media is ubiquitous in environmental, industrial, and biological processes, including the removal of non-aqueous phase liquids from underground water bodies, the geological storage of CO2, and current challenges in energy technologies, such as enhanced geothermal systems, unconventional hydrocarbon resources or enhanced oil recovery techniques. Using numerical simulation, we study the interplay between viscous-driven flow instabilities (viscous fingering) and rock mechanics, and elucidate the structure of the displacement patterns as a function of viscosity contrast, injection rate and rock mechanical properties. Finally, we discuss the role of medium deformation on transport and mixing processes in porous media.
Evaluation of mercury in the liquid waste processing facilities

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

Jain, Vijay; Shah, Hasmukh; Occhipinti, John E.

2015-08-13

This report provides a summary of Phase I activities conducted to support an Integrated Evaluation of Mercury in Liquid Waste System (LWS) Processing Facilities. Phase I activities included a review and assessment of the liquid waste inventory and chemical processing behavior of mercury using a system by system review methodology approach. Gaps in understanding mercury behavior as well as action items from the structured reviews are being tracked. 64% of the gaps and actions have been resolved.
Adding Some Gas Can Completely Change How an Object in a Liquid-Filled Housing Responds to Vibration

NASA Astrophysics Data System (ADS)

Torczynski, J. R.; O'Hern, T. J.; Clausen, J. R.

2015-11-01

Adding a little gas can completely change the motion of an object in a liquid-filled housing during vibration. A common system exhibiting this behavior is a spring-supported piston in a liquid-filled cylinder, where the gaps between them are narrow and depend on the piston position. When gas is absent, the piston's vibrational response is highly overdamped due to forcing viscous liquid through narrow gaps. When a small amount of gas is added, Bjerknes forces cause some of the gas to migrate below the piston. The resulting two gas regions form a pneumatic spring that enables the liquid to move with the piston, with the result that very little liquid is forced through the narrow gaps. This ``Couette mode'' has low damping and thus has a strong resonance near the frequency given by the pneumatic spring constant and the piston mass. At this frequency, the piston response is large, and the nonlinearity from the gap geometry produces a net force on the piston. This ``rectified'' force can be many times the piston's weight and can cause the piston to compress its supporting spring. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Dynamics of miscible displacements in round tubes

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

Meiburg, E.; Maxworthy, T.; Chen, C.Y.

A combined experimental and numerical investigation of miscible two-phase flow in a capillary tube is reported. The fraction of fluid left behind on the wall is obtained as a function of the Peclet, Atwood, and Froude numbers. Scaling arguments are presented for two distinct flow regimes, dominated by diffusion and convection, respectively. In the latter one, an effective surface tension value can be estimated.
Evolved Rocks in Ocean Islands Formed by Melting of Metasomatized Mantle

NASA Astrophysics Data System (ADS)

Ashwal, L. D.; Torsvik, T. H.; Horvath, P.; Harris, C.; Webb, S. J.; Werner, S. C.; Corfu, F.

2015-12-01

Evolved rocks like trachyte occur as minor components of many plume-related basaltic ocean islands (e.g. Hawaii, Gran Canaria, Azores, Réunion), and are typically interpreted as products of extreme fractional crystallization from broadly basaltic magmas. Trachytes from Mauritius (Indian Ocean) suggest otherwise. Here, 6.8 Ma nepheline-bearing trachytes (SiO2 ~63%, Na2O + K2O ~12%) are enriched in all incompatible elements except Ba, Sr and Eu, which show prominent negative anomalies. Initial eNd values cluster at 4.03 ± 0.15 (n = 13), near the lower end of the range for Mauritian basalts (eNd = 3.70 - 5.75), but initial Sr is highly variable (ISr = 0.70408 - 0.71034) suggesting secondary deuteric alteration. Fractional crystallization models starting with a basaltic parent fail, because when plagioclase joins olivine in the crystallizing assemblage, residual liquids become depleted in Al2O3, produce no nepheline, and do not approach trachytic compositions. Mauritian basalts and trachytes do not fall near the ends of known miscibility gaps, eliminating liquid immiscibility processes. Partial melting of extant gabbroic bodies, either from the oceanic crust or from Réunion plume-related magmas should yield quartz-saturated melts different from the critically undersaturated Mauritian trachytes. A remaining possibility is that the trachytes represent direct, small-degree partial melts of fertile, perhaps metasomatized mantle. This is supported by the presence of trachytic glasses in many mantle xenoliths, and experimental results show that low-degree trachytic melts can be produced from mantle peridotites even under anhydrous conditions. If some feldspar is left behind as a residual phase, this would account for the negative Ba, Sr and Eu anomalies observed in Mauritian trachytes. Two trachyte samples that are less depleted in these elements contain xenocrysts of anorthoclase, Al-rich cpx and Cl-rich kaersutite that are out of equilibrium with host trachyte magmas; these may represent fragments of a refertilized mantle source. A model of direct, low-degree partial melting of metasomatized mantle may apply to other worldwide examples of evolved rocks in ocean islands.
Metastability Gap in the Phase Diagram of Monoclonal IgG Antibody.

PubMed

Rowe, Jacob B; Cancel, Rachel A; Evangelous, Tyler D; Flynn, Rhiannon P; Pechenov, Sergei; Subramony, J Anand; Zhang, Jifeng; Wang, Ying

2017-10-17

Crystallization of IgG antibodies has important applications in the fields of structural biology, biotechnology, and biopharmaceutics. However, a rational approach to crystallize antibodies is still lacking. In this work, we report a method to estimate the solubility of antibodies at various temperatures. We experimentally determined the full phase diagram of an IgG antibody. Using the full diagram, we examined the metastability gaps, i.e., the distance between the crystal solubility line and the liquid-liquid coexistence curve, of IgG antibodies. By comparing our results to the partial phase diagrams of other IgGs reported in literature, we found that IgG antibodies have similar metastability gaps. Thereby, we present an equation with two phenomenological parameters to predict the approximate location of the solubility line of IgG antibodies with respect to their liquid-liquid coexistence curves. We have previously shown that the coexistence curve of an antibody solution can be readily determined by the polyethylene glycol-induced liquid-liquid phase separation method. Combining the polyethylene glycol-induced liquid-liquid phase separation measurements and the phenomenological equation in this article, we provide a general and practical means to predict the thermodynamic conditions for crystallizing IgG antibodies in the solution environments of interest. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.
Theory of First Order Chemical Kinetics at the Critical Point of Solution.

PubMed

Baird, James K; Lang, Joshua R

2017-10-26

Liquid mixtures, which have a phase diagram exhibiting a miscibility gap ending in a critical point of solution, have been used as solvents for chemical reactions. The reaction rate in the forward direction has often been observed to slow down as a function of temperature in the critical region. Theories based upon the Gibbs free energy of reaction as the driving force for chemical change have been invoked to explain this behavior. With the assumption that the reaction is proceeding under relaxation conditions, these theories expand the free energy in a Taylor series about the position of equilibrium. Since the free energy is zero at equilibrium, the leading term in the Taylor series is proportional to the first derivative of the free energy with respect to the extent of reaction. To analyze the critical behavior of this derivative, the theories exploit the principle of critical point isomorphism, which is thought to govern all critical phenomena. They find that the derivative goes to zero in the critical region, which accounts for the slowing down observed in the reaction rate. As has been pointed out, however, most experimental rate investigations have been carried out under irreversible conditions as opposed to relaxation conditions [Shen et al. J. Phys. Chem. A 2015, 119, 8784-8791]. Below, we consider a reaction governed by first order kinetics and invoke transition state theory to take into account the irreversible conditions. We express the apparent activation energy in terms of thermodynamic derivatives evaluated under standard conditions as well as the pseudoequilibrium conditions associated with the reactant and the activated complex. We show that these derivatives approach infinity in the critical region. The apparent activation energy follows this behavior, and its divergence accounts for the slowing down of the reaction rate.
Phase Behaviour and Miscibility Studies of Collagen/Silk Fibroin Macromolecular System in Dilute Solutions and Solid State.

PubMed

Ghaeli, Ima; de Moraes, Mariana A; Beppu, Marisa M; Lewandowska, Katarzyna; Sionkowska, Alina; Ferreira-da-Silva, Frederico; Ferraz, Maria P; Monteiro, Fernando J

2017-08-18

Miscibility is an important issue in biopolymer blends for analysis of the behavior of polymer pairs through the detection of phase separation and improvement of the mechanical and physical properties of the blend. This study presents the formulation of a stable and one-phase mixture of collagen and regenerated silk fibroin (RSF), with the highest miscibility ratio between these two macromolecules, through inducing electrostatic interactions, using salt ions. For this aim, a ternary phase diagram was experimentally built for the mixtures, based on observations of phase behavior of blend solutions with various ratios. The miscibility behavior of the blend solutions in the miscible zones of the phase diagram was confirmed quantitatively by viscosimetric measurements. Assessing the effects of biopolymer mixing ratio and salt ions, before and after dialysis of blend solutions, revealed the importance of ion-specific interactions in the formation of coacervate-based materials containing collagen and RSF blends that can be used in pharmaceutical, drug delivery, and biomedical applications. Moreover, the conformational change of silk fibroin from random coil to beta sheet, in solution and in the final solid films, was detected by circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR), respectively. Scanning electron microscopy (SEM) exhibited alterations of surface morphology for the biocomposite films with different ratios. Surface contact angle measurement illustrated different hydrophobic properties for the blended film surfaces. Differential scanning calorimetry (DSC) showed that the formation of the beta sheet structure of silk fibroin enhances the thermal stability of the final blend films. Therefore, the novel method presented in this study resulted in the formation of biocomposite films whose physico-chemical properties can be tuned by silk fibroin conformational changes by applying different component mixing ratios.
Evaluation of Mercury in Liquid Waste Processing Facilities - Phase I Report

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

Jain, V.; Occhipinti, J.; Shah, H.

2015-07-01

This report provides a summary of Phase I activities conducted to support an Integrated Evaluation of Mercury in Liquid Waste System (LWS) Processing Facilities. Phase I activities included a review and assessment of the liquid waste inventory and chemical processing behavior of mercury using a system by system review methodology approach. Gaps in understanding mercury behavior as well as action items from the structured reviews are being tracked. 64% of the gaps and actions have been resolved.
Evaluation of mercury in liquid waste processing facilities - Phase I report

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

Jain, V.; Occhipinti, J. E.; Shah, H.

2015-07-01

This report provides a summary of Phase I activities conducted to support an Integrated Evaluation of Mercury in Liquid Waste System (LWS) Processing Facilities. Phase I activities included a review and assessment of the liquid waste inventory and chemical processing behavior of mercury using a system by system review methodology approach. Gaps in understanding mercury behavior as well as action items from the structured reviews are being tracked. 64% of the gaps and actions have been resolved.
Pure wurtzite GaP nanowires grown on zincblende GaP substrates by selective area vapor liquid solid epitaxy

NASA Astrophysics Data System (ADS)

Halder, Nripendra N.; Kelrich, Alexander; Cohen, Shimon; Ritter, Dan

2017-11-01

We report on the growth of single phase wurtzite (WZ) GaP nanowires (NWs) on GaP (111) B substrates by metal organic molecular beam epitaxy following the selective area vapor-liquid-solid (SA-VLS) approach. During the SA-VLS process, precursors are supplied directly to the NW sidewalls, and the short diffusion length of gallium (or its precursors) does not significantly limit axial growth. Transmission electron microscopy (TEM) images reveal that no stacking faults are present along a 600 nm long NW. The lattice constants of the pure WZ GaP obtained from the TEM images agree with values determined previously by x-ray diffraction from non-pure NW ensembles.
Pure wurtzite GaP nanowires grown on zincblende GaP substrates by selective area vapor liquid solid epitaxy.

PubMed

Halder, Nripendra N; Kelrich, Alexander; Cohen, Shimon; Ritter, Dan

2017-11-17

We report on the growth of single phase wurtzite (WZ) GaP nanowires (NWs) on GaP (111) B substrates by metal organic molecular beam epitaxy following the selective area vapor-liquid-solid (SA-VLS) approach. During the SA-VLS process, precursors are supplied directly to the NW sidewalls, and the short diffusion length of gallium (or its precursors) does not significantly limit axial growth. Transmission electron microscopy (TEM) images reveal that no stacking faults are present along a 600 nm long NW. The lattice constants of the pure WZ GaP obtained from the TEM images agree with values determined previously by x-ray diffraction from non-pure NW ensembles.
Salting-out assisted liquid-liquid extraction with the aid of experimental design for determination of benzimidazole fungicides in high salinity samples by high-performance liquid chromatography.

PubMed

Wen, Yingying; Li, Jinhua; Yang, Fangfang; Zhang, Weiwei; Li, Weiran; Liao, Chunyang; Chen, Lingxin

2013-03-15

A novel method for the simultaneous separation and determination of four benzimidazole fungicides (i.e., carbendazim, fuberidazole, thiophanate-methyl and thiophanate) in high salinity samples was developed by using salting-out assisted liquid-liquid extraction (SALLE) via water-miscible acetonitrile as the extractant coupled with high-performance liquid chromatography. Box-Behnken design and response surface were employed to assist the optimization of SALLE conditions, including volume of salting-out solvent, the pH of sample solution and salting-out solvent as variable factors. The optimal salting-out parameters were obtained as follows: 2 mL of acetonitrile was added to 2 mL of sample solution with pH=4 and then 2 mL salting-out solvent containing 5 mol L(-1) sodium chloride at a pH of 7 was added to the solution for extraction. This procedure afforded a convenient and cost-saving operation with good cleanup ability for the benzimidazole fungicides, such as good linear relationships (R>0.996) between peak area and concentration from 2.5 ng mL(-1) to 500 ng mL(-1), low limits of detection between 0.14 ng mL(-1) and 0.38 ng mL(-1) and the intra-day precisions of retention time below 1.0%. The method recoveries obtained at fortified three concentrations for three seawater samples ranged from 60.4% to 99.1%. The simple, rapid and eco-benign SALLE based method proved potentially applicable for trace benzimidazole fungicides analysis in high salinity samples. Copyright © 2012 Elsevier B.V. All rights reserved.
Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid-liquid microextraction for determination of 2,4,6-trinitrotoluene.

PubMed

Fernández, Elena; Vidal, Lorena; Iniesta, Jesús; Metters, Jonathan P; Banks, Craig E; Canals, Antonio

2014-03-01

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

PubMed

Fernández, Elena; Vidal, Lorena; Martín-Yerga, Daniel; Blanco, María del Carmen; Canals, Antonio; Costa-García, Agustín

2015-04-01

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid-liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L(-1) was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L(-1), which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L(-1) and 1 µg L(-1), respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L(-1)) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.
Mobility control experience in the Joffre Viking miscible CO[sub 2] flood

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

Luhning, R.W.; Stephenson, D.J.; Graham, A.G.

1993-08-01

This paper discusses mobility control in the Joffre Viking field miscible CO[sub 2] flood. Since 1984, three injection strategies have been tried: water-alternating-CO[sub 2] (WACO[sub 2]), continuous CO[sub 2], and simultaneous CO[sub 2] and water. The studies showed that simultaneous injection results in the best CO[sub 2] conformance. CO[sub 2]-foam injection has also been investigated.
Post Waterflood CO2 Miscible Flood in Light Oil, Fluvial-Dominated Deltaic Reservoir (Pre-Work and Project Proposal), Class I

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

Bou-Mikael, Sami

This project outlines a proposal to improve the recovery of light oil from waterflooded fluvial dominated deltaic (FDD) reservoir through a miscible carbon dioxide (CO2) flood. The site is the Port Neches Field in Orange County, Texas. The field is well explored and well exploited. The project area is 270 acres within the Port Neches Field.
Implications of surfactant-induced flow for miscible-displacement estimation of air-water interfacial areas in unsaturated porous media.

PubMed

Costanza-Robinson, Molly S; Zheng, Zheng; Henry, Eric J; Estabrook, Benjamin D; Littlefield, Malcolm H

2012-10-16

Surfactant miscible-displacement experiments represent a conventional means of estimating air-water interfacial area (A(I)) in unsaturated porous media. However, changes in surface tension during the experiment can potentially induce unsaturated flow, thereby altering interfacial areas and violating several fundamental method assumptions, including that of steady-state flow. In this work, the magnitude of surfactant-induced flow was quantified by monitoring moisture content and perturbations to effluent flow rate during miscible-displacement experiments conducted using a range of surfactant concentrations. For systems initially at 83% moisture saturation (S(W)), decreases of 18-43% S(W) occurred following surfactant introduction, with the magnitude and rate of drainage inversely related to the surface tension of the surfactant solution. Drainage induced by 0.1 mM sodium dodecyl benzene sulfonate, commonly used for A(I) estimation, resulted in effluent flow rate increases of up to 27% above steady-state conditions and is estimated to more than double the interfacial area over the course of the experiment. Depending on the surfactant concentration and the moisture content used to describe the system, A(I) estimates varied more than 3-fold. The magnitude of surfactant-induced flow is considerably larger than previously recognized and casts doubt on the reliability of A(I) estimation by surfactant miscible-displacement.
Understanding How the Presence of Uniform Electric Fields Can Shift the Miscibility of Polystyrene/Poly(vinyl methyl ether) Blends

NASA Astrophysics Data System (ADS)

Kriisa, Annika; Roth, Connie B.

2015-03-01

Techniques which can externally control and manipulate the phase behavior of polymeric systems, without altering chemistry on a molecular level, have great practical benefits. One such possible mechanism is the use of electric fields, shown to cause interfacial instabilities, orientation of morphologies, and phase transitions in polymer blends and block copolymers. We have recently demonstrated that the presence of uniform electric fields can also strongly enhance the miscibility of polystyrene (PS) / poly(vinyl methyl ether) (PVME) blends [J. Chem. Phys. 2014, 141, 134908]. Using fluorescence to measure the phase separation temperature Ts of PS/PVME blends with and without electric fields, we show that Ts can be reproducibly and reversibly increased by 13.5 +/- 1.4 K for electric fields of 17 kV/mm for this lower critical solution temperature (LCST) blend. This increase in blend miscibility with electric fields represents some of the largest absolute shifts in Ts ever recorded, well outside of experimental error. The best theoretical prediction for the expected shift in Ts with electric field for this system is still two orders of magnitude smaller than that observed experimentally. We discuss the limitations of this theoretical prediction and consider possible factors affecting miscibility that may need to be also included.
Solubility and Speciation in the Water-Carbon Dioxide System

NASA Astrophysics Data System (ADS)

Abramson, E.; Bollengier, O.; Brown, J. M.

2016-12-01

The fluid-fluid miscibility surface of the water-carbon dioxide system contains broad regions (in pressure-composition space) exhibiting gradual variations in the temperature of miscibility; this is as expected. However, there is additionally a line of pressure, extending from roughly 2 GPa and 20 mole% CO2 to 6 GPa and 40 mole%, above which the temperature necessary to complete miscibility falls precipitously. This line, which closely approximates a hard limit, is hypothesized to demark a shift in speciation of dissolved CO2. In the same region of pressure the equilibrium limits of a new solid phase, composed of both water and CO2, have been determined. This new phase, the IR and Raman spectra of which led Wang et al.* to ascribe it to carbonic acid, has an observed associated aqueous form which must, in addition to the well-known bicarbonate and carbonate ions, affect the miscibilities of the system. Since zones of rapid subduction are expected to experience the regions of temperatures and pressures at which these equilibria are observed to shift, the chemical nature of these fluids is expected to undergo significant changes during the subduction process. * Wang H., Zeuschner J., Eremets M., Troyan I. and Willams J. (2016) Sci. Rep. 6, 19902-1-8

Evidence for transbilayer, tail-to-tail cholesterol dimers in dipalmitoylglycerophosphocholine liposomes.

PubMed

Harris, J S; Epps, D E; Davio, S R; Kézdy, F J

1995-03-21

The behavior of multilamellar liposomes of 2,3-dipalmitoyl-sn-glycero-1-phosphocholine (DPPC) was studied by differential scanning calorimetry (DSC) in the presence of < or = 5 mol % of the amphiphilic solutes methyl oleate, cholesterol, pregnenolone, and dehydroandrosterone. The DSC thermograms indicate that the solutes are miscible only with the liquid-disordered (Id) phase, and not with the solid-ordered (so) phase. The slopes of the Tm vs solute concentration curves confirm this conclusion: It appears that the so-1d phase transition of DPPC, which corresponds to the melting of the phospholipid chains, can be treated as a simple melting process and, thus, could be used as a cryoscopic system. In that case, its melting point depression constant, Kf, can be calculated a priori from the experimentally measured heat of fusion per gram of DPPC, lf, and the temperature of the phase transition of pure DPPC, T(o), by the equation Kf = RTo2/(1000lf) = 12.3 +/- 0.9 K g M-1 cm3. With methyl oleate as the solute, the Tm vs methyl oleate concentration plot is linear, and from the slope we calculate Kf = 12.9 +/- 0.8 K g M-1 cm3. Thus, methyl oleate appears to form an ideal cryoscopic system with dipalmitoyllecithin liposomes: It is fully miscible with the 1d phase but is apparently insoluble in the s(o) phase. Pregnenolone and dehydroandrosterone also form ideal cryoscopic systems with dipalmitoyllecithin liposomes: The Tm vs solute concentration plots are linear and yield the correct MWs for these solutes.(ABSTRACT TRUNCATED AT 250 WORDS)
Widely tunable chiral nematic liquid crystal optical filter with microsecond switching time.

PubMed

Mohammadimasoudi, Mohammad; Beeckman, Jeroen; Shin, Jungsoon; Lee, Keechang; Neyts, Kristiaan

2014-08-11

A wavelength shift of the photonic band gap of 141 nm is obtained by electric switching of a partly polymerized chiral liquid crystal. The devices feature high reflectivity in the photonic band gap without any noticeable degradation or disruption and have response times of 50 µs and 20 µs for switching on and off. The device consists of a mixture of photo-polymerizable liquid crystal, non-reactive nematic liquid crystal and a chiral dopant that has been polymerized with UV light. We investigate the influence of the amplitude of the applied voltage on the width and the depth of the reflection band.
Atomic-scale structure and electronic properties of GaN/GaAs superlattices

NASA Astrophysics Data System (ADS)

Goldman, R. S.; Feenstra, R. M.; Briner, B. G.; O'Steen, M. L.; Hauenstein, R. J.

1996-12-01

We have investigated the atomic-scale structure and electronic properties of GaN/GaAs superlattices produced by nitridation of a molecular beam epitaxially grown GaAs surface. Using cross-sectional scanning tunneling microscopy (STM) and spectroscopy, we show that the nitrided layers are laterally inhomogeneous, consisting of groups of atomic-scale defects and larger clusters. Analysis of x-ray diffraction data in terms of fractional area of clusters (determined by STM), reveals a cluster lattice constant similar to bulk GaN. In addition, tunneling spectroscopy on the defects indicates a conduction band state associated with an acceptor level of NAs in GaAs. Therefore, we identify the clusters and defects as nearly pure GaN and NAs, respectively. Together, the results reveal phase segregation in these arsenide/nitride structures, in agreement with the large miscibility gap predicted for GaAsN.
Numerical simulation of miscible viscous fingering with viscosity change in a displacing fluid by chemical reaction

NASA Astrophysics Data System (ADS)

Omori, Keiichiro; Nagatsu, Yuichiro

2017-11-01

Viscous fingering (VF) with viscosity changes by chemical reactions in case of miscible systems have been investigated both experimentally and theoretically in the recent years. Nagatsu et al. investigated experimentally miscible VF in which viscosity of the displaced fluid or the displacing one is changed by fast chemical reaction They showed that VF was more dense by the viscosity increase whereas less dense by the viscosity increase regardless of whether the viscosity change occurs in the displaced fluid or displacing one. From a theoretical viewpoint, numerical simulation performed on the reactive VF where viscosity of the displaced fluid is changed by instantaneously fast chemical reaction. The results had a good agreement with those in the corresponding experiment. In this work, we have conducted numerical simulation on such reactive VF where viscosity of the displacing fluid is changed. We have found the results have a good agreement with the corresponding experimental ones.
Miscibility phase diagram of ring-polymer blends: A topological effect.

PubMed

Sakaue, Takahiro; Nakajima, Chihiro H

2016-04-01

The miscibility of polymer blends, a classical problem in polymer science, may be altered, if one or both of the component do not have chain ends. Based on the idea of topological volume, we propose a mean-field theory to clarify how the topological constraints in ring polymers affect the phase behavior of the blends. While the large enhancement of the miscibility is expected for ring-linear polymer blends, the opposite trend toward demixing, albeit comparatively weak, is predicted for ring-ring polymer blends. Scaling formulas for the shift of critical point for both cases are derived. We discuss the valid range of the present theory, and the crossover to the linear polymer blends behaviors, which is expected for short chains. These analyses put forward a view that the topological constraints could be represented as an effective excluded-volume effects, in which the topological length plays a role of the screening factor.
Analytical and variational numerical methods for unstable miscible displacement flows in porous media

NASA Astrophysics Data System (ADS)

Scovazzi, Guglielmo; Wheeler, Mary F.; Mikelić, Andro; Lee, Sanghyun

2017-04-01

The miscible displacement of one fluid by another in a porous medium has received considerable attention in subsurface, environmental and petroleum engineering applications. When a fluid of higher mobility displaces another of lower mobility, unstable patterns - referred to as viscous fingering - may arise. Their physical and mathematical study has been the object of numerous investigations over the past century. The objective of this paper is to present a review of these contributions with particular emphasis on variational methods. These algorithms are tailored to real field applications thanks to their advanced features: handling of general complex geometries, robustness in the presence of rough tensor coefficients, low sensitivity to mesh orientation in advection dominated scenarios, and provable convergence with fully unstructured grids. This paper is dedicated to the memory of Dr. Jim Douglas Jr., for his seminal contributions to miscible displacement and variational numerical methods.
Computer-aided method for the determination of Hansen solubility parameters. Application to the miscibility of refrigerating lubricant and new refrigerant

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

Remigy, J.C.; Nakache, E.; Brechot, P.D.

This article presents a method which allows one to find the Hansen solubility parameters by means of data processing. In the first part, the authors present the thermodynamical principle of Hansen parameters, and then they explain the model used to find parameters from experimental data. They validate the method by studying the solubility parameters of CFC-12 (dichlorodifluoromethane), HFC-134a (1,1,1,2-tetrafluoroethane), neopentylglycol esters, trimethylolpropane esters, dipentaerythritol esters, and pentaerythritol esters. Then, the variation of Hansen parameters are studied as well as the relation between the miscibility temperature (the temperature at which a blend passes from the miscible state to the immiscible state)more » and the interaction distance. The authors establish the critical interaction distance of HFC-134a which determines the solubility limit and they study its variation with temperature.« less
Thermoelectric Power in Bilayer Graphene Device with Ionic Liquid Gating.

PubMed

Chien, Yung-Yu; Yuan, Hongtao; Wang, Chang-Ran; Lee, Wei-Li

2016-02-08

The quest for materials showing large thermoelectric power has long been one of the important subjects in material science and technology. Such materials have great potential for thermoelectric cooling and also high figure of merit ZT thermoelectric applications. We have fabricated bilayer graphene devices with ionic-liquid gating in order to tune its band gap via application of a perpendicular electric field on a bilayer graphene. By keeping the Fermi level at charge neutral point during the cool-down, we found that the charge puddles effect can be greatly reduced and thus largely improve the transport properties at low T in graphene-based devices using ionic liquid gating. At (Vig, Vbg) = (-1 V, +23 V), a band gap of about 36.6 ± 3 meV forms, and a nearly 40% enhancement of thermoelectric power at T = 120 K is clearly observed. Our works demonstrate the feasibility of band gap tuning in a bilayer graphene using ionic liquid gating. We also remark on the significant influence of the charge puddles effect in ionic-liquid-based devices.
Transition-Metal Mixing and Redox Potentials in Li x (M 1–y M' y )PO 4 (M, M' = Mn, Fe, Ni) Olivine Materials from First-Principles Calculations

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

Snydacker, David H.; Wolverton, Chris

The performance of olivine cathode materials can be improved using core/shell structures such as LiMnPO 4/LiFePO 4 and LiMnPO 4/LiNiPO 4. We use density functional theory to calculate the energetics, phase stability, and voltages of transition-metal mixing for a series of olivine phosphate materials. For LiMn 1–yFe yPO 4, LiFe 1–yNi yPO 4, and LiMn 1–yNi yPO 4, we find phase-separating tendencies with (mean-field) maximum miscibility gap temperatures of 120, 320, and 760 K respectively. At room temperature, we find that Mn is completely miscible in LiFePO 4, whereas Mn solubility in LiNiPO 4 is just 0.3%. Therefore, we suggestmore » that core/shell LiMnPO 4/LiNiPO 4 particles could be more effective at containing Mn in the particle core and limiting Mn dissolution into the electrolyte relative to LiMnPO 4/LiFePO 4 particles. We calculate shifts in redox potentials for dilute transition metals, M, substituted into Li xM'PO 4 host materials. Unmixed Li xMnPO 4 exhibits a redox potential of 4.0 V, but we find that dilute Mn in a LiNiPO 4 shell exhibits a redox potential of 4.3 V and therefore remains redox inactive at lower cathode potentials. We find that strain plays a large role in the redox potentials of some mixed systems (Li xMn 1–yFe yPO 4) but not others (Li xMn 1–yNi yPO 4).« less
Microstructure, mixing rules and interfacial behavior in high k barium titanate epoxy composite

NASA Astrophysics Data System (ADS)

Shi, Yitong (Thomas)

2001-07-01

In this thesis, we have demonstrated the importance of two issues in BaTiO3/epoxy composites. They are (1) the miscibility of a particle blend in organic vehicle, i.e. the capability of particles with different particle sizes to mix at the particle level, and (2) the ceramic/polymer interface as a role in determining the effective dielectric constant. The epoxy matrix between the BaTiO3 particles is not homogeneous and has to be modeled as a two-layer structure. The inhomogeneity causes not only failure of the existing mixing rules but also the particle size dependence of the effective dielectric constant. Since the interfacial behavior is determined by the materials chemistry, the effective dielectric properties experimentally demonstrate strong dependence on the materials selection and processing. If BaTiO3 particles in liquid epoxy resin has a bimodal particle size distribution, the smaller particles do not experimentally fit into the interstitial spaces between the larger spheres in an organic vehicle. ESEM observations indicated that the large particles separated from the small ones. Depending on the paste formula, the particle separation led to either a layer-like or cluster-like microstructure. The mixing free energy of blending smaller particles with larger particles explains the observed phenomena and suggests general criteria for particle miscibility. Whenever the mixing free energy is negative and the mixing free energy curve is convex, the particle blend remains in a random particle distribution. Otherwise, the particles separate into a larger-particle rich "phase" and a smaller-particle rich "phase". A random particle distribution may be the largest degree of mixing we can achieve in an organic vehicle. If there is no specific interaction between the small particles and the large particles, there is no thermodynamic driving force for small particles to fill preferentially into the interstitial spaces between the large spheres. The Hamaker constant H significantly influences the miscibility of a particle blend. An increase in Hamaker constant H causes not only greater driving force for a particle blend to separate but also a more narrowed convex shape---the mixing window. At a specific composition, a particle blend separates in one vehicle but may remain in a random distribution in another vehicle if the later vehicle has significantly reduced the Hamaker constant H.
Effect of carbon, sulfur and silicon on iron melting at high pressure: Implications for composition and evolution of the planetary terrestrial cores

NASA Astrophysics Data System (ADS)

Deng, Liwei; Fei, Yingwei; Liu, Xi; Gong, Zizheng; Shahar, Anat

2013-08-01

High-pressure melting experiments in the Fe-S-C ternary and Fe-S-Si-C quaternary systems have been conducted in the range of 3.5-20 GPa and 920-1700 °C in the multi-anvil press. The mutual solubility, melting relations, and crystallization sequences were systematically investigated with changes of pressure, temperature and bulk composition. Five starting materials of Fe(84.69 wt%)-C(4.35 wt%)-S(7.85 wt%), Fe(84.87 wt%)-C(2.08 wt%)-S(11.41 wt%), Fe(86.36 wt%)-C(0.96 wt%)-S(10.31 wt%), Fe(85.71 wt%)-C(0.33 wt%)-S(11.86 wt%) and Fe(82.95 wt%)-C(0.66 wt%)-S(13.7 wt%)-Si(2.89 wt%) were employed. For Fe(84.69 wt%)-C(4.35 wt%)-S(7.85 wt%), the first crystallized phase is Fe3C at 5 GPa and Fe7C3 at 10-20 GPa. For Fe(84.87 wt%)-C(2.08 wt%)-S(11.41 wt%), Fe3C is the stable carbide at subsolidus temperature at 5-15 GPa. For Fe(86.36 wt%)-C(0.96 wt%)-S(10.31 wt%) and Fe(85.71 wt%)-C(0.33 wt%)-S(11.86 wt%), the first crystallized phase is metallic Fe instead of iron carbide at 5-10 GPa. The cotectic curves in Fe-S-C ternary system indicate only a small amount of C is needed to form an iron carbide solid inner core with the presence of S. Experiments on Fe(82.95 wt%)-C(0.66 wt%)-S(13.7 wt%)-Si(2.89 wt%) showed that a small amount of C does not significantly change the closure pressure of miscibility gap compared with that in Fe-S-Si system. It is observed that S preferentially partitions into molten iron while a significant amount of Si enters the solid phase with temperature decrease. Meanwhile, the C concentration in the liquid and solid iron metal changes little with temperature variations. If S, C and Si partitioning behavior between molten iron and solid iron metal with temperature remains the same under Earth's present core pressure conditions, the solid inner core should be iron dominated with dissolved Si. On the other hand, the liquid outer core will be S rich and Si poor. Moderate carbon will be evenly present in both solid and liquid cores. Based on our melting data in a multi-component system, no layered liquid core should exist in the Earth, Mars and Mercury.
Comparison of GaP nanowires grown from Au and Sn vapor-liquid-solid catalysts as photoelectrode materials

NASA Astrophysics Data System (ADS)

Lee, Sudarat; Wen, Wen; Cheek, Quintin; Maldonado, Stephen

2018-01-01

Gallium phosphide (GaP) nanowire film electrodes have been prepared via solid sublimation of GaP powder using both gold (Au) and tin (Sn) nanoparticles as the vapor-liquid-solid (VLS) catalysts on Si(1 1 1) and GaP(1 1 1)B substrates. The resultant GaP nanowires are compared and contrasted in terms of structures and photoactivity in photoelectrochemical half cells. Raman spectra implicated a difference in the surface condition of the two types of nanowires. Complete wet etching removal of metallic VLS catalysts from the as-prepared GaP nanowires was possible with Sn catalysts but not with Au catalysts. The photoresponses of both Sn- and Au-seeded GaP nanowire films were collected and examined under 100 mW cm-2 white light illumination. Au-seeded nanowire films exhibited strong n-type characteristics when measured in nonaqueous electrolyte with ferrocene/ferricenium as the redox species while Sn-seeded nanowires showed behavior consistent with degenerate n-type doping.
The transition from blueschist to greenschist facies modeled by the reaction glaucophane + 2 diopside + 2 quartz = tremolite + 2 albite

NASA Astrophysics Data System (ADS)

Jenkins, David M.

2011-10-01

The reaction glaucophane + 2 diopside + 2 quartz = tremolite + 2 albite is proposed to model the transition from the blueschist to greenschist facies. This reaction was investigated experimentally over the range of 1.0-2.1 GPa and 500-800°C using synthetic phases in the chemical system Na2O-CaO-MgO-Al2O3-SiO2-H2O. Reversals of this reaction were possible at 500 and 550°C and growth of the low-pressure assemblage at 600°C; however, at temperatures of 600°C and higher and at pressures above 1.6 GPa omphacite nucleation (at the expense of diopside and albite) became quite strong and prevented attaining clear reversals of this reaction. Compositional changes in the amphiboles were determined by both electron microprobe analyses and correlations between unit-cell dimensions and composition. Glaucophane and particularly tremolite showed clear signs of compositional re-equilibration and merged to a single amphibole of winchite composition by about 754°C. These data were used to model the miscibility gap between glaucophane and tremolite using either the asymmetric multicomponent formulism parameters of W TR,GL of 68 kJ with αTR of 1.0 and αGL of 0.75 or a simple two-site asymmetric thermodynamic mixing expression with Margules parameters W NaCa of 13.4 kJ and W CaNa of 19.3 kJ. Combination of these thermodynamic models of the miscibility gap with extant thermodynamic data for the other phases yields a calculated location of the above reaction, involving pure diopside and albite, that is in good agreement with the observed experimental reversals and amphibole compositions over the range of 0.94-1.93 GPa and 400-754°C. The calculated effect of jadeite solid solution into diopside is to reduce the dP/dT slope from 0.0028 to 0.0021 GPa/°C and decrease the pressure by 0.28 GPa at 754°C. The dP/dT slope of this reaction boundary lies close to a linear geotherm of 13°C/km and is consistent with the slopes of other solid-solid reactions that have been used to model the blueschist-to-greenschist facies transition.
Ionic liquid/water mixtures: from hostility to conciliation.

PubMed

Kohno, Yuki; Ohno, Hiroyuki

2012-07-21

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

NASA Astrophysics Data System (ADS)

Yamashita, Nicholas; Jacobs, Jeffrey

2009-11-01

The experiments to be presented utilize an incompressible system of two stratified miscible liquids of different densities that are accelerated in order to produce the Rayleigh-Taylor instability. Three liquid combinations are used: isopropyl alcohol with water, a calcium nitrate solution or a lithium polytungstate solution, giving Atwood numbers of 0.11, 0.22 and 0.57, respectively. The acceleration required to drive the instability is produced by two high-speed linear induction motors mounted to an 8 m tall drop tower. The motors are mounted in parallel and have an effective acceleration length of 1.7 m and are each capable of producing 15 kN of thrust. The liquid system is contained within a square acrylic tank with inside dimensions 76 x76x184 mm. The tank is mounted to an aluminum plate, which is driven by the motors to create constant accelerations in the range of 1-20 g's, though the potential exists for higher accelerations. Also attached to the plate are a high-speed camera and an LED backlight to provide continuous video of the instability. In addition, an accelerometer is used to provide acceleration measurements during each experiment. Experimental image sequences will be presented which show the development of a random three-dimensional instability from an unforced initial perturbation. Measurements of the mixing zone width will be compared with traditional growth models.
The Role of Air-Electrode Structure on the Incorporation of Immiscible PFCs in Nonaqueous Li-O2 Battery.

PubMed

Balaish, Moran; Ein-Eli, Yair

2017-03-22

Perfluorocarbons (PFCs) are considered advantageous additives to nonaqueous Li-O 2 battery due to their superior oxygen solubility and diffusivity compared to common battery electrolytes. Up to now, the main focus was concentrated on PFCs-electrolyte investigation; however, no special attention was granted to the role of carbon structure in the PFCs-Li-O 2 system. In our current research, immiscible PFCs, rather than miscible fluorinated ethers, were added to activated carbon class air electrode due to their higher susceptibility toward O 2 •- attack and to their ability to shift the reaction from two-phase to an artificial three-phase reaction zone. The results showed superior battery performance upon PFCs addition at lower current density (0.05 mA cm -2 ) but unexpectedly failed to do so at higher current density (0.1 and 0.2 mA cm -2 ), where oxygen transport limitation is best illustrated. The last was a direct result of liquid-liquid displacement phenomenon occurring when the two immiscible liquids were introduced into the porous carbon medium. The investigation and role of carbon structure on the mechanism upon PFCs addition to Li-O 2 system are suggested based on electrochemical characterization, wettability behavior studies, and the physical adsorption technique. Finally, we suggest an optimum air-electrode structure enabling the incorporation of immiscible PFCs in a nonaqueous Li-O 2 battery.
Miscibility and Phase Behavior of N-Acylethanolamine/Diacylphosphatidylethanolamine Binary Mixtures of Matched Acyl Chainlengths (n = 14, 16)

PubMed Central

Kamlekar, Ravi Kanth; Satyanarayana, S.; Marsh, Derek; Swamy, Musti J.

2007-01-01

The miscibility and phase behavior of hydrated binary mixtures of two N-acylethanolamines (NAEs), N-myristoylethanolamine (NMEA), and N-palmitoylethanolamine (NPEA), with the corresponding diacyl phosphatidylethanolamines (PEs), dimyristoylphosphatidylethanolamine (DMPE), and dipalmitoylphosphatidylethanolamine (DPPE), respectively, have been investigated by differential scanning calorimetry (DSC), spin-label electron spin resonance (ESR), and 31P-NMR spectroscopy. Temperature-composition phase diagrams for both NMEA/DMPE and NPEA/DPPE binary systems were established from high sensitivity DSC. The structures of the phases involved were determined by 31P-NMR spectroscopy. For both systems, complete miscibility in the fluid and gel phases is indicated by DSC and ESR, up to 35 mol % of NMEA in DMPE and 40 mol % of NPEA in DPPE. At higher contents of the NAEs, extensive solid-fluid phase separation and solid-solid immiscibility occur depending on the temperature. Characterization of the structures of the mixtures formed with 31P-NMR spectroscopy shows that up to 75 mol % of NAE, both DMPE and DPPE form lamellar structures in the gel phase as well as up to at least 65°C in the fluid phase. ESR spectra of phosphatidylcholine spin labeled at the C-5 position in the sn-2 acyl chain present at a probe concentration of 1 mol % exhibit strong spin-spin broadening in the low-temperature region for both systems, suggesting that the acyl chains pack very tightly and exclude the spin label. However, spectra recorded in the fluid phase do not exhibit any spin-spin broadening and indicate complete miscibility of the two components. The miscibility of NAE and diacyl PE of matched chainlengths is significantly less than that found earlier for NPEA and dipalmitoylphosphatidylcholine, an observation that is consistent with the notion that the NAEs are most likely stored as their precursor lipids (N-acyl PEs) and are generated only when the system is subjected to membrane stress. PMID:17369415
When immiscible becomes miscible-Methane in water at high pressures.

PubMed

Pruteanu, Ciprian G; Ackland, Graeme J; Poon, Wilson C K; Loveday, John S

2017-08-01

At low pressures, the solubility of gases in liquids is governed by Henry's law, which states that the saturated solubility of a gas in a liquid is proportional to the partial pressure of the gas. As the pressure increases, most gases depart from this ideal behavior in a sublinear fashion, leveling off at pressures in the 1- to 5-kbar (0.1 to 0.5 GPa) range with solubilities of less than 1 mole percent (mol %). This contrasts strikingly with the well-known marked increase in solubility of simple gases in water at high temperature associated with the critical point (647 K and 212 bar). The solubility of the smallest hydrocarbon, the simple gas methane, in water under a range of pressure and temperature is of widespread importance, because it is a paradigmatic hydrophobe and occurs widely in terrestrial and extraterrestrial geology. We report measurements up to 3.5 GPa of the pressure dependence of the solubility of methane in water at 100°C-well below the latter's critical temperature. Our results reveal a marked increase in solubility between 1 and 2 GPa, leading to a state above 2 GPa where the maximum solubility of methane in water exceeds 35 mol %.
Tribological bench and engine dynamometer tests of a low viscosity SAE 0W-16 engine oil using a combination of ionic liquid and ZDDP as anti-wear additives

DOE PAGES

Barnhill, William C.; Gao, Hong; Kheireddin, Bassem; ...

2015-09-29

We have previously reported an oil-miscible phosphonium-organophosphate ionic liquid (IL) with an effective anti-wear (AW) functionality when added to a base oil by itself or combined with a conventional zinc dialkyldithiophosphate (ZDDP) for a synergistic effect. In this research, we investigated whether this synergy manifests in formulated engine oils. An experimental SAE 0W-16 engine oil was generated containing a combination of IL and ZDDP with equal phosphorus contribution. The prototype engine oil was first evaluated using tribological bench tests: AW performance in boundary lubrication (BL) and friction behavior (Stribeck curves) in elastohydrodynamic, mixed, and BL. In addition, the forthcoming standardmore » Sequence VIE engine dynamometer test was then conducted to demonstrate improved fuel economy. Results were benchmarked against those of another experimental engine oil with almost the same formulation except using ZDDP only without the IL (similar total phosphorus content). The IL-ZDDP formulation consistently outperforms the ZDDP-only formulation in friction reduction and wear protection, and results from the bench and engine tests are well correlated.« less
Preparation of polydopamine nanocapsules in a miscible tetrahydrofuran-buffer mixture.

PubMed

Ni, Yun-Zhou; Jiang, Wen-Feng; Tong, Gang-Sheng; Chen, Jian-Xin; Wang, Jie; Li, Hui-Mei; Yu, Chun-Yang; Huang, Xiao-hua; Zhou, Yong-Feng

2015-01-21

A miscible tetrahydrofuran-tris buffer mixture has been used to fabricate polydopamine hollow capsules with a size of 200 nm and with a shell thickness of 40 nm. An unusual non-emulsion soft template mechanism has been disclosed to explain the formation of capsules. The results indicate that the capsule structure is highly dependent on the volume fraction of tetrahydrofuran as well as the solvent, and the shell thickness of capsules can be controlled by adjusting the reaction time and dopamine concentration.

Video of Miscible Fluid Experiment Conducted on NASA Low Gravity Airplane

NASA Technical Reports Server (NTRS)

2003-01-01

This is a video of dyed water being injected into glycerin in a 2.2 centimeter (cm) diameter test tube. The experiment was conducted on the KC-135 aircraft, a NASA plane that creates microgravity and 2g conditions as it maneuvers through multiple parabolas. The water is less dense and so it rises to the top of the glycerin. The goal of the experiment was to determine if a blob of a miscible fluid would spontaneously become spherical in a microgravity environment.
Tuning the photonic band gap in cholesteric liquid crystals by temperature-dependent dopant solubility.

PubMed

Huang, Yuhua; Zhou, Ying; Doyle, Charlie; Wu, Shin-Tson

2006-02-06

We have investigated the physical and optical properties of the left-handed chiral dopant ZLI-811 mixed in a nematic liquid crystal (LC) host BL006. The solubility of ZLI-811 in BL006 at room temperature is ~24 wt%, but can be enhanced by increasing the temperature. Consequently, the photonic band gap of the cholesteric liquid crystal (CLC) mixed with more than 24 wt% chiral dopant ZLI-811 is blue shifted as the temperature increases. Based on this property, we demonstrate two applications in thermally tunable band-pass filters and dye-doped CLC lasers.
Free volume study on the miscibility of PEEK/PEI blend using positron annihilation and dynamic mechanical thermal analysis

NASA Astrophysics Data System (ADS)

Ramani, R.; Alam, S.

2015-06-01

High performance polymer blend of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) was examined for their free volume behaviour using positron annihilation lifetime spectroscopy and dynamic mechanical thermal analysis methods. The fractional free volume obtained from PALS shows a negative deviation from linear additivity rule implying good miscibility between PEEK and PEI. The dynamic modulus and loss tangent were obtained for the blends at three different frequencies 1, 10 and 100 Hz at temperatures close to and above their glass transition temperature. Applying Time-Temperature-Superposition (TTS) principle to the DMTA results, master curves were obtained at a reference temperature To and the WLF coefficients c01 and c02 were evaluated. Both the methods give similar results for the dependence of fractional free volume on PEI content in this blend. The results reveal that free volume plays an important role in determining the visco-elastic properties in miscible polymer blends.
Comparison between hot-melt extrusion and spray-drying for manufacturing solid dispersions of the graft copolymer of ethylene glycol and vinylalcohol.

PubMed

Guns, Sandra; Dereymaker, Aswin; Kayaert, Pieterjan; Mathot, Vincent; Martens, Johan A; Van den Mooter, Guy

2011-03-01

To investigate the effect of the manufacturing method (spray-drying or hot-melt extrusion) on the kinetic miscibility of miconazole and the graft copolymer poly(ethyleneglycol-g-vinylalcohol). The effect of heat pre-treatment of solutions used for spray-drying and the use of spray-dried copolymer as excipient for hot-melt extrusion was investigated. The solid dispersions were prepared at different drug-polymer ratios and analyzed with modulated differential scanning calorimetry and X-ray powder diffraction. Miconazole either mixed with the PEG-fraction of the copolymer or crystallized in the same or a different polymorph as the starting material. The kinetic miscibility was higher for the solid dispersions obtained from solutions which were pre-heated compared to those spray-dried from solutions at ambient temperature. Hot-melt extrusion resulted in an even higher mixing capability. Here the use of the spray-dried copolymer did not show any benefit concerning the kinetic miscibility of the drug and copolymer, but it resulted in a remarkable decrease in the torque experienced by the extruder allowing extrusion at lower temperature and torque. The manufacturing method has an influence on the mixing capacity and phase behavior of solid dispersions. Heat pre-treatment of the solutions before spray-drying can result in a higher kinetic miscibility. Amorphization of the copolymer by spray-drying before using it as an excipient for hot-melt extrusion can be a manufacturing benefit.
Influence of supercritical CO(2) pressurization on the phase behavior of mixed cholesteryl esters.

PubMed

Huang, Zhen; Feng, Mei; Su, Junfeng; Guo, Yuhua; Liu, Tie-Yan; Chiew, Yee C

2010-09-15

Evidences indicating the presence of phase transformations in the mixed cholesteryl benzoate (CBE) and cholesteryl butyrate (CBU) under the supercritical CO(2) pressurization, by means of differential scanning calorimetry (DSC) and X-ray diffraction (XRD), are presented in this work. These include (1) the DSC heating curve of pure CBU; (2) the DSC heating curves of CBU/CBE mixtures; (3) the XRD spectra of pure CBU; (4) the XRD spectra of CBU/CBE mixtures; (5) CBU and CBE are miscible in either solid phase or liquid phase over the whole composition range. As a result of the presence of these phase transformations induced by pressurization, it could be deduced that a solid solution of the CBU/CBE mixture might have formed at the interfaces under supercritical conditions, subsequently influencing their dissolving behaviors in supercritical CO(2). Copyright 2010 Elsevier B.V. All rights reserved.
Dynamic analysis of the mechanical seals of the rotor of the labyrinth screw pump

NASA Astrophysics Data System (ADS)

Lebedev, A. Y.; Andrenko, P. M.; Grigoriev, A. L.

2017-08-01

A mathematical model of the work of the mechanical seal with smooth rings made from cast tungsten carbide in the condition of liquid friction is drawn up. A special feature of this model is the allowance for the thermal expansion of a liquid in the gap between the rings; this effect acting in the conjunction with the frictional forces creates additional pressure and lift which in its turn depends on the width of the gap and the speed of sliding. The developed model displays the processes of separation, transportation and heat removal in the compaction elements and also the resistance to axial movement of the ring arising in the gap caused by the pumping effect and the friction in the flowing liquid; the inertia of this fluid is taken into account by the mass reduction method. The linearization of the model is performed and the dynamic characteristics of the transient processes and the forced oscillations of the device are obtained. The conditions imposed on the parameters of the mechanical seal are formulated to provide a regime of the liquid friction, which minimizes the wear.
Persistent dopants and phase segregation in organolead mixed-halide perovskites

DOE PAGES

Rosales, Bryan A.; Men, Long; Cady, Sarah D.; ...

2016-07-25

Organolead mixed-halide perovskites such as CH 3NH 3PbX 3–aX' a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the truemore » chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less
Persistent dopants and phase segregation in organolead mixed-halide perovskites

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

Rosales, Bryan A.; Men, Long; Cady, Sarah D.

Organolead mixed-halide perovskites such as CH 3NH 3PbX 3–aX' a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the truemore » chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less
True Shear Parallel Plate Viscometer

NASA Technical Reports Server (NTRS)

Ethridge, Edwin; Kaukler, William

2010-01-01

This viscometer (which can also be used as a rheometer) is designed for use with liquids over a large temperature range. The device consists of horizontally disposed, similarly sized, parallel plates with a precisely known gap. The lower plate is driven laterally with a motor to apply shear to the liquid in the gap. The upper plate is freely suspended from a double-arm pendulum with a sufficiently long radius to reduce height variations during the swing to negligible levels. A sensitive load cell measures the shear force applied by the liquid to the upper plate. Viscosity is measured by taking the ratio of shear stress to shear rate.
Properties of high quality GaP single crystals grown by computer controlled liquid encapsulated Czochralski technique

NASA Astrophysics Data System (ADS)

Kokubun, Y.; Washizuka, S.; Ushizawa, J.; Watanabe, M.; Fukuda, T.

1982-11-01

The properties of GaP single crystals grown by an automatically diameter controlled liquid encapsulated Czochralski technique using a computer have been studied. A dislocation density less than 5×104 cm-2 has been observed for crystal grown in a temperature gradient lower than 70 °C/cm near the solid-liquid interface. Crystals have about 10% higher electron mobility than that of commercially available coracle controlled crystals and have 0.2˜0.5 compensation ratios. Yellow light emitting diodes using computer controlled (100) substrates have shown extremely high external quantum efficiency of 0.3%.
Entanglement in miscible blends

NASA Astrophysics Data System (ADS)

Watanabe, Hiroshi

2010-03-01

The entanglement length Le of polymer chains (corresponding to the entanglement molecular weight Me) is not an intrinsic material parameter but changes with the interaction with surrounding chains. For miscible blends of cis-polyisoprene (PI) and poly(tert-butyl styrene) (PtBS), changes of Le on blending was examined. It turned out that the Le averaged over the number fractions of the Kuhn segments of the components (PI and PtBS) satisfactorily describes the viscoelastic behavior of pseudo-monodisperse blends in which the terminal relaxation time is the same for PI and PtBS.
Post Waterflood CO2 Miscible Flood in Light Oil, Fluvial-Dominated Deltaic Reservoir, Class I

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

Bou-Mikael, Sami

This report demonstrates the effectiveness of the CO2 miscible process in Fluvial Dominated Deltaic reservoirs. It also evaluated the use of horizontal CO2 injection wells to improve the overall sweep efficiency. A database of FDD reservoirs for the gulf coast region was developed by LSU, using a screening model developed by Texaco Research Center in Houston. The results of the information gained in this project is disseminated throughout the oil industry via a series of SPE papers and industry open forums.
Electrical tuning of three-dimensional photonic crystals using polymer dispersed liquid crystals

NASA Astrophysics Data System (ADS)

McPhail, Dennis; Straub, Martin; Gu, Min

2005-01-01

Electrically tunable three-dimensional photonic crystals with a tunable wavelength range of over 70nm of stop gaps between 3 and 4μm have been generated in a liquid crystal-polymer composite. The photonic crystals were fabricated by femtosecond-laser direct writing of void channels in an inverse woodpile configuration with 20 layers providing an extinction of infrared light transmission of 70% in the stacking direction. Stable structures could be manufactured up to a liquid crystal concentration of 24%. Applying a direct voltage of several hundred volts in the stacking direction of the photonic crystal changes the alignment of the liquid crystal directors and hence the average refractive index of the structure. This mechanism permits the direct tuning of the photonic stop gap.
Experimental study of dielectrophoresis and liquid dielectrophoresis mechanisms for particle capture in a droplet.

PubMed

Tsai, Sung-Lin; Hong, Jhih-Lin; Chen, Ming-Kun; Jang, Ling-Sheng

2011-06-01

This work presents a microfluidic system that can transport, concentrate, and capture particles in a controllable droplet. Dielectrophoresis (DEP), a phenomenon in which a force is exerted on a dielectric particle when it is subjected to a non-uniform electric field, is used to manipulate particles. Liquid dielectrophoresis (LDEP), a phenomenon in which a liquid moves toward regions of high electric field strength under a non-uniform electric field, is used to manipulate the fluid. In this study, a mechanism of droplet creation presented in a previous work that uses DEP and LDEP is improved. A driving electrode with a DEP gap is used to prevent beads from getting stuck at the interface between air and liquid, which is actuated with an AC signal of 200 V(pp) at a frequency of 100 kHz. DEP theory is used to calculate the DEP force in the liquid, and LDEP theory is used to analyze the influence of the DEP gap. The increment of the actuation voltage due to the electrode with a DEP gap is calculated. A set of microwell electrodes is used to capture a bead using DEP force, which is actuated with an AC signal of 20 V(pp) at a frequency of 5 MHz. A simulation is carried out to investigate the dimensions of the DEP gap and microwell electrodes. Experiments are performed to demonstrate the creation of a 100-nL droplet and the capture of individual 10-μm polystyrene latex beads in the droplet. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Gas-enabled resonance and rectified motion of a piston in a vibrated housing filled with a viscous liquid

DOE PAGES

Romero, Louis A.; Torczynski, John R.; Clausen, Jonathan R.; ...

2015-11-16

Herein, we show how introducing a small amount of gas can completely change the motion of a solid object in a viscous liquid during vibration. We analyze an idealized system exhibiting this behavior: a piston moving in a liquid-filled housing, where the gaps between the piston and the housing are narrow and depend on the piston position. Recent experiments have shown that vibration causes some gas to move below the piston and the piston to subsequently move downward and compress its supporting spring. Herein, we analyze the analogous but simpler situation in which the gas regions are replaced by bellowsmore » with similar pressure-volume relationships. We show that these bellows form a spring (analogous to the pneumatic spring formed by the gas regions) which enables the piston and the liquid to oscillate in a mode that does not exist without this spring. This mode is referred to here as the Couette mode because the liquid in the gaps moves essentially in Couette flow (i.e., with almost no component of Poiseuille flow). Since Couette flow by itself produces extremely low damping, the Couette mode has a strong resonance. We show that, near this resonance, the dependence of the gap geometry on the piston position produces a large rectified (net) force on the piston during vibration. As a result, this force can be much larger than the piston weight and the strength of its supporting spring and is in the direction that decreases the flow resistance of the gap geometry.« less
Low-energy electron inelastic mean free paths for liquid water

NASA Astrophysics Data System (ADS)

Nguyen-Truong, Hieu T.

2018-04-01

We improve the Mermin–Penn algorithm (MPA) for determining the energy loss function (ELF) within the dielectric formalism. The present algorithm is applicable not only to real metals, but also to materials that have an energy gap in the excitation spectrum. Applying the improved MPA to liquid water, we show that the present algorithm is able to address the ELF overestimation at the energy gap, and the calculated results are in good agreement with experimental data.
Effects of g-Jitter on Diffusion in Binary Liquids

NASA Technical Reports Server (NTRS)

Duval, Walter M. B.

1999-01-01

The microgravity environment offers the potential to measure the binary diffusion coefficients in liquids without the masking effects introduced by buoyancy-induced flows due to Earth s gravity. However, the background g-jitter (vibrations from the shuttle, onboard machinery, and crew) normally encountered in many shuttle experiments may alter the benefits of the microgravity environment and introduce vibrations that could offset its intrinsic advantages. An experiment during STS-85 (August 1997) used the Microgravity Vibration Isolation Mount (MIM) to isolate and introduce controlled vibrations to two miscible liquids inside a cavity to study the effects of g-jitter on liquid diffusion. Diffusion in a nonhomogeneous liquid system is caused by a nonequilibrium condition that results in the transport of mass (dispersion of the different kinds of liquid molecules) to approach equilibrium. The dynamic state of the system tends toward equilibrium such that the system becomes homogeneous. An everyday example is the mixing of cream and coffee (a nonhomogeneous system) via stirring. The cream diffuses into the coffee, thus forming a homogeneous system. At equilibrium the system is said to be mixed. However, during stirring, simple observations show complex flow field dynamics-stretching and folding of material interfaces, thinning of striation thickness, self-similar patterns, and so on. This example illustrates that, even though mixing occurs via mass diffusion, stirring to enhance transport plays a major role. Stirring can be induced either by mechanical means (spoon or plastic stirrer) or via buoyancy-induced forces caused by Earth s gravity. Accurate measurements of binary diffusion coefficients are often inhibited by buoyancy-induced flows. The microgravity environment minimizes the effect of buoyancy-induced flows and allows the true diffusion limit to be achieved. One goal of this experiment was to show that the microgravity environment suppresses buoyancy-induced convection, thereby mass diffusion becomes the dominant mechanism for transport. Since g-jitter transmitted by the shuttle to the experiment can potentially excite buoyancy-induced flows, we also studied the effects of controlled vibrations on the system.
Rapid determination of triclosan in personal care products using new in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction coupled with high performance liquid chromatography-ultraviolet detection.

PubMed

Chen, Ming-Jen; Liu, Ya-Ting; Lin, Chiao-Wen; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2013-03-12

This paper describes the development of a novel, simple and efficient in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction (IT-USA-SI-LLME) technique for the rapid determination of triclosan (TCS) in personal care products by high performance liquid chromatography-ultraviolet (HPLC-UV) detection. IT-USA-SI-LLME method is based on the rapid phase separation of water-miscible organic solvent from the aqueous phase in the presence of high concentration of salt (salting-out phenomena) under ultrasonication. In the present work, an indigenously fabricated home-made glass extraction device (8-mL glass tube inbuilt with a self-scaled capillary tip) was utilized as the phase separation device for USA-SI-LLME. After the extraction, the upper extractant layer was narrowed into the self-scaled capillary tip by pushing the plunger plug; thus, the collection and measurement of the upper organic solvent layer was simple and convenient. The effects of various parameters on the extraction efficiency were thoroughly evaluated and optimized. Under optimal conditions, detection was linear in the concentration range of 0.4-100ngmL(-1) with correlation coefficient of 0.9968. The limit of detection was 0.09ngmL(-1) and the relative standard deviations ranged between 0.8 and 5.3% (n=5). The applicability of the developed method was demonstrated for the analysis of TCS in different commercial personal care products and the relative recoveries ranged from 90.4 to 98.5%. The present method was proven to be a simple, sensitive, less organic solvent consuming, inexpensive and rapid procedure for analysis of TCS in a variety of commercially available personal care products or cosmetic preparations. Copyright © 2013 Elsevier B.V. All rights reserved.
Influence of barrier on partial discharge activity by a conducting particle in liquid nitrogen under AC voltages adopting UHF technique

NASA Astrophysics Data System (ADS)

Sarathi, R.; Giridhar, A. V.; Sethupathi, K.

2011-02-01

The UHF signals are generated due to PD formed by particle movement in liquid nitrogen under AC voltages. The levitation voltage of a particle in liquid nitrogen measured through UHF technique and by conventional PD measurement technique is the same, confirming the sensitivity of UHF technique for identification of PD activity. The frequency content of UHF signal generated due to particle movement in liquid nitrogen, under AC voltages, lies in the range 0.5-1.5 GHz. The characteristics of UHF signal generated due to particle movement between the barrier and high voltage/ground electrode is much similar to the signal generated by particle movement in clean electrode gap. Pseudo resonance phenomena can occur in liquid nitrogen due to particle movement. It is also observed that the partial discharge magnitude, in general, be high when the particle moves between the barrier and high voltage electrode when compared to the barrier and the ground electrode. Percentage of clay in epoxy nanocomposites has not altered the levitation voltage of the particle in the electrode gap. Zero span analysis clearly indicates that pseudo resonance occurs when particle moves (in a short gap) between the barrier and high voltage/ground electrode.
Control of plasma-liquid interaction of atmospheric DC glow discharge using liquid electrode

NASA Astrophysics Data System (ADS)

Shirai, Naoki; Aoki, Ryuta; Nito, Aihito; Aoki, Takuya; Uchida, Satoshi; Tochikubo, Fumiyoshi

2014-10-01

Atmospheric plasma in contact with liquid have a variety of interesting phenomena and applications. Previously, we investigated the fundamental characteristics of an atmospheric dc glow discharge using a liquid electrode with a miniature helium flow. We tried to control the plasma-liquid interaction by changing the plasma parameter such as gas species, liquid, and applied voltage. Sheath flow system enables another gas (N2, O2, Ar) flow to around the helium core flow. It can control the gas species around the discharge. When liquid (NaCl aq.) cathode DC discharge is generated, Na emission (588 nm) can be observed from liquid surface with increasing discharge current. Na emission strongly depends on the discharge current and liquid temperature. However, when Ar sheath flow is used, the intensity of Na becomes weak. When liquid anode DC discharge is generated, self-organized luminous pattern formation can be observed at the liquid surface. The pattern depends on existence of oxygen gas in gap. By changing the oxygen gas ratio in the gap, variety of pattern formation can be observed. The discharge in contact with liquid also can be used for synthesis of metal nanoparticles at plasma-liquid interface. Size and shape of nanoparticles depend on discharge gases. This work was supported financially in part by a Grant-in-Aid for Scientific Research on Innovative Areas (No 21110007) from MEXT, Japan.

Microfluidic and micro-core methods for enhanced oil recovery and carbon storage applications

NASA Astrophysics Data System (ADS)

Nguyen, Phong

Injection of CO2 into the subsurface, for both storage and oil recovery, is an emerging strategy to mitigate atmospheric CO2 emissions and associated climate change. In this thesis microfluidic and micro-core methods were developed to inform combined CO2-storage and oil recovery operations and determine relevant fluid properties. Pore scale studies of nanoparticle stabilized CO2-in-water foam and its application in oil recovery to show significant improvement in oil recovery rate with different oils from around the world (light, medium, and heavy). The CO2 nanoparticle-stabilized CO2 foams generate a three-fold increase in oil recovery (an additional 15% of initial oil in place) as compared to an otherwise similar CO2 gas flood. Nanoparticle-stabilized CO2 foam flooding also results in significantly smaller oil-in-water emulsion sizes. All three oils show substantial additional oil recovery and a positive reservoir homogenization effect. A supporting microfluidic approach is developed to quantify the minimum miscibility pressure (MMP) -- a critical parameter for combined CO 2 storage and enhanced oil recovery. The method leverages the inherent fluorescence of crude oils, is faster than conventional technologies, and provides quantitative, operator-independent measurements. In terms of speed, a pressure scan for a single minimum miscibility pressure measurement required less than 30 min, in stark contrast to days or weeks with existing rising bubble and slimtube methods. In practice, subsurface geology also interacts with injected CO 2. Commonly carbonate dissolution results in pore structure, porosity, and permeability changes. These changes are measured by x-ray microtomography (micro-CT), liquid permeability measurements, and chemical analysis. Chemical composition of the produced liquid analyzed by inductively coupled plasma-atomic emission spectrometer (ICP-AES) shows concentrations of magnesium and calcium. This work leverages established advantages of microfluidics in the new context of core-sample analysis, providing a simple core sealing method, small sample size, small volumes of injection fluids, fast characterization times, and pore scale resolution. Lastly, a microfluidic approach is developed to analyze the complex, multiphase fluid interactions in CO2 enhanced oil recovery at relevant reservoir temperature and pressure. Fluorescence imaging is applied to visualize and measure the effect of CO2 pressure on contact angles changes at the pore scale.
Design Constraints Regarding The Use Of Fluids In Emergency Medical Systems For Space Flight

NASA Technical Reports Server (NTRS)

McQuillen, John

2013-01-01

The Exploration Medical Capability Project of the Human Research Program is tasked with identifying, investigating and addressing gaps existing gaps in either knowledge or technology that need to be addressed in order to enable safer exploration missions. There are several gaps that involve treatment for emergency medical situations. Some of these treatments involve the handling of liquids in the spacecraft environment which involve gas-liquid mixtures handling, dissolution chemistry and thermal issues. Some of the recent technology efforts include the Intravenous fluid generation (IVGEN) experiment, the In-Suit Injection System (ISIS) experiment, and medical suction. Constraints include limited volume, shelf life, handling biohazards, availability of power, crew time and medical training.
Emission-based optical carbon dioxide sensing with HPTS in green chemistry reagents: room-temperature ionic liquids.

PubMed

Oter, Ozlem; Ertekin, Kadriye; Topkaya, Derya; Alp, Serap

2006-11-01

We describe the characterization of a new optical CO(2) sensor based on the change in the fluorescence signal intensity of 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) in green chemistry reagents--room-temperature ionic liquids (RTILs). As far as we are aware, this is the first time RTILs, 1-methyl-3-butylimidazolium tetrafluoroborate (RTIL-I) and 1-methyl-3-butylimidazolium bromide (RTIL-II), have been used as matrix materials with HPTS in an optical CO(2) sensor. It should be noted that the solubility of CO(2) in water-miscible ionic liquids is approximately 10 to 20 times that in conventional solvents, polymer matrices, or water. The response of the sensor to gaseous and dissolved CO(2) has been evaluated. The luminescence intensity of HPTS at 519 and 521 nm decreased with the increasing concentrations of CO(2) by 90 and 75% in RTIL-I and RTIL-II, respectively. The response times of the sensing reagents were in the range 1-2 min for switching from nitrogen to CO(2), and 7-10 min for switching from CO(2) to nitrogen. The signal changes were fully reversible and no significant hysteresis was observed during the measurements. The stability of HPTS in RTILs was excellent and when stored in the ambient air of the laboratory there was no significant drift in signal intensity after 7 months. Our stability tests are still in progress.
Polysiloxanes derived from the controlled hydrolysis of tetraethoxysilane as precursors to silica for use in ceramic processing

NASA Technical Reports Server (NTRS)

Philipp, Warren H.

1990-01-01

Synthesis, properties, and potential applications in ceramic processing for two polysiloxane silica precursors derived from the controlled hydrolysis of tetraethoxysilane (TEOS) are presented. The higher molecular weight TEOS-A is a thick adhesive liquid of viscosity 8000 to 12,000 c.p. having a SiO2 char yield of about 55 percent. The lower molecular weight TEOS-B is a more fluid liquid of viscosity 150 to 200 c.p. having a SiO2 char yield of about 52 percent. The acid catalyzed hydrolysis of TEOS to hydrated silica gel goes through a series of polysiloxane intermediates. The rate of this transition increases with the quantity of water added to the TEOS; thus, for ease of polymer isolation, the amount of water added must be carefully determined so as to produce the desired polymer in a reasonable time. The water to TEOS mole ratio falls in the narrow range of 1.05 for TEOS-A and 0.99 for TEOS-B. Further polymerization or gelation is prevented by storing at -5 C in a freezer. Both polysiloxanes thermoset to a glassy solid at 115 C. The liquid polymers are organic in nature in that they are miscible with toluene and ethanol, slightly souble in heptane, but immiscible with water. For both polymers, results on viscosity versus time are given at several temperatures and water additions. Based on these results, some examples of practical utilization of the precursors for ceramic fabrication are given.
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.
The Dynamics of Miscible Interfaces: Simulations

NASA Technical Reports Server (NTRS)

Meiburg, Eckart

2005-01-01

This research project focuses on the dynamics of interfacial regions between miscible fluids. While much attention has focused on immiscible interfaces in the past, miscible interfaces have been explored to a much lesser degree, so that there are many open questions regarding their dynamics at this time. Among the more pressing issues is the role that nonconventional stresses can play in such interfacial regions. Such stresses are typically not accounted for in efforts to model the dynamics of miscible flows. Our research aims to clarify under which circumstances these stresses do have to be taken into account, and what quantitative approaches are most suitable in this regard. In order to address these issues, we have focused on conducting linear stability analyses and nonlinear simulations for capillary tube and Hele-Shaw flows, and to compare the results with corresponding experiments performed in the labs of our co-investigators Prof. Maxworthy at USC, and Dr. Balasubramaniam at NASA. Over the duration of the project we have, among other things, focused on the effects of variable diffusion coefficients in such flows, and specifically on their influence in the growth of instabilities. Furthermore, our three-dimensional spectral element simulations have made good progress, so that we have come to a point where we can conduct more detailed comparisons with experimental observations. We are currently focusing our efforts on reproducing the tip-splitting instability observed by Maxworthy. Finally, we have discovered a new core-annular flow instability in the Stokes flow regime during the last year. This represents a significant finding, as this instability does not have an immiscible counterpart.
Aqueous Silicate Polymers: An Alternative to `Supercritical' Fluids as Transport Agents in Subduction Zones

NASA Astrophysics Data System (ADS)

Mannig, C. E.

2005-12-01

The chemistry of subduction-zone fluids is complicated by melt-vapor miscibility and the existence of critical end-points in rock-H2O systems. It is commonly assumed that fluids in subduction zones attain properties intermediate in composition between hydrous silicate liquid and H2O, and that such fluids possess enhanced material transport capabilities. However, the relevance of supercritical, intermediate fluids to subduction zones presents four problems. (1) Albite-H2O is typically used as an analogue system, but the favorable position of its critical curve is not representative; critical curves for polymineralic subduction-zone lithologies lie at substantially higher P. (2) Even if albite-H2O is relevant, jadeite may interfere because of its different solubility and the positive clapeyron slope of its solidus, which points to liquid-structure changes that could cause reappearance of the liquid+vapor field. (3) Critical curves are features of very H2O-rich compositions; low-porosity, H2O-poor natural systems will coexist with intermediate fluids only over a narrow PT interval. (4) Intermediate fluids are expected only over short length scales because their migration will likely result in compositional shifts via reaction and mineral precipitation in the mantle wedge. Although supercritical, intermediate fluids are probably relatively unimportant in subduction zones, they reflect a chemical process that may hold the key to understanding high- P mass transfer. Miscibility in melt-vapor systems is a consequence of polymerization of dissolved components, primarily Si ± Al, Na and Ca. This behavior yields, e.g., aqueous Si-Si, Si-Al, Si-Na-Al, and Si-Ca oxide dimers and other multimers of varying stoichiometry (silicate polymers), even in subcritical, dilute, H2O-rich vapor. Silicate polymers in subcritical aqueous solutions have been inferred from high- P mineral-solubility experiments. The abundance of these species at high P shows that the chemistry of aqueous fluids in subduction-zones differs fundamentally from the more familiar ionic solutions of the upper crust. This has important consequences for minor element transport. Measurements of Fe, phosphorous and Ti solubility reveal that dissolved concentrations rise with increased aqueous albite content at fixed P and T, with maximum enhancements exceeding 10X at melt saturation. Subcritical silicate polymerization thus permits transport of low solubility components via their substitution into sites on aqueous multimers constructed of "polymer formers" such as Na, Al, and Si, even in dilute solutions. The partitioning of elements between the bulk fluid, the polymer network, and the rock matrix likely controls the overall compositional evolution of subduction-zone fluids. Because they form over a wider PT and bulk X range, subcritical silicate polymers in dilute solutions are likely responsible for more mass transfer in subduction zones than intermediate, supercritical fluids.
Spontaneous formation of three-dimensionally ordered Bi-rich nanostructures within GaAs1-x Bi x /GaAs quantum wells

NASA Astrophysics Data System (ADS)

Luna, E.; Wu, M.; Hanke, M.; Puustinen, J.; Guina, M.; Trampert, A.

2016-08-01

In this work, we report on the spontaneous formation of ordered arrays of nanometer-sized Bi-rich structures due to lateral composition modulations in Ga(As,Bi)/GaAs quantum wells grown by molecular beam epitaxy. The overall microstructure and chemical distribution is investigated using transmission electron microscopy. The information is complemented by synchrotron x-ray grazing incidence diffraction, which provides insight into the in-plane arrangement. Due to the vertical inheritance of the lateral modulation, the Bi-rich nanostructures eventually shape into a three-dimensional assembly. Whereas the Bi-rich nanostructures are created via two-dimensional phase separation at the growing surface, our results suggest that the process is assisted by Bi segregation which is demonstrated to be strong and more complex than expected, implying both lateral and vertical (surface segregation) mass transport. As demonstrated here, the inherent thermodynamic miscibility gap of Ga(As,Bi) alloys can be exploited to create highly uniform Bi-rich units embedded in a quantum confinement structure.
Assessing the Strength Enhancement of Heterogeneous Networks of Miscible Polymer Blends

NASA Astrophysics Data System (ADS)

Giller, Carl; Roland, Mike

2013-03-01

At the typical crosslink densities of elastomers, the failure properties vary inversely with mechanical stiffness, so that compounding entails a compromise between stiffness and strength. Our approach to circumvent this conventional limitation is by forming networks of two polymers that: (i) are thermodynamically miscible, whereby the chemical composition is uniform on the segmental level; and (ii) have markedly different reactivities for network formation. The resulting elastomer consists of one highly crosslinked component and one that is lightly or uncrosslinked. This disparity in crosslinking causes their respective contributions to the network mechanical response to differ diametrically. Earlier results showed some success with this approach for thermally crosslinked blends of 1,2-polybutadiene (PVE) and polyisoprene (PI), as well as ethylene-propylene copolymer (EPM) and ethylene-propylene-diene random terpolymer (EPDM), taking advantage of their differing reactivities to sulfur. In this work we demonstrate the miscibility of polyisobutylene (PIB) with butyl rubber (BR) (a copolymer of PIB and polyisoprene) and show that networks in which only the BR is crosslinked possess greater tensile strengths than neat BR over the same range of moduli. Office of Naval Research
Viscometric investigation of compatibilization of the poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) blends by terpolymer of maleic anhydride styrene vinyl acetate

NASA Astrophysics Data System (ADS)

İmren, Dilek; Boztuğ, Ali; Yılmaz, Ersen; Zengin, H. Bayram

2008-11-01

In this study, a blend of poly(vinyl chloride) (PVC)/ethylene-co-vinyl acetate (EVA) was compatibilized by terpolymer of maleic anhydride-styrene-vinyl acetate (MAStVA) used as a compatibilizer. It was prepared the blends of 50/50 PVC/EVA containing 2-10% of the terpolymer. The compatibility experiences of these blends were investigated by using viscometric method in the range of concentrations (0.5-2.0 g dL -1) where tetrahydrofuran (THF) is the solvent. The interaction parameter (Δ b) was used to study the miscibility and compatibility of polymer blend in solution, obtained from the modified Krigbaum and Wall theory. Turbidity and FTIR measurements were also used to investigate the miscibility of this pair of polymers. The values of the relative viscosities of the each polymer solution and their blends were measured by a Cannon-Fenske type viscometer. In consequence of the study, it was observed that a considerable improvement was achieved in the miscibility of PVC/EVA blends by adding among 5 and 10 wt% of compatibilizer.
Miscibility of binary monolayers at the air-water interface and interaction of protein with immobilized monolayers by surface plasmon resonance technique.

PubMed

Wang, Yuchun; Du, Xuezhong

2006-07-04

The miscibility and stability of the binary monolayers of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and cationic dioctadecyldimethylammonium bromide (DOMA) at the air-water interface and the interaction of ferritin with the immobilized monolayers have been studied in detail using surface pressure-area isotherms and surface plasmon resonance technique, respectively. The surface pressure-area isotherms indicated that the binary monolayers of DPPC and DOMA at the air-water interface were miscible and more stable than the monolayers of the two individual components. The surface plasmon resonance studies indicated that ferritin binding to the immobilized monolayers was primarily driven by the electrostatic interaction and that the amount of adsorbed protein at saturation was closely related not only to the number of positive charges in the monolayers but also to the pattern of positive charges at a given mole fraction of DOMA. The protein adsorption kinetics was determined by the properties of the monolayers (i.e., the protein-monolayer interaction) and the structure of preadsorbed protein molecules (i.e., the protein-protein interaction).
Characterization of Physical and Mechanical Properties of Miscible Lactose-Sugars Systems.

PubMed

Li, Runjing; Roos, Yrjö H; Miao, Song

2017-09-01

Lactose-sugars systems were produced by spray drying. They were lactose, lactose-glucose (4:1) mixtures, lactose-maltose (4:1) mixtures, lactose-sucrose (4:1) mixtures, lactose-trehalose (4:1) mixtures, and lactose-corn syrup solids (CSS) (4:1) mixtures. The physical characteristics, water sorption behavior, glass transition, and mechanical properties of miscible lactose-sugars systems were investigated. Lactose-glucose mixtures had larger particle size than other lactose-sugars systems after spray drying. The presence of glucose or sucrose in lactose-sugars mixtures decreased the glass transition temperatures of amorphous systems, while the presence of maltose and trehalose had only minor impact on the glass transition temperatures. Moreover, glucose accelerated the crystallization of amorphous system at 0.44 a w , but its presence delayed the loss of sorbed water at higher water activities (≥0.54 a w ). Mechanical property study indicated that glucose and sucrose in amorphous system could result in an increase of molecular mobility, while the presence of CSS could decrease the free volume and maintain the stiffness of the miscible systems. © 2017 Institute of Food Technologists®.
Tunable liquid-crystal microshell-laser based on whispering-gallery modes and photonic band-gap mode lasing.

PubMed

Lu, Yuelan; Yang, Yue; Wang, Yan; Wang, Lei; Ma, Ji; Zhang, Lingli; Sun, Weimin; Liu, Yongjun

2018-02-05

The lasing behaviors of dye-doped cholesteric liquid crystal (DDCLC) microshells fabricated with silica-glass-microsphere coated DDCLCs were examined. Lasing characteristics were studied in a carrier medium with different refractive indices. The lasing in spherical cholesteric liquid crystals (CLCs) was attributed to two mechanisms, photonic band-gap (PBG) lasing and whispering-gallery modes (WGMs), which can independently exist by varying the chiral agent concentration and pumping energy. It was also found that DDCLC microshells can function as highly sensitive thermal sensors, with a temperature sensitivity of 0.982 nm °C -1 in PBG modes and 0.156 nm °C -1 in WGMs.
Ab initio calculations of the structural, electronic, thermodynamic and thermal properties of BaSe1-x Te x alloys

NASA Astrophysics Data System (ADS)

Drablia, S.; Boukhris, N.; Boulechfar, R.; Meradji, H.; Ghemid, S.; Ahmed, R.; Omran, S. Bin; El Haj Hassan, F.; Khenata, R.

2017-10-01

The alkaline earth metal chalcogenides are being intensively investigated because of their advanced technological applications, for example in photoluminescent devices. In this study, the structural, electronic, thermodynamic and thermal properties of the BaSe1-x Te x alloys at alloying composition x = 0, 0.25, 0.50, 0.75 and 1 are investigated. The full potential linearized augmented plane wave plus local orbital method designed within the density functional theory was used to perform the total energy calculations. In this research work the effect of the composition on the results of the parameters and bulk modulus as well as on the band gap energy is analyzed. From our results, we found a deviation of the obtained results for the lattice constants from Vegard’s law as well as a deviation of the value of the bulk modulus from the linear concentration dependence. We also carried out a microscopic analysis of the origin of the band gap energy bowing parameter. Furthermore, the thermodynamic stability of the considered alloys was explored through the measurement of the miscibility critical temperature. The quasi-harmonic Debye model, as implemented in the Gibbs code, was used to predict the thermal properties of the BaSe1-x Te x alloys, and these investigations comprise our first theoretical predictions concerning the BaSe1-x Te x alloys.
Ionic Liquids in Selective Oxidation: Catalysts and Solvents.

PubMed

Dai, Chengna; Zhang, Jie; Huang, Chongpin; Lei, Zhigang

2017-05-24

Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.
Interfacial behavior of Myristic acid in mixtures with DMPC and Cholesterol

NASA Astrophysics Data System (ADS)

Khattari, Z.; Sayyed, M. I.; Qashou, S. I.; Fasfous, I.; Al-Abdullah, T.; Maghrabi, M.

2017-06-01

Binary mixture monolayers of Myristic acid (MA) with the same length of saturated acyl chain lipid viz 1,2-myristoyl-sn-glycero-3-phosphocholine (DMPC) and Cholesterol (Chol), were investigated under different experimental conditions using Langmuir monolayers (LMs). The interfacial pressure-area (π-A) isotherms, excess molecular area, excess free energy and fluorescence microscopy (FM) images were recorded at the air/water interface. Monolayers of both systems (e.g. MA/DMPC, MA/Chol) reach the closest acyl hydrophobic chain packing in the range 0.20 < xMA < 0.70. Thermodynamic analysis indicates miscibility of the binary mixtures when spread at the air/water interface with negative deviation from the ideal behavior. Morphological features of MA/DMPC systems were found to depend strongly on MA mole fraction and pressures by showing two extreme minima in Gibbs free energy of mixing, while MA/Chol systems showed only an effective condensing effect at xMA = 0.90. In the whole range of compositions studied here, the liquid-expanded (LE) to liquid-condensed (LC) phase transition occurs at increasing xAM as it accomplished by a huge increase in the inverse compressibility modulus. FM observations confirmed the phase-transition and condensing effects of both mixture monolayers as evidenced by Gibbs free energy of mixing in a limited range of compositions.
Crystallographic phase induced electro-optic properties of nanorod blend nematic liquid crystal.

PubMed

Kundu, Sudarshan; Hill, Jonathan P; Richards, Gary J; Ariga, Katsuhiko; Khan, Ali Hossain; Thupakula, Umamahesh; Acharya, Somobrata

2011-09-01

Ultrasmall ZnS or PbS nanorods encapsulated in fluid-like soft organic surfactants show excellent miscibility in the nematic liquid crystal (LC ZLI-4792) host resulting in a novel soft matter type blend with enhanced electro-optic properties. The ultranarrow ZnS rods are of wurtzite phase and possess a chemical bipolarity and a net dipole moment. The centrosymmetric ultranarrow PbS rods possess a finite size and shape dependent inherent dipole moment despite their cubic rock-salt structure. When an electric field is applied, the blend aligns along the direction of the field producing a local unidirectional orientation of the rods and LC directors, and defining a unique axis for the system. The local ordering significantly affects the global ordering of the blend allowing a more rapid response of the electro-optic properties. The degree and switching speed of the blends depend upon the magnitude of dipole moments present in the dopant nanorods. We show how a non-mesogenic element designed with preferential crystallographic phase can be introduced within a LC for improvement of the switching properties of the LC blend. These types of unique blends are a model for fundamental conceptual advances in general understanding of interaction behaviour leading consequently to a significant technological advancement for superior device fabrication.
The UC2-x - Carbon eutectic: A laser heating study

NASA Astrophysics Data System (ADS)

Manara, D.; Boboridis, K.; Morel, S.; De Bruycker, F.

2015-11-01

The UC2-x - carbon eutectic has been studied by laser heating and fast multi-wavelength pyrometry under inert atmosphere. The study has been carried out on three compositions, two of which close to the phase boundary of the UC2-x - C miscibility gap (with C/U atomic ratios 2 and 2.1), and one, more crucial, with a large excess of carbon (C/U = 2.82). The first two compositions were synthesised by arc-melting. This synthesis method could not be applied to the last composition, which was therefore completed directly by laser irradiation. The U - C - O composition of the samples was checked by using a combustion method in an ELTRA® analyser. The eutectic temperature, established to be 2737 K ± 20 K, was used as a radiance reference together with the cubic - tetragonal (α → β) solid state transition, fixed at 2050 K ± 20 K. The normal spectral emissivity of the carbon-richer compounds increases up to 0.7, whereas the value 0.53 was established for pure hypostoichiometric uranium dicarbide at the limit of the eutectic region. This increase is analysed in the light of the demixing of excess carbon, and used for the determination of the liquidus temperature (3220 K ± 50 K for UC2.82). Due to fast solid state diffusion, also fostered by the cubic - tetragonal transition, no obvious signs of a lamellar eutectic structure could be observed after quenching to room temperature. The eutectic surface C/UC2-x composition could be qualitatively, but consistently, followed during the cooling process with the help of the recorded radiance spectra. Whereas the external liquid surface is almost entirely constituted by uranium dicarbide, it gets rapidly enriched in demixed carbon upon freezing. Demixed carbon seems to quickly migrate towards the inner bulk during further cooling. At the α → β transition, uranium dicarbide covers again the almost entire external surface.
Symmetry protected topological Luttinger liquids and the phase transition between them

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

None

2018-01-01

We show that a doped spin-1/2 ladder with antiferromagnetic intra-chain and ferromagnetic inter-chain coupling is a symmetry protected topologically non-trivial Luttinger liquid. Turning on a large easy-plane spin anisotropy drives the system to a topologically-trivial Luttinger liquid. Both phases have full spin gaps and exhibit power-law superconducting pair correlation. The Cooper pair symmetry is singletmore » $$d_{xy}$$ in the non-trivial phase and triplet $$S_z=0$$ in the trivial phase. The topologically non-trivial Luttinger liquid exhibits gapless spin excitations in the presence of a boundary, and it has no non-interacting or mean-field theory analog even when the fluctuating phase in the charge sector is pinned. As a function of the strength of spin anisotropy there is a topological phase transition upon which the spin gap closes. We speculate these Luttinger liquids are relevant to the superconductivity in metalized integer spin ladders or chains.« less
Mid-infrared multiple quantum well lasers using digitally-grown aluminum indium arsenic antimonide barriers and strained indium arsenic antimonide wells

NASA Astrophysics Data System (ADS)

Vaughn, Leslie G.

2006-04-01

AlxIn(1-x)AsySb(1-y) quaternary alloys have been used in Type I midwave infrared (MWIR) laser structures as barrier materials with InAs and InAsSb quantum wells. However, growth of these alloys has limited the application because of a large miscibility gap. In this research, quaternary films with compositions well into the miscibility gap (0 ≤ x ≤ 0.50) have been grown for the first time by molecular beam epitaxy (MBE) using a digital alloy technique. These films, lattice-matched to GaSb, have been characterized using double crystal X-ray diffraction (DCXRD), transmission electron microscopy (TEM), and photoluminescence (PL). Results indicate uniform, single-phase, and highly crystalline films. Using PL data, the dependence of the quaternary bandgap on composition has been studied and fit to various theoretical models. Combining the quaternary bandgap equation with strain and quantum size effects, the wavelengths for strained InAsSb wells in AlInAsSb quaternary barriers are predicted and compared to measured values generated from PL experiments. The reasonable agreement of these experimental results with the theoretical model supports the assertion that the AlInAsSb/InAsSb material system is Type I and emits in the target wavelength range of 3.3-4.2 mum. PL spectra of AlInAsSb/InAsSb multiple quantum wells exhibit a substantial increase in intensity with increasing quaternary aluminum content. This is presumably due to increasing valence band offset and, therefore, to better hole confinement. A laser with this active region has been fabricated and tested. Under pulsed optical pumping conditions at 50K, the laser emitted light at ˜3.93 mum. Further work has been done using the digital alloy technique to add gallium to the quaternary alloy to produce an AlGaInAsSb quinary alloy lattice-matched to GaSb. This material is of specific interest for mid-infrared lasers because by adding the fifth element, gallium, the range of material properties is extended. There is some indication from PL testing that the addition of the fifth element may contribute to Auger recombination suppression and may lead to higher operating temperatures. DCXRD and TEM of these quinary alloys give results similar to the quaternary alloys. The stable, single-phase growth of these quinary alloys shows promise for improving the performance of MWIR lasers.

Coexisting calderite and spessartine garnets in eclogite-facies metacherts of the Western Alps

NASA Astrophysics Data System (ADS)

Cenki-Tok, B.; Chopin, C.

2006-09-01

The coexistence of a colourless and a yellow garnet was observed in eclogite-facies manganese concentrations of the Mesozoic ophiolitic Zermatt-Saas Unit, at the Praborna mine near Saint-Marcel, Val d’Aoste, Italy, and in the upper Maurienne Valley, France. They occur both in oxidised metachert with hematite and braunite (+ minor Mn-pyroxenoid and tirodite, rare tiragalloite; with ardennite or piemontite in distinct layers), and in more reduced, carbonate-rich boudins included in it. The co-occurrence takes a variety of textural aspects, from coexisting euhedral garnets (10-100 µm in size for the calderite to mm-size for spessartine) to sharp overgrowths of yellow calderitic garnet on colourless spessartine, to yellow cauliflower-like masses (a few hundreds of µm in size) overgrowing colourless spessartine and showing evidence of oscillatory zoning, resorption stages and resumed growth. Sector zoning and anisotropy are common, although not consistent features. Compositions can be expressed to 95% in the quadrilateral system (Ca, Mn2+)3 (Al, Fe3+)2 Si3O12, with less than 1.0 wt% MgO and 0.8 wt% TiO2 in colourless spessartine, and less than 0.2 wt% MgO and 1.6 wt% TiO2 in yellow garnet. Calcium partitions into the ferric garnet. Coexisting pairs define two compositional gaps, bounded by values of the Fe3+/(Al + Fe3+) ratio of 10 and 15% for the first one, of 40 and 65% for the other. The optically obvious discontinuity (colour change and Becke’s line) corresponds to the narrower gap, between colourless spessartine and yellow spessartine, whereas the broad compositional gap occurs within yellow garnet, between yellow spessartine and yellow calderite, and is only revealed by back-scattered electron images. Only the latter can be a candidate for a miscibility gap, if any.
Multiphase, multicomponent phase behavior prediction

NASA Astrophysics Data System (ADS)

Dadmohammadi, Younas

Accurate prediction of phase behavior of fluid mixtures in the chemical industry is essential for designing and operating a multitude of processes. Reliable generalized predictions of phase equilibrium properties, such as pressure, temperature, and phase compositions offer an attractive alternative to costly and time consuming experimental measurements. The main purpose of this work was to assess the efficacy of recently generalized activity coefficient models based on binary experimental data to (a) predict binary and ternary vapor-liquid equilibrium systems, and (b) characterize liquid-liquid equilibrium systems. These studies were completed using a diverse binary VLE database consisting of 916 binary and 86 ternary systems involving 140 compounds belonging to 31 chemical classes. Specifically the following tasks were undertaken: First, a comprehensive assessment of the two common approaches (gamma-phi (gamma-ϕ) and phi-phi (ϕ-ϕ)) used for determining the phase behavior of vapor-liquid equilibrium systems is presented. Both the representation and predictive capabilities of these two approaches were examined, as delineated form internal and external consistency tests of 916 binary systems. For the purpose, the universal quasi-chemical (UNIQUAC) model and the Peng-Robinson (PR) equation of state (EOS) were used in this assessment. Second, the efficacy of recently developed generalized UNIQUAC and the nonrandom two-liquid (NRTL) for predicting multicomponent VLE systems were investigated. Third, the abilities of recently modified NRTL model (mNRTL2 and mNRTL1) to characterize liquid-liquid equilibria (LLE) phase conditions and attributes, including phase stability, miscibility, and consolute point coordinates, were assessed. The results of this work indicate that the ϕ-ϕ approach represents the binary VLE systems considered within three times the error of the gamma-ϕ approach. A similar trend was observed for the for the generalized model predictions using quantitative structure-property parameter generalizations (QSPR). For ternary systems, where all three constituent binary systems were available, the NRTL-QSPR, UNIQUAC-QSPR, and UNIFAC-6 models produce comparable accuracy. For systems where at least one constituent binary is missing, the UNIFAC-6 model produces larger errors than the QSPR generalized models. In general, the LLE characterization results indicate the accuracy of the modified models in reproducing the findings of the original NRTL model.
Hydrotreating Pyrolytic Lignin to Produce a Refinery Feedstock (Poster)

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

French, R. J.

2013-09-01

Fast pyrolysis of biomass followed by water separation to produce pyrolytic lignin and hydrotreating of the lignin could be used to produce a stable volatile low-oxygen intermediate liquid. Such a liquid could be converted into a finished motor-fuel in a refinery, taking advantage of the existing infrastructure and economies of scale of refineries. Hydrotreating just the lignin would consume less hydrogen while preserving about half of the energy of the original oil. The aqueous by-products could be reformed to produce the needed hydrogen and would contain much of the unwanted acids and unstable oxygenates. To assess such intermediate liquids, severalmore » pyrolytic lignins were prepared by mixing pyrolysis oil with water at 1:1 and 3:1 ratios. The carboxylic acidity in the pyrolytic lignin was reduced to 24 and 10 mg-KOH/g-lignin compared to 81 in the whole oil. These lignins were hydrotreated using Ni-Mo(S)/alumina, Pt/char, or Pd/C(activated) in a semi-batch 1 L stirred autoclave. The oil was stabilized under hydrogen at 150-280 degrees C, then water and light organics were removed by partial depressurization. Hydrodeoxygenation was then performed at 340-400 degrees C. Total pressure was controlled at 70 or 170 bar with hydrogen gas. Organic liquid yields of 39-56% were obtained. For many experiments the organic oxygen content was <7%, acidity was < 7 mg-KOH/g-oil, the volatility was greater than or equal to 94% and, on a carbon basis, the total yield of organic products miscible in hydrocarbons at a 1:10 ratio was over 50%. These properties are probably acceptable to a refinery.The residual liquids left in the reactor at the end of the experiment comprised 60-85% of the organic-phase product while the rest was condensate. 13C-NMR of the residual liquids showed that they were 50-80% aliphatic. 13C-NMR coupled with GC-MS identified phenolic compounds as the main oxygenates in most residual liquids.« less
Miscibility and interactions of animal and plant sterols with choline plasmalogen in binary and multicomponent model systems.

PubMed

Hąc-Wydro, Katarzyna; Luty, Katarzyna

2014-04-01

In this work miscibility and interactions of sterols with choline plasmalogen (PC-plasm) in Langmuir monolayers were studied. Moreover, the properties of cholesterol/phosphatidylcholine/plasmalogen mixtures of different PC-plasm concentration were investigated. The foregoing systems were treated as a model of cancer cell membranes, which are of higher plasmalogen level than normal cells. Finally, the influence of β-sitosterol and stigmasterol (phytosterols differing in anticancer potency) on these mixtures was verified. The properties of monolayers were analyzed based on the parameters derived from the surface pressure-area isotherms and images taken with Brewster Angle Microscope. It was found that at 30% of sterol in sterol/plasmalogen monolayer the lipids are immiscible and 3D crystallites are formed within the film. Cholesterol molecules mix favorably with PC-plasm at Xchol ≥ 0.5, while the investigated phytosterols only at their prevailing proportion in binary system. The increase of choline plasmalogen in cholesterol/phosphatidylcholine monolayer causes destabilization of the system. Moreover, the incorporation of phytosterols into cholesterol/phosphatidylcholine+PC-plasm mixtures disturbed membrane morphology and this effect was stronger for β-sitosterol as compared to stigmasterol. It was concluded that the presence of vinyl ether bond at sn-1 position in PC-plasm molecule strongly affects miscibility of choline plasmalogen with sterols. The comparison of the collected data with those reported in literature allowed one to conclude that miscibility and interactions of sterols with PC-plasm are less favorable than those with phosphatidylcholine. It was also suggested that overexpression of plasmalogens in cancer cell membranes may be a factor differentiating sensitivity of cells to anticancer effect of phytosterols. Copyright © 2014 Elsevier B.V. All rights reserved.
Multiscale structure, interfacial cohesion, adsorbed layers, miscibility and properties in dense polymer-particle mixtures

NASA Astrophysics Data System (ADS)

Schweizer, Ken

2012-02-01

A major goal in polymer nanocomposite research is to understand and predict how the chemical and physical nature of individual polymers and nanoparticles, and thermodynamic state (temperature, composition, solvent dilution, filler loading), determine bulk assembly, miscibility and properties. Microscopic PRISM theory provides a route to this goal for equilibrium disordered mixtures. A major prediction is that by manipulating the net polymer-particle interfacial attraction, miscibility is realizable via the formation of thin thermodynamically stable adsorbed layers, which, however, are destroyed by entropic depletion and bridging attraction effects if interface cohesion is too weak or strong, respectively. This and related issues are quantitatively explored for miscible mixtures of hydrocarbon polymers, silica nanospheres, and solvent using x-ray scattering, neutron scattering and rheology. Under melt conditions, quantitative agreement between theory and silica scattering experiments is achieved under both steric stabilization and weak depletion conditions. Using contrast matching neutron scattering to characterize the collective structure factors of polymers, particles and their interface, the existence and size of adsorbed polymer layers, and their consequences on microstructure, is determined. Failure of the incompressible RPA, accuracy of PRISM theory, the nm thickness of adsorbed layers, and qualitative sensitivity of the bulk modulus to interfacial cohesion and particle size are demonstrated for concentrated PEO-silica-ethanol nanocomposites. Temperature-dependent complexity is discovered when water is the solvent, and nonequilibrium effects emerge for adsorbing entangled polymers that strongly impact structure. By varying polymer chemistry, the effect of polymer-particle attraction on the intrinsic viscosity is explored with striking non-classical effects observed. This work was performed in collaboration with S.Y.Kim, L.M.Hall, C.Zukoski and B.Anderson.
Thaumatin crystallization aboard the International Space Station using liquid-liquid diffusion in the Enhanced Gaseous Nitrogen Dewar (EGN).

PubMed

Barnes, Cindy L; Snell, Edward H; Kundrot, Craig E

2002-05-01

This paper reports results from the first biological crystal-growth experiment on the International Space Station (ISS). Crystals of thaumatin were grown using liquid-liquid diffusion in Tygon tubing transported in the Enhanced Gaseous Nitrogen Dewar (EGN). Different volume ratios and concentrations of protein and precipitant were used to test different adaptations of the vapor-diffusion crystallization recipe to the liquid-liquid diffusion method. The EGN warmed up from 77 to 273 K in about 4 d, about the same time it took to warm from 273 to 293 K. The temperature within the EGN was 293-297 K for the majority of the experiment. Air gaps that blocked liquid-liquid diffusion formed in the tubes. Nonetheless, crystals were grown. Synchrotron diffraction data collected from the best space-grown crystal extended to 1.28 A, comparable to previous studies of space-grown thaumatin crystals. The resolution of the best ground-control crystal was only 1.47 A. It is not clear if the difference in diffraction limit arises from factors other than crystal size. Improvements in temperature control and the elimination of air gaps are needed, but the results show that the EGN on the ISS can be used to produce space-grown crystals that diffract to high resolution.
Thaumatin Crystallization Aboard the International Space Station Using Liquid-Liquid Diffusion in the Enhanced Gaseous Nitrogen Dewar (EGN)

NASA Technical Reports Server (NTRS)

Kundrot, Craig; Barnes, Cindy L.; Snell, Edward H.; Stinson, Thomas N. (Technical Monitor)

2002-01-01

This paper reports results from the first biological crystal growth experiment on the International Space Station (ISS). Crystals of thaumatin were grown using liquid-liquid diffusion in Tygon tubing transported in the Enhanced Gaseous Nitrogen Dewar (EGN). Different Volume ratios and concentrations of protein and precipitant were used to test different adaptations of the vapor diffusion crystallization recipe to the liquid-liquid diffusion method. The EGN warmed up from -196 C to 0 C in about four days, about the same time it took to warm from 0 C to 20 C. The temperature within the EGN was 20 - 24 C for the majority of the experiment. Air gaps that blocked liquid-liquid diffusion formed in the tubes. Nonetheless, crystals were grown. Synchrotron diffraction data collected from the best space grown crystal extended to 1.28 Angstroms, comparable to previous studies of space-grown thaumatin crystals. The resolution of the best ground control crystal was only 1.47 Angstroms. It is not clear if the difference in diffraction limit is due to factors other than crystal size. Improvements in temperature control and the elimination of air gaps are needed, but the results show that EGN on the ISS can be used to produce space grown crystals that diffract to high resolution.
Electrothermally Driven Fluorescence Switching by Liquid Crystal Elastomers Based On Dimensional Photonic Crystals.

PubMed

Lin, Changxu; Jiang, Yin; Tao, Cheng-An; Yin, Xianpeng; Lan, Yue; Wang, Chen; Wang, Shiqiang; Liu, Xiangyang; Li, Guangtao

2017-04-05

In this article, the fabrication of an active organic-inorganic one-dimensional photonic crystal structure to offer electrothermal fluorescence switching is described. The film is obtained by spin-coating of liquid crystal elastomers (LCEs) and TiO 2 nanoparticles alternatively. By utilizing the property of LCEs that can change their size and shape reversibly under external thermal stimulations, the λ max of the photonic band gap of these films is tuned by voltage through electrothermal conversion. The shifted photonic band gap further changes the matching degree between the photonic band gap of the film and the emission spectrum of organic dye mounting on the film. With rhodamine B as an example, the enhancement factor of its fluorescence emission is controlled by varying the matching degree. Thus, the fluorescence intensity is actively switched by voltage applied on the system, in a fast, adjustable, and reversible manner. The control chain of using the electrothermal stimulus to adjust fluorescence intensity via controlling the photonic band gap is proved by a scanning electron microscope (SEM) and UV-vis reflectance. This mechanism also corresponded to the results from the finite-difference time-domain (FDTD) simulation. The comprehensive usage of photonic crystals and liquid crystal elastomers opened a new possibility for active optical devices.
Ferroelectric BaTiO3 and LiNbO3 Nanoparticles Dispersed in Ferroelectric Liquid Crystal Mixtures: Electrooptic and Dielectric (Postprint)

DTIC Science & Technology

2016-10-14

Nematic Liquid Crystals allowing for rapidly changing moving pictures during the time frame below about 5-10 ms. Ferroelectric Liquid Crystals (FLCs...could fill this gap bearing some advantages over Nematic Liquid Crystals , mainly a fast switching time in the microsecond range, better optical...AFRL-RX-WP-JA-2017-0210 FERROELECTRIC BaTiO3 AND LiNbO3 NANOPARTICLES DISPERSED IN FERROELECTRIC LIQUID CRYSTAL MIXTURES: ELECTROOPTIC
A study examining the effects of water-miscible cutting fluids for end milling process of carbon fiber reinforced plastic

NASA Astrophysics Data System (ADS)

Anan, Ruito; Matsuoka, Hironori; Ono, Hajime; Ryu, Takahiro; Nakae, Takashi; Shuto, Schuichi; Watanabe, Suguru; Sato, Yuta

2017-04-01

This study examined the improvements to the tool life and finished surface roughness by using water-miscible cutting fluids in carbon fiber reinforced plastics end milling. In cutting tests, it was found that the use of emulsion type, soluble type, and solution type cutting fluids improved tool life compared with the case of dry cutting. Specifically, significant differences in tool life were observed at a high cutting speed of 171 m/min. In addition, the finished surface exhibited a low level of roughness when the solution type cutting fluid was used, regardless of the cutting speed.
Instability patterns in a miscible core annular flow

NASA Astrophysics Data System (ADS)

D'Olce, Marguerite; Martin, Jerome; Rakotomalala, Nicole; Salin, Dominique; Talon, Laurent

2006-11-01

Laboratoire FAST, batiment 502, campus universitaire, 91405 Orsay Cedex (France). Experiments are performed with two miscible fluids of equal density but different viscosities. The fluids are injected co-currently and concentrically into a cylindrical pipe. The so-obtained base state is an axisymmetric parallel flow, for which the ratio of the flow rates of the two fluids monitors the relative amount (and so the radius) of the fluids. Depending on this relative amount and on the total flow rate of the fluids, unstable axisymmetric patterns such as mushrooms and pearls are observed. We delineate the diagram of occurrence of the two patterns and characterize the instabilities.
Improved Efficiency of Miscible CO(2) Floods and Enhanced Prospects for CO(2) Flooding Heterogeneous Reservoirs.

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

Grigg, R.B.; Schechter, D.S.

The overall goal of this project was to improve the efficiency of miscible C0{sub 2} floods and enhance the prospects for flooding heterogeneous reservoirs. This objective was accomplished through experimental and modeling research in three task areas: (1) foams for selective mobility control in heterogeneous reservoirs,( 2) reduction of the amount of C0{sub 2} required in C0{sub 2} floods, and (3) low IFT processe and the possibility of C0{sub 2} flooding in fractured reservoirs. This report provides results from the three-year project for each of the three task areas.
Buoyancy driven mixing of miscible fluids by volumetric energy deposition of microwaves.

PubMed

Wachtor, Adam J; Mocko, Veronika; Williams, Darrick J; Goertz, Matthew P; Jebrail, Farzaneh F

2013-01-01

An experiment that seeks to investigate buoyancy driven mixing of miscible fluids by microwave volumetric energy deposition is presented. The experiment involves the use of a light, non-polar fluid that initially rests on top of a heavier fluid which is more polar. Microwaves preferentially heat the polar fluid, and its density decreases due to thermal expansion. As the microwave heating continues, the density of the lower fluid eventually becomes less than that of the upper, and buoyancy driven Rayleigh-Taylor mixing ensues. The choice of fluids is crucial to the success of the experiment, and a description is given of numerous fluid combinations considered and characterized. After careful consideration, the miscible pair of toluene/tetrahydrofuran (THF) was determined as having the best potential for successful volumetric energy deposition buoyancy driven mixing. Various single fluid calibration experiments were performed to facilitate the development of a heating theory. Thereafter, results from two-fluid mixing experiments are presented that demonstrate the capability of this novel Rayleigh-Taylor driven experiment. Particular interest is paid to the onset of buoyancy driven mixing and unusual aspects of the experiment in the context of typical Rayleigh-Taylor driven mixing.
Lifecycle of miscible viscous fingering: onset to shutdown

NASA Astrophysics Data System (ADS)

Nijjer, Japinder S.; Hewitt, Duncan R.; Neufeld, Jerome A.

2017-11-01

When a viscous fluid is injected into a porous medium or Hele-Shaw cell that is initially saturated with a more viscous fluid, the flow can be unstable to viscous fingering. We investigate the long-time dynamics of miscible viscous fingering in a homogeneous, planar, two-dimensional porous medium using high-resolution numerical simulations. At late times, we identify a new flow regime which consists of a pair of counter-propagating fingers that diffuse and slow, leaving a linearly well-mixed interior. We derive an analytic solution for this regime, and show that, in contrast to previous suggestions, the flow always evolves to this regime irrespective of the viscosity ratio and Peclet number. As a consequence, we find the instability can only ever generate a finite amount of advective mixing. We also describe the full life-cycle of miscible viscous fingering, which can be partitioned into three regimes: an early-time linearly unstable regime, an intermediate-time non-linear regime, and a late-time exchange-flow regime. We identify, using linear stability theory, a critical Peclet number below which the flow is always stable, and derive a model for the evolution of the transversely averaged concentration in the intermediate-time regime, which extends previous empirical models.
Competing Stereocomplexation and Homocrystallization of Poly(l-lactic acid)/Poly(d-lactic acid) Racemic Mixture: Effects of Miscible Blending with Other Polymers.

PubMed

Bao, Jianna; Xue, Xiaojia; Li, Kai; Chang, Xiaohua; Xie, Qing; Yu, Chengtao; Pan, Pengju

2017-07-20

Promoting the stereocomplexation ability of high-molecular-weight poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) is an efficient way to improve the thermal resistance of the resulting materials. Herein, we studied the competing crystallization kinetics, polymorphic crystalline structure, and lamellae structure of the PLLA/PDLA component in its miscible blends with poly(vinyl acetate) (PVAc) and proposed a method to improve the stereocomplexation ability of PLLA and PDLA through miscible blending with the other polymer. Crystallization of the PLLA/PDLA component is suppressed after the addition of PVAc, due to the dilution effect. The stereocomplexation ability of PLLA and PDLA is enhanced by blending with PVAc; this becomes more obvious at a high PVAc content (≥50 wt %) but less significant with the further increase of PLLA, PDLA molecular weights. Almost exclusive formation of SCs is achieved for PLLA and PDLA after blending with a large proportion of PVAc (e.g., 75 wt %). Incorporation of PVAc also facilitates the HC-to-SC structural reorganization upon heating. The increased chain mobility, decreased equilibrium melting point, and enhanced intermolecular interactions may account for the preferential stereocomplexation in PLLA/PDLA/PVAc blends.
Permanganate gel (PG) for groundwater remediation: compatibility, gelation, and release characteristics.

PubMed

Lee, Eung Seok; Olson, Pamela R; Gupta, Neha; Solpuker, Utku; Schwartz, Franklin W; Kim, Yongje

2014-02-01

Permanganate (MnO4(-)) is a strong oxidant that is widely used for treating chlorinated ethylenes in groundwater. This study aims to develop hyper-saline MnO4(-) solution (MnO4(-) gel; PG) that can be injected into aquifers via wells, slowly gelates over time, and slowly release MnO4(-) to flowing water. In this study, compatibility and miscibility of gels, such as chitosan, aluminosilicate, silicate, and colloidal silica gels, with MnO4(-) were tested. Of these gels, chitosan was reactive with MnO4(-). Aluminosilicates were compatible but not readily miscible with MnO4(-). Silicates and colloidal silica were both compatible and miscible with MnO4(-), and gelated with addition of KMnO4 granules. Colloidal silica has low initial viscosity (<15cP), exhibited delayed gelation characteristics with the lag times ranging from 0 to 200min. Release of MnO4(-) from the colloidal silica-based PG gel occurred in a delayed fashion, with maximum duration of 24h. These results suggested that colloidal silica can be used to create PG or delayed-gelling forms containing other oxidants which can be used for groundwater remediation. Copyright © 2013 Elsevier Ltd. All rights reserved.
Photonic gaps in cholesteric elastomers under deformation

NASA Astrophysics Data System (ADS)

Cicuta, P.; Tajbakhsh, A. R.; Terentjev, E. M.

2004-07-01

Cholesteric liquid crystal elastomers have interesting and potentially very useful photonic properties. In an ideal monodomain configuration of these materials, one finds a Bragg reflection of light in a narrow wavelength range and a particular circular polarization. This is due to the periodic structure of the material along one dimension. In many practical cases, the cholesteric rubber possesses a sufficient degree of quenched disorder, which makes the selective reflection broadband. We investigate experimentally the problem of how the transmittance of light is affected by mechanical deformation of the elastomer, and the relation to changes in liquid crystalline structure. We explore a series of samples which have been synthesized with photonic stop gaps across the visible range. This allows us to compare results with detailed theoretical predictions regarding the evolution of stop gaps in cholesteric elastomers.
Skylab 3 and 4 science demonstrations: Preliminary report

NASA Technical Reports Server (NTRS)

Bannister, T. C.

1974-01-01

Twelve science demonstrations were accomplished on the Skylab 3 and 4 missions. These were defined in response to crew requests for time-gap fillers and were designed to be accomplished using onboard equipment. The following 12 are described and the preliminary results are given: liquid floating zone; diffusion in liquids; ice melting; immiscible liquids; liquid films; gyroscope; Rochelle salt growth; deposition of silver crystals; fluid mechanics series; neutron environment; orbital mechanics; and charged particle mobility.
Petroleum geology of the Cusiana Field, Llanos Basin Foothills, Colombia

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

Cazier, E.C.; Hayward, A.B.; Espinosa, G.

1995-10-01

Cusiana field is located in the Llanos Foothills, 150 mi (240km) northeast of Bogota, Colombia. Light oil, gas, and condensate in Cusiana occur at drilling depths that average 15,000 ft (4575 m) in an asymmetric, hanging-wall anticlinal trap 15 mi (25 km) long and 3-4 mi (5-6 km) across, formed during the Miocene-Holocene deformation of the Eastern Cordillera. Top and lateral seals are provided by marine mudstones of the Oligocene Carbonera Group, and support a hydrocarbon column of over 1500 ft (460 m). Biomarker data from the hydrocarbons indicate a marine mudstone source interpreted to be the Turonian-Coniacian Gacheta Formation.more » Over 50% of the reserves occur in upper Eocene Mirador Formation sandstones, which were deposited predominantly in estuarine environments. Additional, deeper reservoirs include estuarine sandstones of the Paleocene Barco Formation and the shallow-marine Santonian-Campanian Upper Guadalupe Sandstone. Porosity in Cusiana is relatively low. Good permeability is retained, however, because the reservoirs are pure quartz-cemented quartzarenites that lack permeability-reducing authigenic clays and carbonate cements. Core and well test analyses indicate matrix permeability, not fracture permeability, provides the high deliverability of Cusiana wells. Cusiana hydrocarbon phases exist in a near-miscible, critical-point state. Reservoir simulation indicates very high liquid hydrocarbon recoveries should be possible from all reservoirs by using the reinjection of produced gas to maintain reservoir pressure and to vaporize residual liquids. The field contains up to 1.5 MSTB of hydrocarbon liquid reserves and 3.4 Tcf of gas.« less
Comparison of simulation and experimental results for a model aqueous tert-butanol solution

NASA Astrophysics Data System (ADS)

Overduin, S. D.; Patey, G. N.

2017-07-01

Molecular dynamics simulations are used to investigate the behavior of aqueous tert-butanol (TBA) solutions for a range of temperatures, using the CHARMM generalized force field (CGenFF) to model TBA and the TIP4P/2005 or TIP4P-Ew water model. Simulation results for the density, isothermal compressibility, constant pressure heat capacity, and self-diffusion coefficients are in good accord with experimental measurements. Agreement with the experiment is particularly good at low TBA concentration, where experiments have revealed anomalies in a number of thermodynamic properties. Importantly, the CGenFF model does not exhibit liquid-liquid demixing at temperatures between 290 and 320 K (for systems of 32 000 molecules), in contrast with the situation for several other common TBA models [R. Gupta and G. N. Patey, J. Chem. Phys. 137, 034509 (2012)]. However, whereas real water and TBA are miscible at all temperatures where the liquid is stable, we observe some evidence of demixing at 340 K and above. To evaluate the structural properties at low concentrations, we compare with both neutron scattering and recent spectroscopic measurements. This reveals that while the CGenFF model is a definite improvement over other models that have been considered, the TBA molecules still exhibit a tendency to associate at low concentrations that is somewhat stronger than that indicated by experiments. Finally, we discuss the range and decay times of the long-range correlations, providing an indication of the system size and simulation times that are necessary in order to obtain reliable results for certain properties.

Genetic significance of the 867 cm- 1 out-of-plane Raman mode in graphite associated with V-bearing green grossular

NASA Astrophysics Data System (ADS)

Thomas, Rainer; Rericha, Adolf; Pohl, Walter L.; Davidson, Paul

2018-03-01

SE Kenya is the world's largest producer of green vanadium grossular gemstones (tsavorite). Samples from one of the mines near Mwatate, and of occurrences in Tanzania yielded remarkable new insights into the genesis of tsavorite. Graphite is intimately associated with V-grossular and is one of the keys to understanding its origin. In the course of this study we found five different types of graphite. Surprisingly, in one graphite type the "Raman-forbidden" and IR-active 867 cm- 1 band was observed. In this communication, we attempt to find an explanation for this unusual phenomenon. Additionally, our observations also address some of the issues pertaining to the origin of the green grossular-dominated rocks (grossularites), as well as the gem quality tsavorite crystals, since we propose that the anomalous spectroscopic behavior of the graphite is related to the unusual conditions during crystallization of both the grossular and graphite from a near-supercritical volatile- and sulfur-rich silicate melt. The massive green vanadium grossular contains abundant unequivocal crystallized melt inclusions, while the transparent gem quality grossular (tsavorite) displays only fluid inclusions. On the basis of inclusion studies we suggest that anatectic melts originated in the peculiar evaporitic host lithology of the tsavorite deposits. Near peak metamorphic temperatures ( 700 °C) these liquids occurred as a supercritical volatile-rich "fluid/melt phase" characterized by complete miscibility between H2O and silicate liquid. Relatively dry liquid batches precipitated non-transparent green grossular, whereas wet batches segregated fluids that formed transparent tsavorite.
Global phase diagram and quantum spin liquids in a spin- 1 2 triangular antiferromagnet

DOE PAGES

Gong, Shou-Shu; Zhu, Wei; Zhu, Jianxin; ...

2017-08-09

For this research, we study the spin-1/2 Heisenberg model on the triangular lattice with the nearest-neighbor J 1 > 0 , the next-nearest-neighobr J 2 > 0 Heisenberg interactions, and the additional scalar chiral interaction Jχ (more » $$\\vec{S}$$ i × $$\\vec{S}$$ j ) · $$\\vec{S}$$ k for the three spins in all the triangles using large-scale density matrix renormalization group calculation on cylinder geometry. With increasing J 2 (J 2 / J 1 ≤ 0.3 ) and Jχ (Jχ / J 1 ≤ 1.0 ) interactions, we establish a quantum phase diagram with the magnetically ordered 120°, stripe, and noncoplanar tetrahedral phase. In between these magnetic order phases, we find a chiral spin liquid (CSL) phase, which is identified as a ν = 1/2 bosonic fractional quantum Hall state with possible spontaneous rotational symmetry breaking. By switching on the chiral interaction, we find that the previously identified spin liquid in the J 1 - J 2 triangular model (0.08 ≲ J 2 / J 1 ≲ 0.15) shows a phase transition to the CSL phase at very small Jχ. We also compute the spin triplet gap in both spin liquid phases, and our finite-size results suggest a large gap in the odd topological sector but a small or vanishing gap in the even sector. Lastly, we discuss the implications of our results on the nature of the spin liquid phases.« less
Gas driven displacement in a Hele-Shaw cell with chemical reaction

NASA Astrophysics Data System (ADS)

White, Andrew; Ward, Thomas

2011-11-01

Injecting a less viscous fluid into a more viscous fluid produces instabilities in the form of fingering which grow radially from the less viscous injection point (Saffman & Taylor, Proc. R. Soc. Lon. A, 1958). For two non-reacting fluids in a radial Hele-Shaw cell the ability of the gas phase to penetrate the liquid phase is largely dependent on the gap height, liquid viscosity and gas pressure. In contrast combining two reactive fluids such as aqueous calcium hydroxide and carbon dioxide, which form a precipitate, presents a more complex but technically relevant system. As the two species react calcium carbonate precipitates and increases the aqueous phase visocosity. This change in viscosity may have a significant impact on how the gas phase penetrates the liquid phase. Experimental are performed in a radial Hele-Shaw cell with gap heights O(10-100) microns by loading a single drop of aqueous calcium hydroxide and injecting carbon dioxide into the drop. The calcium hydroxide concentration, carbon dioxide pressure and gap height are varied and images of the gas penetration are analyzed to determine residual film thickness and bursting times.
Thermally triggered phononic gaps in liquids at THz scale

DOE PAGES

Bolmatov, Dima; Zhernenkov, Mikhail; Zavyalov, Dmitry; ...

2016-01-14

In this study we present inelastic X-ray scattering experiments in a diamond anvil cell and molecular dynamic simulations to investigate the behavior of phononic excitations in liquid Ar. The spectra calculated using molecular dynamics were found to be in a good agreement with the experimental data. Furthermore, we observe that, upon temperature increases, a low-frequency transverse phononic gap emerges while high-frequency propagating modes become evanescent at the THz scale. The effect of strong localization of a longitudinal phononic mode in the supercritical phase is observed for the first time. The evidence for the high-frequency transverse phononic gap due to themore » transition from an oscillatory to a ballistic dynamic regimes of motion is presented and supported by molecular dynamics simulations. This transition takes place across the Frenkel line thermodynamic limit which demarcates compressed liquid and non-compressed fluid domains on the phase diagram and is supported by calculations within the Green-Kubo phenomenological formalism. These results are crucial to advance the development of novel terahertz thermal devices, phononic lenses, mirrors, and other THz metamaterials.« less
Axial dispersion of non-Newtonian fluids in porous media

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

Payne, L.W.; Parker, H.W.

1973-01-01

Mixing of liquids in the direction parallel to flow through porous media, usually termed axial dispersion, is a significant factor in regard to chromatography columns, packed bed reactors, and miscible displacement methods for the recovery of petroleum. For this reason, axial dispersion rates have frequently been investigated, but practically investigations have employed low viscosity Newtonian fluid such as water and light hydrocarbons. In this research, pseudoplastic fluids having a power law exponent as low as 0.6 were employed at very low flow rates to facilitate the observation of non-Newtonian effects on axial dispersion rates. The flow system used in thismore » investigation was a vertically oriented glass bead pack. Glass beads of 470 mu nominal size were packed into the flow cell while vibrating the cell. The studies were conducted by displacing an undyed solution from the bead pack with a dyed solution at a constant rate aor visa versa. Vertical, downward flow was used in all displacements. (10 refs.)« less
Process for separating dissolved solids from a liquid using an anti-solvent and multiple effect evaporators

DOEpatents

Daniels, Edward J.; Jody, Bassam J.; Bonsignore, Patrick V.

1994-01-01

A process and system for treating aluminum salt cake containing water soluble halide salts by contacting the salt cake with water to dissolve water soluble halide salts forming a saturated brine solution. Transporting a portion of about 25% of the saturated brine solution to a reactor and introducing into the saturated brine solution at least an equal volume of a water-miscible low-boiling organic material such as acetone to precipitate a portion of the dissolved halide salts forming a three-phase mixture of an aqueous-organic-salt solution phase and a precipitated salt phase and an organic rich phase. The precipitated salt phase is separated from the other phases and the organic rich phase is recycled to the reactor. The remainder of the saturated brine solution is sent to a multiple effect evaporator having a plurality of stages with the last stage thereof producing low grade steam which is used to boil off the organic portion of the solution which is recycled.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnhill, William C.; Gao, Hong; Kheireddin, Bassem

We have previously reported an oil-miscible phosphonium-organophosphate ionic liquid (IL) with an effective anti-wear (AW) functionality when added to a base oil by itself or combined with a conventional zinc dialkyldithiophosphate (ZDDP) for a synergistic effect. In this research, we investigated whether this synergy manifests in formulated engine oils. An experimental SAE 0W-16 engine oil was generated containing a combination of IL and ZDDP with equal phosphorus contribution. The prototype engine oil was first evaluated using tribological bench tests: AW performance in boundary lubrication (BL) and friction behavior (Stribeck curves) in elastohydrodynamic, mixed, and BL. In addition, the forthcoming standardmore » Sequence VIE engine dynamometer test was then conducted to demonstrate improved fuel economy. Results were benchmarked against those of another experimental engine oil with almost the same formulation except using ZDDP only without the IL (similar total phosphorus content). The IL-ZDDP formulation consistently outperforms the ZDDP-only formulation in friction reduction and wear protection, and results from the bench and engine tests are well correlated.« less
Process for separating dissolved solids from a liquid using an anti-solvent and multiple effect evaporators

DOEpatents

Daniels, E.J.; Jody, B.J.; Bonsignore, P.V.

1994-07-19

A process and system are disclosed for treating aluminum salt cake containing water soluble halide salts by contacting the salt cake with water to dissolve water soluble halide salts forming a saturated brine solution. Transporting a portion of about 25% of the saturated brine solution to a reactor and introducing into the saturated brine solution at least an equal volume of a water-miscible low-boiling organic material such as acetone to precipitate a portion of the dissolved halide salts forming a three-phase mixture of an aqueous-organic-salt solution phase and a precipitated salt phase and an organic rich phase. The precipitated salt phase is separated from the other phases and the organic rich phase is recycled to the reactor. The remainder of the saturated brine solution is sent to a multiple effect evaporator having a plurality of stages with the last stage thereof producing low grade steam which is used to boil off the organic portion of the solution which is recycled. 3 figs.
Evidence for a Field-Induced Quantum Spin Liquid in α -RuCl3

NASA Astrophysics Data System (ADS)

Baek, S.-H.; Do, S.-H.; Choi, K.-Y.; Kwon, Y. S.; Wolter, A. U. B.; Nishimoto, S.; van den Brink, Jeroen; Büchner, B.

2017-07-01

We report a 35Cl nuclear magnetic resonance study in the honeycomb lattice α -RuCl3 , a material that has been suggested to potentially realize a Kitaev quantum spin liquid (QSL) ground state. Our results provide direct evidence that α -RuCl3 exhibits a magnetic-field-induced QSL. For fields larger than ˜10 T , a spin gap opens up while resonance lines remain sharp, evidencing that spins are quantum disordered and locally fluctuating. The spin gap increases linearly with an increasing magnetic field, reaching ˜50 K at 15 T, and is nearly isotropic with respect to the field direction. The unusual rapid increase of the spin gap with increasing field and its isotropic nature are incompatible with conventional magnetic ordering and, in particular, exclude that the ground state is a fully polarized ferromagnet. The presence of such a field-induced gapped QSL phase has indeed been predicted in the Kitaev model.
Complementary Constrains on Component based Multiphase Flow Problems, Should It Be Implemented Locally or Globally?

NASA Astrophysics Data System (ADS)

Shao, H.; Huang, Y.; Kolditz, O.

2015-12-01

Multiphase flow problems are numerically difficult to solve, as it often contains nonlinear Phase transition phenomena A conventional technique is to introduce the complementarity constraints where fluid properties such as liquid saturations are confined within a physically reasonable range. Based on such constraints, the mathematical model can be reformulated into a system of nonlinear partial differential equations coupled with variational inequalities. They can be then numerically handled by optimization algorithms. In this work, two different approaches utilizing the complementarity constraints based on persistent primary variables formulation[4] are implemented and investigated. The first approach proposed by Marchand et.al[1] is using "local complementary constraints", i.e. coupling the constraints with the local constitutive equations. The second approach[2],[3] , namely the "global complementary constrains", applies the constraints globally with the mass conservation equation. We will discuss how these two approaches are applied to solve non-isothermal componential multiphase flow problem with the phase change phenomenon. Several benchmarks will be presented for investigating the overall numerical performance of different approaches. The advantages and disadvantages of different models will also be concluded. References[1] E.Marchand, T.Mueller and P.Knabner. Fully coupled generalized hybrid-mixed finite element approximation of two-phase two-component flow in porous media. Part I: formulation and properties of the mathematical model, Computational Geosciences 17(2): 431-442, (2013). [2] A. Lauser, C. Hager, R. Helmig, B. Wohlmuth. A new approach for phase transitions in miscible multi-phase flow in porous media. Water Resour., 34,(2011), 957-966. [3] J. Jaffré, and A. Sboui. Henry's Law and Gas Phase Disappearance. Transp. Porous Media. 82, (2010), 521-526. [4] A. Bourgeat, M. Jurak and F. Smaï. Two-phase partially miscible flow and transport modeling in porous media : application to gas migration in a nuclear waste repository, Comp.Geosciences. (2009), Volume 13, Number 1, 29-42.
CO/sub 2/ line design needs

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

Recht, D.L.

Large volumes of carbon dioxide are required for tertiary oil recovery projects that utilize the carbon dioxide miscible flooding method. Carbon dioxide can be successfully transported as a supercritical fluid through a pipeline designed and operated similar to a natural gas pipeline, with careful consideration given to specific differences in design and materials of construction. Carbon dioxide is a colorless, odorless, nonflammable, non-toxic substance that may exist as a gas, as a liquid, as a solid, or in all three forms at its triple point. The critical pressure and temperature of CO/sub 2/ are 1,070 psia and 88/sup 0/F, respectively.more » It is present in the normal atmosphere in a concentration of approximately 330 ppm, and somewhat higher concentrations may occur in occupied buildings. Air in lungs contains approximately 5.5% (55,000 ppm) of CO/sub 2/. Although it is non-toxic, air containing 10% to 20% CO/sub 2/ concentrations by volume is immediately hazardous to life by causing unconsciousness, failure of respiratory muscles, and a change in the pH of the blood stream. Carbon dioxide is commonly used for carbonated beverages, aerosol propellants, fire extinguishers, enrichment of air in greenhouses, fracturing and acidizing of oil wells, as a shielding gas for welding, and as dry ice for refrigeration. In tertiary recovery projects of suitable oil reservoirs, CO/sub 2/ is injected into the formation where it dissolves in the oil, swells the oil, reduces the oil's viscosity, exerts an acidic effect on the reservoir rock (in some cases), and vaporizes some of the oil. As a rough rule of thumb, approximately 6 to 10 mcf of CO/sub 2/ are required to be injected for recovery of 1 bbl of oil. Carbon dioxide miscible flooding will recover approximately 10% to 15% of the oil remaining in place after a waterflood program.« less
Characterization of the influence of 1-butyl-3-methylimidazolium chloride on the structure and thermal stability of green fluorescent protein

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

Heller, William T; O'Neill, Hugh Michael; Zhang, Qiu

2010-01-01

Ionic liquids (ILs) are finding a vast array of applications as novel solvents for a wide variety of processes that include enzymatic chemistry, particularly as more biocompatible ILs are designed and discovered. While it is assumed that a native or near-native structure is required for enzymatic activity, there is some evidence that ILs alter protein structure and oligomerization states in a manner than can negatively impact function. The IL 1-butyl-3-methylimidazolium chloride, [bmim]Cl, is a well-studied, water-miscible member of the popular 1-alkyl-3-methylimidazolium IL family. To improve our understanding of the impact of water-miscible ILs on proteins, we have characterized the structuremore » and oligomerization state of green fluorescent protein (GFP) in aqueous solutions containing 25 and 50 vol % [bmim]Cl using a combination of optical spectroscopy and small-angle neutron scattering (SANS). Measurements were also performed as a function of temperature to provide insight into the effect of the IL on the thermal stability of GFP. While GFP exists as a dimer in water, the presence of 25 vol % [bmim]Cl causes GFP to transition to a monomeric state. The SANS data indicate that GFP is a great deal less compact in 50 vol % [bmim]Cl than in neat water, indicative of unfolding from the native structure. The oligomerization state of the protein in IL-containing aqueous solution changes from a dimer to a monomer in response to the IL, but does not change as a function of temperature in the IL-containing solution. The SANS and spectroscopic results also demonstrate that the addition of [bmim]Cl to the solution decreases the thermal stability of GFP, allowing the protein to unfold at lower temperatures than in aqueous solution.« less
Fast response liquid crystal devices

NASA Astrophysics Data System (ADS)

Wu, Yung-Hsun

Liquid crystal (LC) has been widely used for displays, spatial light modulators, variable optical attenuators (VOAs) and other tunable photonic devices. The response time of these devices is mainly determined by the employed liquid crystal material. The response time of a LC device depends on the visco-elastic coefficient (gamma1/K11), LC cell gap (d), and applied voltage. Hence, low visco-elastic coefficient LC materials and thinner cell gap are favorable for reducing the response time. However, low visco-elastic coefficient LCs are usually associated with a low birefringence because of shorter molecular conjugation. For display applications, such as LCD TVs, low birefringence (Deltan<0.1) LCs are commonly used. However, for optical communications at 1550 nm, low birefringence requires to a thick cell gap which, in turn, increases the response time. How to obtain fast response for the LC devices is a fundamentally important and technically challenging task. In this dissertation, we investigate several methods to improve liquid crystal response time, for examples, using dual-frequency liquid crystals, polymer stabilized liquid crystals, and sheared polymer network liquid crystals. We discover a new class of material, denoted as sheared polymer network liquid crystal (SPNLC) which exhibits a submillisecond response time. Moreover, this response time is insensitive to the LC cell gap. This is the first LC device exhibiting such an interesting property. Chapters 1 and 2 describe the motivation and background of this dissertation. From chapter 3 to chapter 6, dual-frequency liquid crystals and polymer network methods are demonstrated as examples for the variable optical attenuators. Variable optical attenuator (VOA) is a key component in optical communications. Especially, the sheared PNLC VOA shows the best result; its dynamic range reaches 43 dB while the response time is in the submillisecond range at 1550 nm wavelength, which is 50 times faster than the commercial LC-based VOA. In Chapter 7, we report a new device called axially-symmetric sheared polymer network liquid crystals (AS-SPNLC) and use it as LC devices. Through analyzing the structure of this axially-symmetric SPNLC, we construct a 3-D model to explain the observed phenomena. An axially-symmetric sheared polymer network liquid crystal has several attractive features: (1) it is polarization independent, (2) it has gradient phase change, and (3) its response time is fast. It can be used for polarization converter and divergent LC lens. In addition, a new method for simultaneously measuring the phase retardation and optic axis of a compensation film is demonstrated using an axially-symmetric sheared polymer network liquid crystal. By overlaying a tested compensation film with a calibrated SPNLC cell between crossed polarizers, the optic axis and phase retardation value of the compensation film can be determined. This simple technique can be used for simultaneously measuring the optic axis and phase retardations of both A- and C-plates. These compensation films have been used extensively in wide-view LCD industry. Therefore, this method will make an important impact to the LCD industry.
Microscopic understanding of heavy-tailed return distributions in an agent-based model

NASA Astrophysics Data System (ADS)

Schmitt, Thilo A.; Schäfer, Rudi; Münnix, Michael C.; Guhr, Thomas

2012-11-01

The distribution of returns in financial time series exhibits heavy tails. It has been found that gaps between the orders in the order book lead to large price shifts and thereby to these heavy tails. We set up an agent-based model to study this issue and, in particular, how the gaps in the order book emerge. The trading mechanism in our model is based on a double-auction order book. In situations where the order book is densely occupied with limit orders we do not observe fat-tailed distributions. As soon as less liquidity is available, a gap structure forms which leads to return distributions with heavy tails. We show that return distributions with heavy tails are an order-book effect if the available liquidity is constrained. This is largely independent of specific trading strategies.
Solvent for urethane adhesives and coatings and method of use

DOEpatents

Simandl, Ronald F.; Brown, John D.; Holt, Jerrid S.

2010-08-03

A solvent for urethane adhesives and coatings, the solvent having a carbaldehyde and a cyclic amide as constituents. In some embodiments the solvent consists only of miscible constituents. In some embodiments the carbaldehyde is benzaldehyde and in some embodiments the cyclic amide is N-methylpyrrolidone (M-pyrole). An extender may be added to the solvent. In some embodiments the extender is miscible with the other ingredients, and in some embodiments the extender is non-aqueous. For example, the extender may include isopropanol, ethanol, tetrahydro furfuryl alcohol, benzyl alcohol, Gamma-butyrolactone or a caprolactone. In some embodiments a carbaldehyde and a cyclic amide are heated and used to separate a urethane bonded to a component.
Molecular Probe Fluorescence Monitoring of Polymerization

NASA Technical Reports Server (NTRS)

Bunton, Patrick

2002-01-01

This project investigated the feasibility of using fluorescence spectroscopy to determine viscosity of polymer/monomer in support of Transient Interfacial Phenomena in Miscible Polymer Systems (TIPMPS). This project will attempt to measure gradient induced flow at a miscible interface during and / or after in-flight polymerization of dodecyl acrylate (lauryl acrylate). Concentration and temperature gradients will be intentionally introduced during polymerization and the resultant fluid flow determined by Particle Imaging Velocimetry (PIV). This report describes an investigation of the feasibility of using fluorescence of a probe molecule to monitor viscosity and/or concentration during and after polymerization. The probe used was pyrene which has been shown to be sensitive to its local environment in methyl methacrylate.
Photo-switchable bistable twisted nematic liquid crystal optical switch.

PubMed

Wang, Chun-Ta; Wu, Yueh-Chi; Lin, Tsung-Hsien

2013-02-25

This work demonstrates a photo-switchable bistable optical switch that is based on an azo-chiral doped liquid crystal (ACDLC). The photo-induced isomerization of the azo-chiral dopant can change the chirality of twisted nematic liquid crystal and the gap/pitch ratio of an ACDLC device, enabling switching between 0° and 180° twist states in a homogeneous aligned cell. The bistable 180° and 0° twist states of the azo-chiral doped liquid crystal between crossed polarizers correspond to the ON and OFF states of a light shutter, respectively, and they can be maintained stably for tens of hours. Rapid switching between 180° and 0° twist states can be carried out using 408 and 532 nm addressing light. Such a photo-controllable optical switch requires no specific asymmetric alignment layer or precise control of the cell gap/pitch ratio, so it is easily fabricated and has the potential for use in optical systems.
Liquid crystal dynamic flow control by bidirectional alignment surface

NASA Astrophysics Data System (ADS)

Li, Y. W.; Lee, C. Y.; Kwok, H. S.

2009-02-01

We investigate the behavior of liquid crystal dynamic flow in a cell with a bidirectional alignment (BDA) surface. Numerical simulations show that with a BDA surface having a pitch comparable to the cell gap d, the liquid crystal dynamic flow direction can be controlled by the driving voltage. Such an effect can be applied to bistable twisted nematic displays without the need for anchoring breaking.
Liquid Level Sensing System

NASA Technical Reports Server (NTRS)

Korman, Valentin (Inventor); Wiley, John T. (Inventor); Duffell, Amanda G. (Inventor)

2014-01-01

A liquid level sensing system includes waveguides disposed in a liquid and distributed along a path with a gap between adjacent waveguides. A source introduces electromagnetic energy into the waveguides at a first end of the path. A portion of the electromagnetic energy exits the waveguides at a second end of the path. A detector measures the portion of the electromagnetic energy exiting the second end of the path.
Effect of neurosteroids on a model lipid bilayer including cholesterol: An Atomic Force Microscopy study.

PubMed

Sacchi, Mattia; Balleza, Daniel; Vena, Giulia; Puia, Giulia; Facci, Paolo; Alessandrini, Andrea

2015-05-01

Amphiphilic molecules which have a biological effect on specific membrane proteins, could also affect lipid bilayer properties possibly resulting in a modulation of the overall membrane behavior. In light of this consideration, it is important to study the possible effects of amphiphilic molecule of pharmacological interest on model systems which recapitulate some of the main properties of the biological plasma membranes. In this work we studied the effect of a neurosteroid, Allopregnanolone (3α,5α-tetrahydroprogesterone or Allo), on a model bilayer composed by the ternary lipid mixture DOPC/bSM/chol. We chose ternary mixtures which present, at room temperature, a phase coexistence of liquid ordered (Lo) and liquid disordered (Ld) domains and which reside near to a critical point. We found that Allo, which is able to strongly partition in the lipid bilayer, induces a marked increase in the bilayer area and modifies the relative proportion of the two phases favoring the Ld phase. We also found that the neurosteroid shifts the miscibility temperature to higher values in a way similarly to what happens when the cholesterol concentration is decreased. Interestingly, an isoform of Allo, isoAllopregnanolone (3β,5α-tetrahydroprogesterone or isoAllo), known to inhibit the effects of Allo on GABAA receptors, has an opposite effect on the bilayer properties. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrical Characterization of Glycerin: Water Mixtures: Implications for Use as a Coupling Medium in Microwave Tomography

PubMed Central

Meaney, Paul M.; Fox, Colleen J.; Geimer, Shireen D.; Paulsen, Keith D.

2016-01-01

We examine the broadband behavior of complex electrical properties of glycerin and water mixtures over the frequency range of 0.1 – 25.0 GHz, especially as they relate to using these liquids as coupling media for microwave tomographic imaging. Their combination is unique in that they are mutually miscible over the full range of concentrations which allows them to be tailored to dielectric property matching for biological tissues. While the resultant mixture properties are partially driven by differences in the inherent low frequency permittivity of each constituent, relaxation frequency shifts play a disproportionately larger role in increasing the permittivity dispersion while also dramatically increasing the effective conductivity over the frequency range of 1 to 3 GHz. For the full range of mixture ratios, the relaxation frequency shifts from 17.5 GHz for 0% glycerin to less than 0.1 GHz for 100% glycerin. Of particular interest is the fact that the conductivity stays above 1.0 S/m over the 1–3 GHz range for glycerin mixture ratios (70–90% glycerin) we use for microwave breast tomography. The high level of attenuation is critical for suppressing unwanted multipath signals. This paper presents a full characterization of these liquids along with a discussion of their benefits and limitations in the context of microwave tomography. PMID:28507391
A coupled chemo-thermo-hygro-mechanical model of concrete at high temperature and failure analysis

NASA Astrophysics Data System (ADS)

Li, Xikui; Li, Rongtao; Schrefler, B. A.

2006-06-01

A hierarchical mathematical model for analyses of coupled chemo-thermo-hygro-mechanical behaviour in concretes at high temperature is presented. The concretes are modelled as unsaturated deforming reactive porous media filled with two immiscible pore fluids, i.e. the gas mixture and the liquid mixture, in immiscible-miscible levels. The thermo-induced desalination process is particularly integrated into the model. The chemical effects of both the desalination and the dehydration processes on the material damage and the degradation of the material strength are taken into account. The mathematical model consists of a set of coupled, partial differential equations governing the mass balance of the dry air, the mass balance of the water species, the mass balance of the matrix components dissolved in the liquid phases, the enthalpy (energy) balance and momentum balance of the whole medium mixture. The governing equations, the state equations for the model and the constitutive laws used in the model are given. A mixed weak form for the finite element solution procedure is formulated for the numerical simulation of chemo-thermo-hygro-mechanical behaviours. Special considerations are given to spatial discretization of hyperbolic equation with non-self-adjoint operator nature. Numerical results demonstrate the performance and the effectiveness of the proposed model and its numerical procedure in reproducing coupled chemo-thermo-hygro-mechanical behaviour in concretes subjected to fire and thermal radiation.
Quantum oscillations in a two-dimensional electron gas at the rocksalt/zincblende interface of PbTe/CdTe (111) heterostructures

DOE PAGES

Zhang, Bingpo; Lu, Ping; Liu, Henan; ...

2015-06-05

Quantum oscillations are observed in the 2DEG system at the interface of novel heterostructures, PbTe/CdTe (111), with nearly identical lattice parameters (a PbTe = 0.6462 nm, a CdTe = 0.648 nm) but very different lattice structures (PbTe: rock salt, CdTe: zinc blende). The 2DEG formation mechanism, a mismatch in the bonding configurations of the valence electrons at the interface, is uniquely different from the other known 2DEG systems. The aberration-corrected scanning transmission electron microscope (AC-STEM) characterization indicates an abrupt interface without cation interdiffusion due to a large miscibility gap between the two constituent materials. As a result, electronic transport measurementsmore » under magnetic field up to 60 T, with the observation of Landau level filling factor ν = 1, unambiguously reveal a π Berry phase, suggesting the Dirac Fermion nature of the 2DEG at the heterostructure interface, and the PbTe/CdTe heterostructure being a new candidate for 2D topological crystalline insulators.« less
In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles

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

Zhong, Li; Liu, Yang; Han, Wei-Qiang

Although a non-equilibrium single-phase reaction, with the absence of nucleation and growth of a second phase, is believed to be a key factor for high-rate performance of lithium-ion batteries, it is thermodynamically unfavorable and usually proceeds in electrode materials with small particle sizes (tens of nanometers). Unfortunately, the phase evolutions inside such small particles are often shrouded by the macroscopic inhomogeneous reactions of electrodes containing millions of particles, leading to intensive debate over the size-dependent microscopic reaction mechanisms. Here, we provide a generally applicable methodology based on in-situ electron diffraction study on a multi-particle system to track the lithiation pathwaysmore » in individual nanoparticles, and unambiguously reveal that lithiation of anatase TiO 2, previously long believed to be biphasic, converts to a single-phase reaction when the particle size is below ~25 nm. Our results imply the prevalence of such a size-dependent transition in lithiation mechanism among intercalation compounds whose lithium miscibility gaps are associated with a prominent size effect, and therefore provide important guidelines for designing high-power electrodes, especially cathodes.« less
Growth far from equilibrium: Examples from III-V semiconductors

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

Kuech, Thomas F.; Babcock, Susan E.; Mawst, Luke

The development of new applications has driven the field of materials design and synthesis to investigate materials that are not thermodynamically stable phases. Materials which are not thermodynamically stable can be synthesized and used in many applications. These materials are kinetically stabilized during use. The formation of such metastable materials requires both an understanding of the associated thermochemistry and the key surface transport processes present during growth. Phase separation is most easily accomplished at the growth surface during synthesis where mass transport is most rapid. These surface transport processes are sensitive to the surface stoichiometry, reconstruction, and chemistry as wellmore » as the growth temperature. The formation of new metastable semiconducting alloys with compositions deep within a compositional miscibility gap serves as model systems for the understanding of the surface chemical and physical processes controlling their formation. The GaAs{sub 1−y}Bi{sub y} system is used here to elucidate the role of surface chemistry in the formation of a homogeneous metastable composition during the chemical vapor deposition of the alloy system.« less
Laser-induced reversion of δ' precipitates in an Al-Li alloy: Study on temperature rise in pulsed laser atom probe.

PubMed

Khushaim, Muna; Gemma, Ryota; Al-Kassab, Talaat

2016-08-01

The influence of tuning the laser pulse energy during the analyses on the resulting microstructure in a specimen utilizing an ultra-fast laser assisted atom probe was demonstrated by a case study of a binary Al-Li alloy. The decomposition parameters, such as the size, number density, volume fraction, and composition of δ' precipitates, were carefully monitored after each analysis. A simple model was employed to estimate the corresponding specimen temperature for each value of the laser energy. The results indicated that the corresponding temperatures for the laser pulse energy in the range of 10 to 80 pJ are located inside the miscibility gap of the binary Al-Li phase diagram and fall into the metastable equilibrium field. In addition, the corresponding temperature for a laser pulse energy of 100 pJ was in fairly good agreement with reported range of δ' solvus temperature, suggesting a result of reversion upon heating due to laser pulsing. Microsc. Res. Tech. 79:727-737, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.
In Situ Observation of Single-Phase Lithium Intercalation in Sub-25-nm Nanoparticles

DOE PAGES

Zhong, Li; Liu, Yang; Han, Wei-Qiang; ...

2017-05-05

Although a non-equilibrium single-phase reaction, with the absence of nucleation and growth of a second phase, is believed to be a key factor for high-rate performance of lithium-ion batteries, it is thermodynamically unfavorable and usually proceeds in electrode materials with small particle sizes (tens of nanometers). Unfortunately, the phase evolutions inside such small particles are often shrouded by the macroscopic inhomogeneous reactions of electrodes containing millions of particles, leading to intensive debate over the size-dependent microscopic reaction mechanisms. Here, we provide a generally applicable methodology based on in-situ electron diffraction study on a multi-particle system to track the lithiation pathwaysmore » in individual nanoparticles, and unambiguously reveal that lithiation of anatase TiO 2, previously long believed to be biphasic, converts to a single-phase reaction when the particle size is below ~25 nm. Our results imply the prevalence of such a size-dependent transition in lithiation mechanism among intercalation compounds whose lithium miscibility gaps are associated with a prominent size effect, and therefore provide important guidelines for designing high-power electrodes, especially cathodes.« less
Thermodynamic modeling of solid solutions between monosulfate and monochromate 3CaO Bullet Al{sub 2}O{sub 3} Bullet Ca[(CrO{sub 4}){sub x}(SO{sub 4}){sub 1-x}] Bullet nH{sub 2}O

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

Leisinger, Sabine M., E-mail: sabine.leisinger@eawag.ch; Institute of Biogeochemistry and Pollutant Dynamics, ETH, CH-8092 Zurich; Lothenbach, Barbara

2012-01-15

In hydrated cement paste AFm-phases are regarded to play an important role in the binding of the toxic contaminant chromate through isomorphic substitution with sulfate. Solid solutions formation can lower the solubility of the solids, thus reducing chromate leaching concentrations. Solid solutions between monosulfate and monochromate were synthesized and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Based on the measured ion concentrations in solution total solubility products of the solid solution series were determined. For pure monochromate a logK = - 28.4more » {+-} 0.7 was determined. Results from solid and solution analysis showed that limited solid solutions exist. Based on XRD diffractograms a solid solution with a miscibility gap 0.15 < Crx < 0.85 with a dimensionless Guggenheim parameter of 2.43 was proposed.« less
Upgrade plans for the ATLAS Forward Calorimeter at the HL-LHC

NASA Astrophysics Data System (ADS)

Rutherfoord, John; ATLAS Liquid Argon Calorimeter Group

2012-12-01

Although data-taking at CERN's Large Hadron Collider (LHC) is expected to continue for a number of years, plans are already being developed for operation of the LHC and associated detectors at an increased instantaneous luminosity about 5 times the original design value of 1034 cm-2 s-1. The increased particle flux at this high luminosity (HL) will have an impact on many sub-systems of the ATLAS detector. In particular, in the liquid argon forward calorimeter (FCal), which was designed for operation at LHC luminosities, the associated increase in the ionization load at HL-LHC luminosities creates a number of problems which can degrade its performance. These include space-charge effects in the liquid argon gaps, excessive drop in potential across the gaps due to large HV supply currents through the protection resistors, and an increase in temperature which may cause the liquid argon to boil. One solution, which would require opening both End-Cap cryostats, is the construction and installation of new FCals with narrower liquid argon gaps, lowering the values of the protection resistors, and the addition of cooling loops. A second proposed solution, which does not require opening the cryostat cold volume, is the addition of a small, warm calorimeter in front of each existing FCal, resulting in a reduction of the particle flux to levels at which the existing FCal can operate normally.
Microsecond-range optical shutter for unpolarized light with chiral nematic liquid crystal

NASA Astrophysics Data System (ADS)

Mohammadimasoudi, Mohammad; Shin, Jungsoon; Lee, Keechang; Neyts, Kristiaan; Beeckman, Jeroen

2015-04-01

A fast electro-optic shutter is fabricated and demonstrated. The device works independently of the polarization state of the incoming light beam. Modulation between 3% transmission and 60% transmission is obtained within a wavelength range of 50 nm with a response time of 20 μs. The device consists of two partly polymerized chiral nematic liquid crystal layers separated by a half wave plate. The transmission modulation is due to a 50 nm wavelength shift of the photonic band gap of the chiral liquid crystal realized by applying an electric field over a mixture of photo-polymerized LC and non-reactive nematic LC containing a chiral dopant. The shutter features high reflectivity in the photonic band gap. We investigate the influence of the amplitude of the applied voltage on the width and the depth of the reflection band.
Entanglement Length in Miscible Blends of cis-Polyisoprene and Poly(ptert-butylstyrene)

NASA Astrophysics Data System (ADS)

Watanabe, Hiroshi; Matsumiya, Yumi

In miscible polymer blends, the entanglement length is common for the components, but its changes with the composition w remain unclear. For this problem, this study analyzed viscoelastic data for miscible blends of cis-polyisoprene (PI) and poly(ptert-butylstyrene) (PtBS), considering the basic feature that the local relaxation is determined only by wPI. On the basis of this feature, a series of unentangled low- M PI/PtBS blends having various M and a given wPI were utilized as references for well-entangled high- M PI/PtBS blends having the same wPI, and the modulus data of the references were subtracted from the high- M blend data. For an optimally chosen reference, the storage modulus Ge'of the high- M blends obtained after the subtraction exhibited a clear entanglement plateau GN and the corresponding Ge' ' decreased in proportion to 1/ ω at high frequencies ω. Thus, the onset of entanglement relaxation was detected. The GN values were well described by a linear mixing rule of the entanglement length with the number fraction of Kuhn segments of the components being utilized as the averaging weight. This result, not explained by a mean-field picture of entanglement, is discussed in relation to local packing of bulky PtBS chains and skinny PI chains.
Amorphous stabilization and dissolution enhancement of amorphous ternary solid dispersions: combination of polymers showing drug-polymer interaction for synergistic effects.

PubMed

Prasad, Dev; Chauhan, Harsh; Atef, Eman

2014-11-01

The purpose of this study was to understand the combined effect of two polymers showing drug-polymer interactions on amorphous stabilization and dissolution enhancement of indomethacin (IND) in amorphous ternary solid dispersions. The mechanism responsible for the enhanced stability and dissolution of IND in amorphous ternary systems was studied by exploring the miscibility and intermolecular interactions between IND and polymers through thermal and spectroscopic analysis. Eudragit E100 and PVP K90 at low concentrations (2.5%-40%, w/w) were used to prepare amorphous binary and ternary solid dispersions by solvent evaporation. Stability results showed that amorphous ternary solid dispersions have better stability compared with amorphous binary solid dispersions. The dissolution of IND from the ternary dispersion was substantially higher than the binary dispersions as well as amorphous drug. Melting point depression of physical mixtures reveals that the drug was miscible in both the polymers; however, greater miscibility was observed in ternary physical mixtures. The IR analysis confirmed intermolecular interactions between IND and individual polymers. These interactions were found to be intact in ternary systems. These results suggest that the combination of two polymers showing drug-polymer interaction offers synergistic enhancement in amorphous stability and dissolution in ternary solid dispersions. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.
The Dynamics of Miscible Fluids: A Space Flight Experiment (MIDAS)

NASA Technical Reports Server (NTRS)

Maxworthy, T.; Meiburg, E.; Balasubramaniam, R.; Rashidnia, N.; Lauver, R.

2001-01-01

We propose a space flight experiment to study the dynamics of miscible interfaces. A less viscous fluid displaces one of higher viscosity within a tube. The two fluids are miscible in all proportions. An intruding "finger" forms that occupies a fraction of the tube. As time progresses diffusion at the interface combined with flow induced straining between the two fluids modifies the concentration and velocity distributions within the whole tube. Also, under such circumstances it has been proposed that the interfacial stresses could depend on the local concentration gradients (Korteweg stresses) and that the divergence of the velocity need not be zero, even though the flow is incompressible. We have obtained reasonable agreement for the tip velocity between numerical simulations (that ignored the Korteweg stress and divergence effects) and physical experiments only at high Peelet Numbers. However at moderate to low Pe agreement was poor. As one possibility we attributed this lack of agreement to the disregard of these effects. We propose a space experiment to measure the finger shape, tip velocity, and the velocity and concentration fields. From intercomparisons between the experiment and the calculations we can then extract values for the coefficients of the Korteweg stress terms and confirm or deny the importance of these stresses.
The Dynamics of Miscible Fluids: A Space Flight Experiment (MIDAS)

NASA Technical Reports Server (NTRS)

Maxworthy, T.; Meiburg, E.; Balasubramaniam, R.; Rashidnia, N.; Lauver, R.

2001-01-01

We propose a space flight experiment to study the dynamics of miscible interfaces. A less viscous fluid displaces one of higher viscosity within a tube. The two fluids are miscible in all proportions. An intruding "finger" forms that occupies a fraction of the tube. As time progresses diffusion at the interface combined with flow induced straining between the two fluids modifies the concentration and velocity distributions within the whole tube. Also, under such circumstances it has been proposed that the interfacial stresses could depend on the local concentration gradients (Korteweg stresses) and that the divergence of the velocity need not be zero, even though the flow is incompressible. We have obtained reasonable agreement for the tip velocity between numerical simulations (that ignored the Korteweg stress and divergence effects) and physical experiments only at high Peclet Numbers. However at moderate to low Pe agreement was poor. As one possibility we attributed this lack of agreement to the disregard of these effects. We propose a space experiment to measure the finger shape, tip velocity, and the velocity and concentration fields. From intercomparisons between the experiment and the calculations we can then extract values for the coefficients of the Korteweg stress terms and confirm or deny the importance of these stresses.
A Molecular-Level View of the Physical Stability of Amorphous Solid Dispersions

NASA Astrophysics Data System (ADS)

Yuan, Xiaoda

Many pharmaceutical compounds being developed in recent years are poorly soluble in water. This has led to insufficient oral bioavailability of many compounds in vitro. The amorphous formulation is one of the promising techniques to increase the oral bioavailability of these poorly water-soluble compounds. However, an amorphous drug substance is inherently unstable because it is a high energy form. In order to increase the physical stability, the amorphous drug is often formulated with a suitable polymer to form an amorphous solid dispersion. Previous research has suggested that the formation of an intimately mixed drug-polymer mixture contributes to the stabilization of the amorphous drug compound. The goal of this research is to better understand the role of miscibility, molecular interactions and mobility on the physical stability of amorphous solid dispersions. Methods were developed to detect different degrees of miscibility on nanometer scale and to quantify the extent of hydrogen-bonding interactions between the drug and the polymer. Miscibility, hydrogen-bonding interactions and molecular mobility were correlated with physical stability during a six-month period using three model systems. Overall, this research provides molecular-level insights into many factors that govern the physical stability of amorphous solid dispersions which can lead to a more effective design of stable amorphous formulations.
Miscibility of choline-substituted polyphosphazenes with PLGA and osteoblast activity on resulting blends.

PubMed

Weikel, Arlin L; Owens, Steven G; Morozowich, Nicole L; Deng, Meng; Nair, Lakshmi S; Laurencin, Cato T; Allcock, Harry R

2010-11-01

The preparation of phosphazene tissue engineering scaffolds with bioactive side groups has been accomplished using the biological buffer, choline chloride. Mixed-substituent phosphazene cyclic trimers (as model systems) and polymers with choline chloride and glycine ethyl ester, alanine ethyl ester, valine ethyl ester, or phenylalanine ethyl ester were synthesized. Two different synthetic protocols were examined. A sodium hydride mediated route resulted in polyphosphazenes with a low choline content, while a cesium carbonate mediated process produced polyphosphazenes with higher choline content. The phosphazene structures and physical properties were studied using multinuclear NMR, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC) techniques. The resultant polymers were then blended with PLGA (50:50) or PLGA (85:15) and characterized by DSC analysis and scanning electron microscopy (SEM). Polymer products obtained via the sodium hydride route produced miscible blends with both ratios of PLGA, while the cesium carbonate route yielded products with reduced blend miscibility. Heterophase hydrolysis experiments in aqueous media revealed that the polymer blends hydrolyzed to near-neutral pH media (∼5.8 to 6.8). The effect of different molecular structures on cellular adhesion showed osteoblast proliferation with an elevated osteoblast phenotype expression compared to PLGA over a 21-day culture period. Copyright © 2010 Elsevier Ltd. All rights reserved.
Ternary Solar Cells Based on Two Small Molecule Donors with Same Conjugated Backbone: The Role of Good Miscibility and Hole Relay Process.

PubMed

Xiao, Liangang; Liang, Tianxiang; Gao, Ke; Lai, Tianqi; Chen, Xuebin; Liu, Feng; Russell, Thomas P; Huang, Fei; Peng, Xiaobin; Cao, Yong

2017-09-06

Ternary organic solar cells (OSCs) are very attractive for further enhancing the power conversion efficiencies (PCEs) of binary ones but still with a single active layer. However, improving the PCEs is still challenging because a ternary cell with one more component is more complicated on phase separation behavior. If the two donors or two acceptors have similar chemical structures, good miscibility can be expected to reduce the try-and-error work. Herein, we report ternary devices based on two small molecule donors with the same backbone but different substituents. Whereas both binary devices show PCEs about 9%, the PCE of the ternary cells is enhanced to 10.17% with improved fill factor and short-circuit current values and external quantum efficiencies almost in the whole absorption wavelength region from 440 to 850 nm. The same backbone enables the donors miscible at molecular level, and the donor with a higher HOMO level plays hole relay process to facilitate the charge transportation in the ternary devices. Since side-chain engineering has been well performed to tune the active materials' energy levels in OSCs, our results suggest that their ternary systems are promising for further improving the binary cells' performance although their absorptions are not complementary.
Three-dimensional Rayleigh-Taylor convection of miscible fluids in a porous medium

NASA Astrophysics Data System (ADS)

Suekane, Tetsuya; Nakanishi, Yuji; Wang, Lei

2017-11-01

Natural convection of miscible fluids in a porous medium is relevant for fields, such as geoscience and geoengineering, and for the geological storage of CO2. In this study, we use X-ray computer tomography to visualize 3D fingering structures associated with the Rayleigh-Taylor instability between miscible fluids in a porous medium. In the early stages of the onset of the Rayleigh-Taylor instability, a fine crinkling pattern gradually appears at the interface. As the wavelength and amplitude increase, descending fingers form on the interface and extend vertically downward; moreover, ascending and highly symmetric fingers form. The adjacent fingers are cylindrical in shape and coalesce to form large fingers. Fingers appearing on the interface tend to become finer with increasing Rayleigh number, which is consistent with linear perturbation theory. If the Péclet number exceeds 10, the transverse dispersion increases the finger diameter and enhances finger coalescence, strongly impacting the decay in finger number density. When mechanical dispersion is negligible, the finger-extension velocity, the mass-transfer rate, and the onset time scale with Rayleigh number. Mechanical dispersion not only reduces the onset time but also enhances mass transport, which indicates that mechanical dispersion influences the long-term dissolution process of CO2 injected into aquifers.
Behavior of CO2/water flow in porous media for CO2 geological storage.

PubMed

Jiang, Lanlan; Yu, Minghao; Liu, Yu; Yang, Mingjun; Zhang, Yi; Xue, Ziqiu; Suekane, Tetsuya; Song, Yongchen

2017-04-01

A clear understanding of two-phase fluid flow properties in porous media is of importance to CO 2 geological storage. The study visually measured the immiscible and miscible displacement of water by CO 2 using MRI (magnetic resonance imaging), and investigated the factor influencing the displacement process in porous media which were filled with quartz glass beads. For immiscible displacement at slow flow rates, the MR signal intensity of images increased because of CO 2 dissolution; before the dissolution phenomenon became inconspicuous at flow rate of 0.8mLmin -1 . For miscible displacement, the MR signal intensity decreased gradually independent of flow rates, because supercritical CO 2 and water became miscible in the beginning of CO 2 injection. CO 2 channeling or fingering phenomena were more obviously observed with lower permeable porous media. Capillary force decreases with increasing particle size, which would increase permeability and allow CO 2 and water to invade into small pore spaces more easily. The study also showed CO 2 flow patterns were dominated by dimensionless capillary number, changing from capillary finger to stable flow. The relative permeability curve was calculated using Brooks-Corey model, while the results showed the relative permeability of CO 2 slightly decreases with the increase of capillary number. Copyright Â© 2016 Elsevier Inc. All rights reserved.
Multi-scale diffuse interface modeling of multi-component two-phase flow with partial miscibility

NASA Astrophysics Data System (ADS)

Kou, Jisheng; Sun, Shuyu

2016-08-01

In this paper, we introduce a diffuse interface model to simulate multi-component two-phase flow with partial miscibility based on a realistic equation of state (e.g. Peng-Robinson equation of state). Because of partial miscibility, thermodynamic relations are used to model not only interfacial properties but also bulk properties, including density, composition, pressure, and realistic viscosity. As far as we know, this effort is the first time to use diffuse interface modeling based on equation of state for modeling of multi-component two-phase flow with partial miscibility. In numerical simulation, the key issue is to resolve the high contrast of scales from the microscopic interface composition to macroscale bulk fluid motion since the interface has a nanoscale thickness only. To efficiently solve this challenging problem, we develop a multi-scale simulation method. At the microscopic scale, we deduce a reduced interfacial equation under reasonable assumptions, and then we propose a formulation of capillary pressure, which is consistent with macroscale flow equations. Moreover, we show that Young-Laplace equation is an approximation of this capillarity formulation, and this formulation is also consistent with the concept of Tolman length, which is a correction of Young-Laplace equation. At the macroscopical scale, the interfaces are treated as discontinuous surfaces separating two phases of fluids. Our approach differs from conventional sharp-interface two-phase flow model in that we use the capillary pressure directly instead of a combination of surface tension and Young-Laplace equation because capillarity can be calculated from our proposed capillarity formulation. A compatible condition is also derived for the pressure in flow equations. Furthermore, based on the proposed capillarity formulation, we design an efficient numerical method for directly computing the capillary pressure between two fluids composed of multiple components. Finally, numerical tests are carried out to verify the effectiveness of the proposed multi-scale method.

Multi-scale diffuse interface modeling of multi-component two-phase flow with partial miscibility

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

Kou, Jisheng; Sun, Shuyu, E-mail: shuyu.sun@kaust.edu.sa; School of Mathematics and Statistics, Xi'an Jiaotong University, Xi'an 710049

2016-08-01

In this paper, we introduce a diffuse interface model to simulate multi-component two-phase flow with partial miscibility based on a realistic equation of state (e.g. Peng–Robinson equation of state). Because of partial miscibility, thermodynamic relations are used to model not only interfacial properties but also bulk properties, including density, composition, pressure, and realistic viscosity. As far as we know, this effort is the first time to use diffuse interface modeling based on equation of state for modeling of multi-component two-phase flow with partial miscibility. In numerical simulation, the key issue is to resolve the high contrast of scales from themore » microscopic interface composition to macroscale bulk fluid motion since the interface has a nanoscale thickness only. To efficiently solve this challenging problem, we develop a multi-scale simulation method. At the microscopic scale, we deduce a reduced interfacial equation under reasonable assumptions, and then we propose a formulation of capillary pressure, which is consistent with macroscale flow equations. Moreover, we show that Young–Laplace equation is an approximation of this capillarity formulation, and this formulation is also consistent with the concept of Tolman length, which is a correction of Young–Laplace equation. At the macroscopical scale, the interfaces are treated as discontinuous surfaces separating two phases of fluids. Our approach differs from conventional sharp-interface two-phase flow model in that we use the capillary pressure directly instead of a combination of surface tension and Young–Laplace equation because capillarity can be calculated from our proposed capillarity formulation. A compatible condition is also derived for the pressure in flow equations. Furthermore, based on the proposed capillarity formulation, we design an efficient numerical method for directly computing the capillary pressure between two fluids composed of multiple components. Finally, numerical tests are carried out to verify the effectiveness of the proposed multi-scale method.« less
Improvement of Sweep Efficiency in Gasflooding

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

Kishore Mohanty

2008-12-31

Miscible and near-miscible gasflooding has proven to be one of the few cost effective enhance oil recovery techniques in the past twenty years. As the scope of gas flooding is being expanded to medium viscosity oils in shallow sands in Alaska and shallower reservoirs in the lower 48, there are questions about sweep efficiency in near-miscible regions. The goal of this research is to evaluate sweep efficiency of various gas flooding processes in a laboratory model and develop numerical tools to estimate their effectiveness in the field-scale. Quarter 5-spot experiments were conducted at reservoir pressure to evaluate the sweep efficiencymore » of gas, WAG and foam floods. The quarter 5-spot model was used to model vapor extraction (VAPEX) experiments at the lab scale. A streamline-based compositional simulator and a commercial simulator (GEM) were used to model laboratory scale miscible floods and field-scale pattern floods. An equimolar mixture of NGL and lean gas is multicontact miscible with oil A at 1500 psi; ethane is a multicontact miscible solvent for oil B at pressures higher than 607 psi. WAG improves the microscopic displacement efficiency over continuous gas injection followed by waterflood in corefloods. WAG improves the oil recovery in the quarter 5-spot over the continuous gas injection followed by waterflood. As the WAG ratio increases from 1:2 to 2:1, the sweep efficiency in the 5-spot increases, from 39.6% to 65.9%. A decrease in the solvent amount lowers the oil recovery in WAG floods, but significantly higher amount of oil can be recovered with just 0.1 PV solvent injection over just waterflood. Use of a horizontal production well lowers the oil recovery over the vertical production well during WAG injection phase in this homogeneous 5-spot model. Estimated sweep efficiency decreases from 61.5% to 50.5%. In foam floods, as surfactant to gas slug size ratio increases from 1:10 to 1:1, oil recovery increases. In continuous gasflood VAPEX processes, as the distance between the injection well and production well decreases, the oil recovery and rate decreases in continuous gasflood VAPEX processes. Gravity override is observed for gas injection simulations in vertical (X-Z) cross-sections and 3-D quarter five spot patterns. Breakthrough recovery efficiency increases with the viscous-to-gravity ratio in the range of 1-100. The speed up for the streamline calculations alone is almost linear with the number of processors. The overall speed up factor is sub-linear because of the overhead time spent on the finite-difference calculation, inter-processor communication, and non-uniform processor load. Field-scale pattern simulations showed that recovery from gas and WAG floods depends on the vertical position of high permeability regions and k{sub v}/k{sub h} ratio. As the location of high permeability region moves down and k{sub v}/k{sub h} ratio decreases, oil recovery increases. There is less gravity override. The recovery from the field model is lower than that from the lab 5-spot model, but the effect of WAG ratio is similar.« less
Magnetic particles as liquid carriers in the microfluidic lab-in-tube approach to detect phase change.

PubMed

Blumenschein, Nicholas A; Han, Daewoo; Caggioni, Marco; Steckl, Andrew J

2014-06-11

Magnetic beads (MBs) with ∼1.9 μm average diameter were used to transport specific microliter-scale volumes of liquids between adjacent reservoirs within a closed tube under the influence of a magnetic field. The tube's inner surface is coated with a hydrophobic layer, enabling the formation of a surface tension valve by inserting an air gap between reservoirs. This transfer process was implemented by keeping the MBs stationary with a fixed external magnet while the liquid reservoirs were translated by a computer-controlled syringe pump system. The magnet induces the aggregation of MBs in a loosely packed cluster (void volume ∼90-95%) against the tube's inner wall. The liquid trapped in the MB cluster is transported across the air gap between reservoirs. Fluorescence intensity from a dye placed in one reservoir is used to measure the volume of liquid transferred between reservoirs. The carry-over liquid volume is controlled by the mass of the MBs within the device. The typical volume of liquid carried by the MB cluster is ∼2 to 3 μL/mg of beads, allowing the use of small samples. This technique can be used to study the effect of small compositional variation on the properties of fluid mixtures. The feasibility of this "lab-in-tube" approach for binary phase diagram determination in a water-surfactant (C12E5) system was demonstrated.
Novel Approach for Modeling of Nonuniform Slag Layers and Air Gap in Continuous Casting Mold

NASA Astrophysics Data System (ADS)

Wang, Xudong; Kong, Lingwei; Yao, Man; Zhang, Xiaobing

2017-02-01

Various kinds of surface defects on the continuous casting slab usually originate from nonuniform heat transfer and mechanical behavior, especially during the initial solidification inside the mold. In this article, a model-coupled inverse heat transfer problem incorporating the effect of slag layers and air gap is developed to study the nonuniform distribution of liquid slag, solid slag, and air gap layers. The model considers not only the formation and evolution of slag layers and air gap but also the temperatures in the mold copper as measured by thermocouples. The simulation results from the model and the measured temperatures from experiments are shown to be in good agreement with each other. At the casting speed of 0.65 m/min, the liquid slag film disappears and transforms into solid slag entirely at about 400 mm away from meniscus, and an air gap begins to form. Until the mold exit, the maximum thickness of the solid slag layer and air gap gradually increases to 1.34 and 0.056 mm, respectively. The results illustrate that the magnitude and nonuniform distribution of the slag layers and air gap along the cross direction, correlating with heat flux between the shell and mold, eventually determine the temperature profiles of the mold hot face and slab surface. The proposed model may provide a convenient approach for analyzing nonuniform heat transfer and mechanical behaviors between the mold and slab in the real casting process.
Influence of the solid dielectric over the electric field from the ozone cell gap with double dielectric barrier

NASA Astrophysics Data System (ADS)

Ganea, I.

2017-05-01

The distilled water has the advantage of high value dielectric constant (ε = 81) in relation to ceramic glass materials, currently used for constructing the dielectric barrier. It was necessary to build a thin-walled enclosure of solid insulating material that contain distilled water to achieve a dielectric barrier. This was necessary to avoid exposing the liquid to the direct action of ozone. Dielectric permittivity of the solid dielectric material and the thickness of these walls have diminished the value of the electric field form the gaseous gap of the ozone cell compared to the case with the dielectric barrier from distilled water. The author of this work deduced theoretical relationships that express the values of the electric field intensity in the gap of the cell with two dielectrics and compared them with similar relationships of the intensity of the electric field from the gap of the ozone cell with one dielectric. In this work the author presenting experimental results which confirm the theoretical deducting regarding the use of the solid dielectric as enclosure for the liquid dielectric.
Lattice strain measurements of deuteride phase formation in epitaxial niobium on sapphire

NASA Astrophysics Data System (ADS)

Allain, Monica Marie Cortez

Deuteride phase formation in epitaxial niobium on sapphire was investigated for two film thicknesses (200 and 1200A). A palladium cap of approximately 40A facilitated deuterium absorption from the gas phase and each exposure condition ensured that the film passed through the miscibility gap. In situ resistivity and x-ray diffraction (XRD) provided a correlation between the film resistance and each of the phases. This correlation was used during helium-3 nuclear reaction analysis to determine the deuterium concentration at the beginning and end of the miscibility gap providing a closer look at the strain behavior vs. deuterium concentration within the single and two-phase region. Three orthogonal reciprocal lattice points, the out-of-plane (1--10), the in-plane (002), and the in-plane (110), were monitored with XRD during deuterium absorption to saturation. Cycling effects on the 1200A Nb film were analyzed and found not to influence the strain behavior. The strain was anisotropic for both films, giving an enhanced out-of-plane expansion relative to the two in-plane directions. This is consistent with a clamping force inhibiting in-plane expansion. The observed out-of-plane strain can be used to estimate the in-plane clamping stress; the result is approximately 1 and 2 GPa for the 1200 and 200A Nb films respectively. The volumetric expansion determined from in situ XRD measurements demonstrate that the know value of the specific volume of deuterium, Deltanu/O, in bulk Nb (Deltanu/O = 0.174) does not hold for thin-film, epitaxial geometry (Deltanu/O ≈ 1). Further, the behavior of the specific volume shows a discontinuity at the phase boundary that does not exist in bulk. Lattice strain and overall film expansion from simultaneous XRD and x-ray reflectivity (XRR) measurements, respectively, were performed on both films. These results demonstrate a larger out-of-plane film expansion compared to the out-of-plane lattice strain for the 1200A Nb film compared to the 200A Nb film. It is believe that this is a consequence of greater plasticity within the 1200A film and associated dislocation generation. The enhance plasticity is also confirmed by a greater loss in structural coherence for the 1200A film and the fact that the in-plane clamping stress is greater for the 200A film. Evidence of significant dislocation formation has been confirmed with high-resolution electron microscopy (HREM) for the 1200A Nb film. The HREM images were used to estimate a dislocation density of 1012 cm-2 after repeated cycling. A residual out-of-plane compressive strain was observed in the 1200A Nb film after complete deuterium evolution. This observation can be explained by irreversible interstitial dislocation loop formation.
Buoyancy-driven instabilities around miscible A+B→C reaction fronts: a general classification.

PubMed

Trevelyan, P M J; Almarcha, C; De Wit, A

2015-02-01

Upon contact between miscible solutions of reactants A and B along a horizontal interface in the gravity field, various buoyancy-driven instabilities can develop when an A+B→C reaction takes place and the density varies with the concentrations of the various chemicals. To classify the possible convective instability scenarios, we analyze the spatial dependence of the large time asymptotic density profiles as a function of the key parameters of the problem, which are the ratios of diffusion coefficients and of solutal expansion coefficients of species A, B, and C. We find that 62 different density profiles can develop in the reactive problem, whereas only 6 of them can be obtained in the nonreactive one.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Djabbarah, N.F.

A miscible displacement process for recovering oil from a subterranean, oil-containing formation penetrated by at least one injection well and at least one spaced-apart production well and having fluid communication between the injection and the production wells is described comprising: (a) injecting a slug of til oil into the formation through the injection well; (b) injecting a slug of a displacing fluid into the formation through the injection well, the displacing fluid being selected from the group consisting of carbon monoxide, carbon dioxide, methane, nitrogen, air, flue gas, combustion gas and mixtures thereof, the injection of the tall oil loweringmore » the minimum miscibility pressure of the displacing fluid in the formation oil; and (c) recovering the oil through the production well.« less
Osmosis-driven viscous fingering of oil-in-water emulsions

NASA Astrophysics Data System (ADS)

Liu, Ying; Rallabandi, Bhargav; Baskaran, Mrudhula; Stone, Howard

2017-11-01

Viscous fingering occurs when a low viscosity fluid invades a more viscous fluid. Fingering of two miscible fluids is more complicated than that of immiscible fluids in that there is no sharp fluid-fluid interface and diffusion occurs between the phases. We experimentally studied the fingering of two miscible fluids: an oil-in-water emulsion and a sodium chloride solution. When the concentration of sodium chloride in the water phase in the emulsion exceeds that in the sodium chloride solution, the consequent osmotic flow automatically facilitates the occurrence of the fingering. On the contrary, when the sodium chloride solution has higher concentration, the spreading of emulsion is more uniform than the case without the concentration difference. We provide a model to rationalize and quantify these observations.
Dynamically reconfigurable complex emulsions via tunable interfacial tensions

PubMed Central

Zarzar, Lauren D.; Sresht, Vishnu; Sletten, Ellen M.; Kalow, Julia A.; Blankschtein, Daniel; Swager, Timothy M.

2015-01-01

Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including multiple emulsions and Janus droplets which contain hemispheres of differing material, are of increasing importance1 in pharmaceuticals and medical diagnostics2, in the fabrication of microparticles and capsules3–5 for food6, in chemical separations7, in cosmetics8, and in dynamic optics9. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets’ physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes10, to small-volume but more precise microfluidic methods11,12. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have greatly increased utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with controllably reconfigurable morphologies and the potential to create a wide range of responsive materials. PMID:25719669
Dynamically reconfigurable complex emulsions via tunable interfacial tensions.

PubMed

Zarzar, Lauren D; Sresht, Vishnu; Sletten, Ellen M; Kalow, Julia A; Blankschtein, Daniel; Swager, Timothy M

2015-02-26

Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including Janus droplets (that is, droplets with faces of differing chemistries) and multiple emulsions, are of increasing importance in pharmaceuticals and medical diagnostics, in the fabrication of microparticles and capsules for food, in chemical separations, in cosmetics, and in dynamic optics. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets' physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes, to small-volume but more precise microfluidic methods. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have great utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with controllably reconfigurable morphologies and the potential to create a wide range of responsive materials.
Dynamically reconfigurable complex emulsions via tunable interfacial tensions

NASA Astrophysics Data System (ADS)

Zarzar, Lauren D.; Sresht, Vishnu; Sletten, Ellen M.; Kalow, Julia A.; Blankschtein, Daniel; Swager, Timothy M.

2015-02-01

Emulsification is a powerful, well-known technique for mixing and dispersing immiscible components within a continuous liquid phase. Consequently, emulsions are central components of medicine, food and performance materials. Complex emulsions, including Janus droplets (that is, droplets with faces of differing chemistries) and multiple emulsions, are of increasing importance in pharmaceuticals and medical diagnostics, in the fabrication of microparticles and capsules for food, in chemical separations, in cosmetics, and in dynamic optics. Because complex emulsion properties and functions are related to the droplet geometry and composition, the development of rapid, simple fabrication approaches allowing precise control over the droplets' physical and chemical characteristics is critical. Significant advances in the fabrication of complex emulsions have been made using a number of procedures, ranging from large-scale, less precise techniques that give compositional heterogeneity using high-shear mixers and membranes, to small-volume but more precise microfluidic methods. However, such approaches have yet to create droplet morphologies that can be controllably altered after emulsification. Reconfigurable complex liquids potentially have great utility as dynamically tunable materials. Here we describe an approach to the one-step fabrication of three- and four-phase complex emulsions with highly controllable and reconfigurable morphologies. The fabrication makes use of the temperature-sensitive miscibility of hydrocarbon, silicone and fluorocarbon liquids, and is applied to both the microfluidic and the scalable batch production of complex droplets. We demonstrate that droplet geometries can be alternated between encapsulated and Janus configurations by varying the interfacial tensions using hydrocarbon and fluorinated surfactants including stimuli-responsive and cleavable surfactants. This yields a generalizable strategy for the fabrication of multiphase emulsions with controllably reconfigurable morphologies and the potential to create a wide range of responsive materials.
Empirical parameters for solvent acidity, basicity, dipolarity, and polarizability of the ionic liquids [BMIM][BF4] and [BMIM][PF6].

PubMed

del Valle, J C; García Blanco, F; Catalán, J

2015-04-02

The empirical solvent scales for polarizability (SP), dipolarity (SdP), acidity (SA), and basicity (SB) have been successfully used to interpret the solvatochromism of compounds dissolved in organic solvents and their solvent mixtures. Providing that the published solvatochromic parameters for the ionic liquids 1-(1-butyl)-3-methylimidazolium tetrafluoroborate, [BMIM][BF4] and 1-(1-butyl)-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], are excessively widespread, their SP, SdP, SA, and SB values are measured herein at temperatures from 293 to 353 K. Four key points are emphasized herein: (i) the origin of the solvatochromic solvent scales--the gas phase, that is the absence of any medium perturbation--; (ii) the separation of the polarizability and dipolarity effects; (iii) the simplification of the probing process in order to obtain the solvatochromic parameters; and (iv) the SP, SdP, SA, and SB solvent scales can probe the polarizability, dipolarity, acidity, and basicity of ionic liquids as well as of organic solvents and water-organic solvent mixtures. From the multiparameter approach using the four pure solvent scales one can draw the conclusion that (a) the solvent influence of [BMIM][BF4] parallels that of formamide at 293 K, both of them miscible with water; (b) [BMIM][PF6] shows a set of solvatochromic parameters similar to that of chloroacetonitrile, both of them water insoluble; and (c) that the corresponding solvent acidity and basicity of the ionic liquids can be explained to a great extent from the cation species by comparing the empirical parameters of [BMIM](+) with those of the solvent 1-methylimidazole. The insolubility of [BMIM][PF6] in water as compared to [BMIM][BF4] is tentatively connected to some extent to the larger molar volume of the anion [PF6](-), and to the difference in basicity of [PF6](-) and [BF4](-).
Computer Simulations and Theoretical Studies of Complex Systems: from complex fluids to frustrated magnets

NASA Astrophysics Data System (ADS)

Choi, Eunsong

Computer simulations are an integral part of research in modern condensed matter physics; they serve as a direct bridge between theory and experiment by systemactically applying a microscopic model to a collection of particles that effectively imitate a macroscopic system. In this thesis, we study two very differnt condensed systems, namely complex fluids and frustrated magnets, primarily by simulating classical dynamics of each system. In the first part of the thesis, we focus on ionic liquids (ILs) and polymers--the two complementary classes of materials that can be combined to provide various unique properties. The properties of polymers/ILs systems, such as conductivity, viscosity, and miscibility, can be fine tuned by choosing an appropriate combination of cations, anions, and polymers. However, designing a system that meets a specific need requires a concrete understanding of physics and chemistry that dictates a complex interplay between polymers and ionic liquids. In this regard, molecular dynamics (MD) simulation is an efficient tool that provides a molecular level picture of such complex systems. We study the behavior of Poly (ethylene oxide) (PEO) and the imidazolium based ionic liquids, using MD simulations and statistical mechanics. We also discuss our efforts to develop reliable and efficient classical force-fields for PEO and the ionic liquids. The second part is devoted to studies on geometrically frustrated magnets. In particular, a microscopic model, which gives rise to an incommensurate spiral magnetic ordering observed in a pyrochlore antiferromagnet is investigated. The validation of the model is made via a comparison of the spin-wave spectra with the neutron scattering data. Since the standard Holstein-Primakoff method is difficult to employ in such a complex ground state structure with a large unit cell, we carry out classical spin dynamics simulations to compute spin-wave spectra directly from the Fourier transform of spin trajectories. We conclude the study by showing an excellent agreement between the simulation and the experiment.
Microsecond-range optical shutter for unpolarized light with chiral nematic liquid crystal

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

Mohammadimasoudi, Mohammad, E-mail: Mohammad.Mohammadimasoudi@elis.ugent.be; Neyts, Kristiaan; Beeckman, Jeroen

2015-04-15

A fast electro-optic shutter is fabricated and demonstrated. The device works independently of the polarization state of the incoming light beam. Modulation between 3% transmission and 60% transmission is obtained within a wavelength range of 50 nm with a response time of 20 μs. The device consists of two partly polymerized chiral nematic liquid crystal layers separated by a half wave plate. The transmission modulation is due to a 50 nm wavelength shift of the photonic band gap of the chiral liquid crystal realized by applying an electric field over a mixture of photo-polymerized LC and non-reactive nematic LC containingmore » a chiral dopant. The shutter features high reflectivity in the photonic band gap. We investigate the influence of the amplitude of the applied voltage on the width and the depth of the reflection band.« less
Evidence for a gapped spin-liquid ground state in a kagome Heisenberg antiferromagnet

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

Fu, Mingxuan; Imai, Takahashi; Han, Tian -Heng

2015-11-06

Here, the kagome Heisenberg antiferromagnet is a leading candidate in the search for a spin system with a quantum spin-liquid ground state. The nature of its ground state remains a matter of active debate. We conducted oxygen-17 single-crystal nuclear magnetic resonance (NMR) measurements of the spin-1/2 kagome lattice in herbertsmithite [ZnCu 3(OH) 6Cl 2], which is known to exhibit a spinon continuum in the spin excitation spectrum. We demonstrated that the intrinsic local spin susceptibility χkagome, deduced from the oxygen-17 NMR frequency shift, asymptotes to zero below temperatures of 0.03J, where J ~ 200 kelvin is the copper-copper superexchange interaction.more » Combined with the magnetic field dependence of χ kagome that we observed at low temperatures, these results imply that the kagome Heisenberg antiferromagnet has a spin-liquid ground state with a finite gap.« less
Features and applications of the Groove Analysis Program (GAP)

NASA Technical Reports Server (NTRS)

Ku, Jentung; Nguyen, Tu M.; Brennan, Patrick J.

1995-01-01

An IBM Personal Computer (PC) version of the Groove Analysis program (GAP) was developed to predict the steady state heat transport capability of an axially grooved heat pipe for a specified groove geometry and working fluid. In the model, the capillary limit is determined by the numerical solution of the differential equation for momentum conservation with the appropriate boundary conditions. This governing equation accounts for the hydrodynamic losses due to friction in liquid and vapor flows and due to liquid/vapor shear interaction. Back-pumping in both 0-g and 1-g is accounted for in the boundary condition at the condenser end. Slug formation in 0-g and puddle flow in 1-g are also considered in the model. At the user's discretion, the code will perform the analysis for various fluid inventories (undercharge, nominal charge, overcharge, or a fixed fluid charge) and heat pipe elevations. GAP will also calculate the minimum required heat pipe wall thickness for pressure containment at design temperatures that are greater than or lower than the critical temperature of the working fluid. This paper discusses the theory behind the development of the GAP model. It also presents the many useful and powerful capabilities of the model. Furthermore, a correlation of flight test performance data and the predictions using GAP are presented and discussed.
Plugging the Patient Evidence Gap: What Patients with Swallowing Disorders Post-Stroke Say about Thickened Liquids

ERIC Educational Resources Information Center

McCurtin, Arlene; Healy, Chiara; Kelly, Linda; Murphy, Fiona; Ryan, Jean; Walsh, Joanne

2018-01-01

Background: Oropharyngeal dysphagia post-stroke is well known, with its presence increasing the risk of poor outcomes in particular aspiration and aspiration pneumonia. Management to minimize the risk of aspiration and improve swallow safety post-stroke includes the treatment of thickened liquids (TL), an established bolus modification…
Designing Quantum Spin-Orbital Liquids in Artificial Mott Insulators

PubMed Central

Dou, Xu; Kotov, Valeri N.; Uchoa, Bruno

2016-01-01

Quantum spin-orbital liquids are elusive strongly correlated states of matter that emerge from quantum frustration between spin and orbital degrees of freedom. A promising route towards the observation of those states is the creation of artificial Mott insulators where antiferromagnetic correlations between spins and orbitals can be designed. We show that Coulomb impurity lattices on the surface of gapped honeycomb substrates, such as graphene on SiC, can be used to simulate SU(4) symmetric spin-orbital lattice models. We exploit the property that massive Dirac fermions form mid-gap bound states with spin and valley degeneracies in the vicinity of a Coulomb impurity. Due to electronic repulsion, the antiferromagnetic correlations of the impurity lattice are driven by a super-exchange interaction with SU(4) symmetry, which emerges from the bound states degeneracy at quarter filling. We propose that quantum spin-orbital liquids can be engineered in artificially designed solid-state systems at vastly higher temperatures than achievable in optical lattices with cold atoms. We discuss the experimental setup and possible scenarios for candidate quantum spin-liquids in Coulomb impurity lattices of various geometries. PMID:27553516
Packaging of ferroelectric liquid crystal-on-silicon spatial light modulators

NASA Astrophysics Data System (ADS)

Lin, W.; Morozova, Nina D.; Ju, TehHua; Zhang, Weidong; Lee, Yung-Cheng; McKnight, Douglas J.; Johnson, Kristina M.

1996-11-01

A self-pulling soldering technology has been demonstrated for assembling liquid crystal on silicon (LCOS) spatial light modulators (SLMs). One of the major challenges in manufacturing the LCOS modules is to reproducibly control the thickness of the gap between the very large scale integrated circuit (VLSI) chip and the cover glass. The liquid crystal material is sandwiched between the VLSI chop and the cover glass which is coated with a transparent conductor. Solder joints with different profiles and sizes have been designed to provide surface tension forces to control the gap accommodating the ferroelectric liquid crystal layer in the range of a micron level with sub- micron uniformity. The optimum solder joint design is defined as a joint that results in the maximum pulling force. This technology provides an automatic, batch assembly process for a LCOS SLM through one reflow process. Fluxless soldering technology is used to assemble the module. This approach avoids residues from chemical of flux and oxides, and eliminates potential contamination to the device. Two different LCOS SLM designs and the process optimization are described.

Prediction of Phase Behavior of Spray-Dried Amorphous Solid Dispersions: Assessment of Thermodynamic Models, Standard Screening Methods and a Novel Atomization Screening Device with Regard to Prediction Accuracy

PubMed Central

Chavez, Pierre-François; Meeus, Joke; Robin, Florent; Schubert, Martin Alexander; Somville, Pascal

2018-01-01

The evaluation of drug–polymer miscibility in the early phase of drug development is essential to ensure successful amorphous solid dispersion (ASD) manufacturing. This work investigates the comparison of thermodynamic models, conventional experimental screening methods (solvent casting, quench cooling), and a novel atomization screening device based on their ability to predict drug–polymer miscibility, solid state properties (Tg value and width), and adequate polymer selection during the development of spray-dried amorphous solid dispersions (SDASDs). Binary ASDs of four drugs and seven polymers were produced at 20:80, 40:60, 60:40, and 80:20 (w/w). Samples were systematically analyzed using modulated differential scanning calorimetry (mDSC) and X-ray powder diffraction (XRPD). Principal component analysis (PCA) was used to qualitatively assess the predictability of screening methods with regards to SDASD development. Poor correlation was found between theoretical models and experimentally-obtained results. Additionally, the limited ability of usual screening methods to predict the miscibility of SDASDs did not guarantee the appropriate selection of lead excipient for the manufacturing of robust SDASDs. Contrary to standard approaches, our novel screening device allowed the selection of optimal polymer and drug loading and established insight into the final properties and performance of SDASDs at an early stage, therefore enabling the optimization of the scaled-up late-stage development. PMID:29518936
Miscibility and interaction between 1-alkanol and short-chain phosphocholine in the adsorbed film and micelles.

PubMed

Takajo, Yuichi; Matsuki, Hitoshi; Kaneshina, Shoji; Aratono, Makoto; Yamanaka, Michio

2007-09-01

The miscibility and interaction of 1-hexanol (C6OH) and 1-heptanol (C7OH) with 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) in the adsorbed films and micelles were investigated by measuring the surface tension of aqueous C6OH-DHPC and aqueous C7OH-DHPC solutions. The surface density, the mean molecular area, the composition of the adsorbed film, and the excess Gibbs energy of adsorption g(H,E), were estimated. Further, the critical micelle concentration of the mixtures was determined from the surface tension versus molality curves; the micellar composition was calculated. The miscibility of the 1-alkanols and DHPC molecules in the adsorbed film and micelles was examined using the phase diagram of adsorption (PDA) and that of micellization (PDM). The PDA and the composition dependence of g(H,E) indicated the non-ideal mixing of the 1-alkanols and DHPC molecules due to the attractive interaction between the molecules in the adsorbed film, while the PDM indicated that the 1-alkanol molecules were not incorporated in the micelles within DHPC rich region. The dependence of the mean molecular area of the mixtures on the surface composition suggested that the packing property of the adsorbed film depends on the chain length of 1-alkanol: C6OH expands the DHPC adsorbed film more than C7OH.
Molecular Dynamics Simulation of Amorphous Hydroxypropylmethylcellulose and Its Mixtures With Felodipine and Water.

PubMed

Xiang, Tian-Xiang; Anderson, Bradley D

2017-03-01

Understanding drug-polymer molecular interactions, their miscibility, supersaturation potential, and the effects of water uptake may be invaluable for selecting amorphous polymer dispersions that can maximize the oral bioavailability of poorly water-soluble drugs. Molecular dynamics simulations were performed using a model for hydroxypropylmethylcellulose (HPMC) resembling the substitution patterns found experimentally. HPMC at low and high water contents (0.9%-23.0% wt/wt) and mixtures with a hydrophobic drug, felodipine (FEL), were constructed. T g values and densities after ∼30 ns aging at 298 K were close to published results. Except for hydrogen bonds (HBs) between the 5-O- and a 3-OH group in a neighboring repeat unit, HPMC oxygen atoms have a low HB probability (p < 0.1) perhaps due to shielding by surrounding substituents. Water molecules tend to be isolated at low water content while clusters were prevalent at ≥10.7% water. The Flory-Huggins FEL-HPMC interaction parameter (-0.20 ± 0.07) predicts complete miscibility at all HPMC compositions, in agreement with experiments. However, HBs between the FEL-N-H and HPMC favoring miscibility are disrupted with increasing water. Apparent diffusion coefficients versus water content were generated for water and FEL and a theory for the non-Einsteinian nature of water diffusion is proposed. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.
Pseudolatex preparation using a novel emulsion-diffusion process involving direct displacement of partially water-miscible solvents by distillation.

PubMed

Quintanar-Guerrero, D; Allémann, E; Fessi, H; Doelker, E

1999-10-25

Pseudolatexes were obtained by a new process based on an emulsification-diffusion technique involving partially water-miscible solvents. The preparation method consisted of emulsifying an organic solution of polymer (saturated with water) in an aqueous solution of a stabilizing agent (saturated with solvent) using conventional stirrers, followed by direct solvent distillation. The technique relies on the rapid displacement of the solvent from the internal into the external phase which thereby provokes polymer aggregation. Nanoparticle formation is believed to occur because rapid solvent diffusion produces regions of local supersaturation near the interface, and nanoparticles are formed due to the ensuing interfacial phase transformations and polymer aggregation that occur in these interfacial domains. Using this method, it was possible to prepare pseudolatexes of biodegradable and non-biodegradable polymers such as poly(D,L-lactic acid) and poly(epsilon-caprolactone), Eudragit E, cellulose acetate phthalate, cellulose acetate trimellitate using ethyl acetate or 2-butanone as partially water-miscible solvents and poly(vinyl alcohol) or poloxamer 407 as stabilizing agent. A transition from nano- to microparticles was observed at high polymer concentrations. At concentrations above 30% w/v of Eudragit E in ethyl acetate or cellulose acetate phthalate in 2-butanone only microparticles were obtained. This behaviour was attributed to decreased transport of polymer molecules into the aqueous phase.
Dependence on sphere size of the phase behavior of mixtures of rods and spheres

NASA Astrophysics Data System (ADS)

Urakami, Naohito; Imai, Masayuki

2003-07-01

By the addition of chondroitin sulfate (Chs) to the aqueous suspension of tobacco mosaic virus (TMV), the aggregation of TMV occurs at very dilute TMV concentration compared with the addition of polyethylene oxide (PEO). The difference of physical behavior between Chs and PEO is the chain conformation in solution. The Chs chain has a semirigid nature, whereas the PEO chain has a flexible nature. In this study, the Chs and PEO chains are simplified to spherical particles having different size, and we use the spherocylinder model for TMV particle. The effect of the sphere size on the phase behaviors in the mixtures of rods and spheres is investigated by Monte Carlo simulations. By the addition of small spheres, the system transforms from the miscible isotropic phase to the miscible nematic phase. On the other hand, by the addition of large spheres, the system changes from the miscible isotropic phase to the immiscible nematic phase through the immiscible isotropic phase. The different phase behaviors between the small and the large spheres originate from the difference of overlapping volume of the depletion zone. In addition, we perform the Monte Carlo simulations in the case that semirigid chains are used as the Chs chain models. The same phase behaviors are observed as the mixtures of rods and large spheres. Thus the sphere model captures the phase behaviors of rod and polymer mixture systems.
Effect of poly(ethylene oxide) homopolymer and two different poly(ethylene oxide-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers on morphological, optical, and mechanical properties of nanostructured unsaturated polyester.

PubMed

Builes, Daniel H; Hernández-Ortiz, Juan P; Corcuera, Ma Angeles; Mondragon, Iñaki; Tercjak, Agnieszka

2014-01-22

Novel nanostructured unsaturated polyester resin-based thermosets, modified with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and two poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymers (BCP), were developed and analyzed. The effects of molecular weights, blocks ratio, and curing temperatures on the final morphological, optical, and mechanical properties were reported. The block influence on the BCP miscibility was studied through uncured and cured mixtures of unsaturated polyester (UP) resins with PEO and PPO homopolymers having molecular weights similar to molecular weights of the blocks of BCP. The final morphology of the nanostructured thermosetting systems, containing BCP or homopolymers, was investigated, and multiple mechanisms of nanostructuration were listed and explained. By considering the miscibility of each block before and after curing, it was determined that the formation of the nanostructured matrices followed a self-assembly mechanism or a polymerization-induced phase separation mechanism. The miscibility between PEO or PPO blocks with one of two phases of UP matrix was highlighted due to its importance in the final thermoset properties. Relationships between the final morphology and thermoset optical and mechanical properties were examined. The mechanisms and physics behind the morphologies lead toward the design of highly transparent, nanostructured, and toughened thermosetting UP systems.
Viscous and gravitational fingering in multiphase compositional and compressible flow

NASA Astrophysics Data System (ADS)

Moortgat, Joachim

2016-03-01

Viscous and gravitational fingering refer to flow instabilities in porous media that are triggered by adverse mobility or density ratios, respectively. These instabilities have been studied extensively in the past for (1) single-phase flow (e.g., contaminant transport in groundwater, first-contact-miscible displacement of oil by gas in hydrocarbon production), and (2) multi-phase immiscible and incompressible flow (e.g., water-alternating-gas (WAG) injection in oil reservoirs). Fingering in multiphase compositional and compressible flow has received much less attention, perhaps due to its high computational complexity. However, many important subsurface processes involve multiple phases that exchange species. Examples are carbon sequestration in saline aquifers and enhanced oil recovery (EOR) by gas or WAG injection below the minimum miscibility pressure. In multiphase flow, relative permeabilities affect the mobility contrast for a given viscosity ratio. Phase behavior can also change local fluid properties, which can either enhance or mitigate viscous and gravitational instabilities. This work presents a detailed study of fingering behavior in compositional multiphase flow in two and three dimensions and considers the effects of (1) Fickian diffusion, (2) mechanical dispersion, (3) flow rates, (4) domain size and geometry, (5) formation heterogeneities, (6) gravity, and (7) relative permeabilities. Results show that fingering in compositional multiphase flow is profoundly different from miscible conditions and upscaling techniques used for the latter case are unlikely to be generalizable to the former.
Miscibility as a factor for component crystallization in multisolute frozen solutions.

PubMed

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

2014-07-01

The relationship between the miscibility of formulation ingredients and their crystallization during the freezing segment of the lyophilization process was studied. The thermal properties of frozen solutions containing myo-inositol and cosolutes were obtained by performing heating scans from -70 °C before and after heat treatment at -20 °C to -5 °C. Addition of dextran 40,000 reduced and prevented crystallization of myo-inositol. In the first scan, some frozen solutions containing an inositol-rich mixture with dextran showed single broad transitions (Tg's: transition temperatures of maximally freeze-concentrated solutes) that indicated incomplete mixing of the concentrated amorphous solutes. Heat treatment of these frozen solutions induced separation of the solutes into inositol-dominant and solute mixture phases (Tg' splitting) following crystallization of myo-inositol (Tg' shifting). The crystal growth involved myo-inositol molecules in the solute mixture phase. The amorphous-amorphous phase separation and resulting loss of the heteromolecular interaction in the freeze-concentrated inositol-dominant phase should allow ordered assembly of the solute molecules required for nucleation. Some dextran-rich and intermediate concentration ratio frozen solutions retained single Tg's of the amorphous solute mixture, both before and after heat treatments. The relevance of solute miscibility on the crystallization of myo-inositol was also indicated in the systems containing glucose or recombinant human albumin. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.
A visual study of radial inward choked flow of liquid nitrogen.

NASA Technical Reports Server (NTRS)

Hendricks, R. C.; Simoneau, R. J.; Hsu, Y. Y.

1973-01-01

Data and high speed movies were acquired on pressurized subcooled liquid nitrogen flowing radially inward through a 0.0076 cm gap. The stagnation pressure ranged from 0.7 to 4 MN/sq m. Steady radial inward choked flow appears equivalent to steady choked flow through axisymmetric nozzles. Transient choked flows through the radial gap are not uniform and the discharge pattern appears as nonuniform impinging jets. The critical mass flow rate data for the transient case appear different from those for the steady case. On the mass flow rate vs pressure map, the slope and separation of the isotherms appear to be less for transient than for steady radial choked flow.
"Freezing" of nanoconfined fluids under an electric field.

PubMed

Xie, Guoxin; Luo, Jianbin; Liu, Shuhai; Guo, Dan; Zhang, Chenhui

2010-02-02

The problem of the solidlike transition of fluids in a nanogap has drawn much fundamental and practical attention. Here, we directly observed the disappearance of the fluidity of liquids confined within a gap with a surface separation of >10 nm under an EF in a ball-plate system, which is called the "freezing" of liquids. The flow of the nanoconfined liquid became very weak as the EF intensity was increased to a critical value and was correlated with the liquid polarity and the film thickness. It is deduced that the EF can induce more liquid molecules to be aligned to form more ordered layers in the nanogap.
Calibration of a spatial light modulator containing dual frequency liquid crystal

NASA Astrophysics Data System (ADS)

Gu, Dong-Feng; Winker, Bruce; Wen, Bing; Taber, Don; Brackley, Andrew; Wirth, Allan; Albanese, Marc; Landers, Frank

2005-08-01

Characterization and calibration process for a liquid crystal (LC) spatial light modulator (SLM) containing dual frequency liquid crystal is described. Special care was taken when dealing with LC cell gap non-uniformity and defect pixels. The calibration results were fed into a closed loop control algorithm to demonstrate correction of wavefront distortions. The performance characteristics of the device were reported. Substantial improvements were made in speed (bandwidth), resolution, power consumption and system weight/volume.
Interface instabilities during displacements of two miscible fluids in a vertical pipe

NASA Astrophysics Data System (ADS)

Scoffoni, J.; Lajeunesse, E.; Homsy, G. M.

2001-03-01

We study experimentally the downward vertical displacement of one miscible fluid by another in a vertical pipe at sufficiently high velocities for diffusive effects to be negligible. For certain viscosity ratios and flow rates, the interface between the two fluids can destabilize. We determine the dimensionless flow rate Uc above which the instability is triggered and its dependence on the viscous ratio M, resulting in a stability map Uc=Uc(M). Two different instability modes have been observed: an asymmetric "corkscrew" mode and an axisymmetric one. We remark that the latter is always eventually disturbed by "corkscrew" type instabilities. We speculate that these instabilities are driven by the viscosity stratification and are analogous to those already observed in core annular flows of immiscible fluids.
DEVELOPMENT AND OPTIMIZATION OF GAS-ASSISTED GRAVITY DRAINAGE (GAGD) PROCESS FOR IMPROVED LIGHT OIL RECOVERY

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

Dandina N. Rao; Subhash C. Ayirala; Madhav M. Kulkarni

This report describes the progress of the project ''Development And Optimization of Gas-Assisted Gravity Drainage (GAGD) Process for Improved Light Oil Recovery'' for the duration of the thirteenth project quarter (Oct 1, 2005 to Dec 30, 2005). There are three main tasks in this research project. Task 1 is a scaled physical model study of the GAGD process. Task 2 is further development of a vanishing interfacial tension (VIT) technique for miscibility determination. Task 3 is determination of multiphase displacement characteristics in reservoir rocks. Section I reports experimental work designed to investigate wettability effects of porous medium, on secondary andmore » tertiary mode GAGD performance. The experiments showed a significant improvement of oil recovery in the oil-wet experiments versus the water-wet runs, both in secondary as well as tertiary mode. When comparing experiments conducted in secondary mode to those run in tertiary mode an improvement in oil recovery was also evident. Additionally, this section summarizes progress made with regard to the scaled physical model construction and experimentation. The purpose of building a scaled physical model, which attempts to include various multiphase mechanics and fluid dynamic parameters operational in the field scale, was to incorporate visual verification of the gas front for viscous instabilities, capillary fingering, and stable displacement. Preliminary experimentation suggested that construction of the 2-D model from sintered glass beads was a feasible alternative. During this reporting quarter, several sintered glass mini-models were prepared and some preliminary experiments designed to visualize gas bubble development were completed. In Section II, the gas-oil interfacial tensions measured in decane-CO{sub 2} system at 100 F and live decane consisting of 25 mole% methane, 30 mole% n-butane and 45 mole% n-decane against CO{sub 2} gas at 160 F have been modeled using the Parachor and newly proposed mechanistic Parachor models. In the decane-CO{sub 2} binary system, Parachor model was found to be sufficient for interfacial tension calculations. The predicted miscibility from the Parachor model deviated only by about 2.5% from the measured VIT miscibility. However, in multicomponent live decane-CO{sub 2} system, the performance of the Parachor model was poor, while good match of interfacial tension predictions has been obtained experimentally using the proposed mechanistic Parachor model. The predicted miscibility from the mechanistic Parachor model accurately matched with the measured VIT miscibility in live decane-CO2 system, which indicates the suitability of this model to predict miscibility in complex multicomponent hydrocarbon systems. In the previous reports to the DOE (15323R07, Oct 2004; 15323R08, Jan 2005; 15323R09, Apr 2005; 15323R10, July 2005 and 154323, Oct 2005), the 1-D experimental results from dimensionally scaled GAGD and WAG corefloods were reported for Section III. Additionally, since Section I reports the experimental results from 2-D physical model experiments; this section attempts to extend this 2-D GAGD study to 3-D (4-phase) flow through porous media and evaluate the performance of these processes using reservoir simulation. Section IV includes the technology transfer efforts undertaken during the quarter. This research work resulted in one international paper presentation in Tulsa, OK; one journal publication; three pending abstracts for SCA 2006 Annual Conference and an invitation to present at the Independents Day session at the IOR Symposium 2006.« less
Glide twinning and pseudotwinning in peristerite: Si,Al diffusional stabilization and implications for the peristerite solvus

NASA Astrophysics Data System (ADS)

Brown, William L.

1989-07-01

Albite glide pseudotwins related to grain-boundary stresses have been observed in an exsolved peristerite (Brown 1989). The glide operation transposes the pre-existing periodic oligoclase/albite lamellae and interfaces into a position rotated by only ˜0.5° in the pseudotwins, but transforms the indices from (1bar 80) outside to ( 081) inside the pseudotwin. The pseudotwin is anti-ordered with respect to Al and Si and both it and the transposed interface are unstable. They should revert to the initial state on stress removal. If however the stresses are maintained for a sufficiently long time, the pseudotwins are stabilized by inversion of Si,Al order and re-orientation of the interface by an angle of about 30° into a position close to \\underline {(1bar 80)} . The continuous lamellae break up into a series of discs by diffusion of NaSi and CaAl, the minimum diffusion path being about the same as the thickness of the lamellae. On extrapolating available interdiffusion data in Ab-rich plagioclases to low temperatures, possible diffusion times may be calculated. The calculated times are long so that either the peristerite miscibility gap must be at a higher temperature than previously supposed or the low-temperature interdiffusion coefficients must be higher than the extrapolated experimental ones, or both. From recent data on ordering in albite, the crest of the gap is estimated to lie close to 650 625° C at low pressure and it is possible that interdiffusion under natural conditions is facilitated by hydrogen (protons) in feldspars.
Ternary lanthanum sulfide selenides {alpha}-LaS{sub 2-x}Se{sub x} (0

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

Bartsch, Christian; Doert, Thomas, E-mail: thomas.doert@chemie.tu-dresden.de

2012-01-15

Mixed lanthanum sulfide selenides LaS{sub 2-x}Se{sub x} (0
High Chloride Doping Levels Stabilize the Perovskite Phase of Cesium Lead Iodide.

PubMed

Dastidar, Subham; Egger, David A; Tan, Liang Z; Cromer, Samuel B; Dillon, Andrew D; Liu, Shi; Kronik, Leeor; Rappe, Andrew M; Fafarman, Aaron T

2016-06-08

Cesium lead iodide possesses an excellent combination of band gap and absorption coefficient for photovoltaic applications in its perovskite phase. However, this is not its equilibrium structure under ambient conditions. In air, at ambient temperature it rapidly transforms to a nonfunctional, so-called yellow phase. Here we show that chloride doping, particularly at levels near the solubility limit for chloride in a cesium lead iodide host, provides a new approach to stabilizing the functional perovskite phase. In order to achieve high doping levels, we first co-deposit colloidal nanocrystals of pure cesium lead chloride and cesium lead iodide, thereby ensuring nanometer-scale mixing even at compositions that potentially exceed the bulk miscibility of the two phases. The resulting nanocrystal solid is subsequently fused into a polycrystalline thin film by chemically induced, room-temperature sintering. Spectroscopy and X-ray diffraction indicate that the chloride is further dispersed during sintering and a polycrystalline mixed phase is formed. Using density functional theory (DFT) methods in conjunction with nudged elastic band techniques, low-energy pathways for interstitial chlorine diffusion into a majority-iodide lattice were identified, consistent with the facile diffusion and fast halide exchange reactions observed. By comparison to DFT-calculated values (with the PBE exchange-correlation functional), the relative change in band gap and the lattice contraction are shown to be consistent with a Cl/I ratio of a few percent in the mixed phase. At these incorporation levels, the half-life of the functional perovskite phase in a humid atmosphere increases by more than an order of magnitude.
Accuracy Test of the OPLS-AA Force Field for Calculating Free Energies of Mixing and Comparison with PAC-MAC

PubMed Central

2017-01-01

We have calculated the excess free energy of mixing of 1053 binary mixtures with the OPLS-AA force field using two different methods: thermodynamic integration (TI) of molecular dynamics simulations and the Pair Configuration to Molecular Activity Coefficient (PAC-MAC) method. PAC-MAC is a force field based quasi-chemical method for predicting miscibility properties of various binary mixtures. The TI calculations yield a root mean squared error (RMSE) compared to experimental data of 0.132 kBT (0.37 kJ/mol). PAC-MAC shows a RMSE of 0.151 kBT with a calculation speed being potentially 1.0 × 104 times greater than TI. OPLS-AA force field parameters are optimized using PAC-MAC based on vapor–liquid equilibrium data, instead of enthalpies of vaporization or densities. The RMSE of PAC-MAC is reduced to 0.099 kBT by optimizing 50 force field parameters. The resulting OPLS-PM force field has a comparable accuracy as the OPLS-AA force field in the calculation of mixing free energies using TI. PMID:28418655
[Analytic evaluation of potential nootropic agents].

PubMed

Opatrilová, R; Sokolová, P

2004-01-01

The paper deals with analytical evaluation of newly prepared substances, derivatives of N-(4-alkoxy-phenyl)-2-(2-oxo-azepan-1-yl)-acetamide. The substances are a homological series (methyl- to hexyl-). The purity of the substances was verified by thin-layer adsorption chromatography, and the principal physical characteristics--melting point and solubility--were determined. Experimental determination of the partition coefficient, extraction of the substances between two liquids miscible to a limited degree (n-octanol--water), determination of RM values by means of TLC partition chromatography (glass plates DC-Fertigplatten RP-8 F254S), determination of the capacity factor by means of HPLC (column C18 Plaris), and calculation by means of computer programmes were employed to determine the lipophilicity of this series of substances. The antiradical activity of the substances was evaluated by the method of extinguishing the stable radical 2,2-diphenyl-1-picryl-hydrazyl. Ascorbic acid, in which an antiradical effect had been demonstrated, was used for the sake of comparison. The substances show a certain activity, but they do not reach the antioxidative effect of ascorbic acid.
Diffusive mixing through velocity profile variation in microchannels

NASA Astrophysics Data System (ADS)

Yakhshi-Tafti, Ehsan; Cho, Hyoung J.; Kumar, Ranganathan

2011-03-01

Rapid mixing does not readily occur at low Reynolds number flows encountered in microdevices; however, it can be enhanced by passive diffusive mixing schemes. This study of micromixing of two miscible fluids is based on the principle that (1) increased velocity at the interface of co-flowing fluids results in increased diffusive mass flux across their interface, and (2) diffusion interfaces between two liquids progress transversely as the flow proceeds downstream. A passive micromixer is proposed that takes advantage of the peak velocity variation, inducing diffusive mixing. The effect of flow variation on the enhancement of diffusive mixing is investigated analytically and experimentally. Variation of the flow profile is confirmed using micro-Particle Image Velocimetry (μPIV) and mixing is evaluated by color variations resulting from the mixing of pH indicator and basic solutions. Velocity profile variations obtained from μPIV show a shift in peak velocities. The mixing efficiency of the Σ-micromixer is expected to be higher than that for a T-junction channel and can be as high as 80%. The mixing efficiency decreases with Reynolds number and increases with downstream length, exhibiting a power law.
Development of a test method for distillation of diesel-biodiesel-alcohols mixtures at reduced pressure

NASA Astrophysics Data System (ADS)

Niculescu, R.; Iosub, I.; Clenci, A.; Zaharia, C.; Iorga-Simăn, V.

2017-10-01

Increased environmental awareness and depletion of fossil petroleum resources are driving the automotive industry to seek out and use alternative fuels. For instance, the biofuel is a major renewable energy source to supplement declining fossil fuel resources. The addition of alcohols like methanol and ethanol is practical in biodiesel blends due to its miscibility with the pure biodiesel. Alcohols also improve physico-chemical properties of biodiesel blends, which lead to improved combustion efficiency. Proper volatility of fuels is critical to the operation of internal combustion engines with respect to both performance and emissions. Volatility may be characterised by various measurements, the most common of which are vapour pressure, distillation and the vapour/liquid ratio. The presence of ethanol or other oxygenates may affect these properties and, as a result, performance and emissions, as well. However, in the case of diesel-biodiesel-alcohols mixtures, the variance of component volatility makes difficult the analysis of the overall volatility. Thus, the paper presents an experimental method of distilling diesel-biodiesel-alcohols mixtures by adjusting the boiler pressure of an i-Fischer Dist equipment.

Calibration-independent measurement of complex permittivity of liquids using a coaxial transmission line

NASA Astrophysics Data System (ADS)

Guoxin, Cheng

2015-01-01

In recent years, several calibration-independent transmission/reflection methods have been developed to determine the complex permittivity of liquid materials. However, these methods experience their own respective defects, such as the requirement of multi measurement cells, or the presence of air gap effect. To eliminate these drawbacks, a fast calibration-independent method is proposed in this paper. There are two main advantages of the present method over those in the literature. First, only one measurement cell is required. The cell is measured when it is empty and when it is filled with liquid. This avoids the air gap effect in the approach, in which the structure with two reference ports connected with each other is needed to be measured. Second, it eliminates the effects of uncalibrated coaxial cables, adaptors, and plug sections; systematic errors caused by the experimental setup are avoided by the wave cascading matrix manipulations. Using this method, three dielectric reference liquids, i.e., ethanol, ethanediol, and pure water, and low-loss transformer oil are measured over a wide frequency range to validate the proposed method. Their accuracy is assessed by comparing the results with those obtained from the other well known techniques. It is demonstrated that this proposed method can be used as a robust approach for fast complex permittivity determination of liquid materials.
Black-White Achievement Gap and Family Wealth. National Poverty Center Working Paper Series #07-02

ERIC Educational Resources Information Center

Yeung, W. Jean; Conley, Dalton

2006-01-01

This paper examines the extent to which family wealth affects the race-child achievement association for young children based on data from the Panel Study of Income Dynamics. We found little evidence that wealth mediates the black-white test scores gap. However, liquid assets, particularly holding in stocks and mutual funds, are positively…
Ionic Liquids as Novel Lubricants and /or Lubricant Additives

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

Qu, J.; Viola, M. B.

2013-10-31

This ORNL-GM CRADA developed ionic liquids (ILs) as novel lubricants or oil additives for engine lubrication. A new group of oil-miscible ILs have been designed and synthesized with high thermal stability, non-corrosiveness, excellent wettability, and most importantly effective anti-scuffing/anti-wear and friction reduction characteristics. Mechanistic analysis attributes the superior lubricating performance of IL additives to their physical and chemical interactions with metallic surfaces. Working with a leading lubricant formulation company, the team has successfully developed a prototype low-viscosity engine oil using a phosphonium-phosphate IL as an anti-wear additive. Tribological bench tests of the IL-additized formulated oil showed 20-33% lower friction inmore » mixed and elastohydrodynamic lubrication and 38-92% lower wear in boundary lubrication when compared with commercial Mobil 1 and Mobil Clean 5W-30 engine oils. High-temperature, high load (HTHL) full-size engine tests confirmed the excellent anti-wear performance for the IL-additized engine oil. Sequence VID engine dynamometer tests demonstrated an improved fuel economy by >2% for this IL-additized engine oil benchmarked against the Mobil 1 5W-30 oil. In addition, accelerated catalyst aging tests suggest that the IL additive may potentially have less adverse impact on three-way catalysts compared to the conventional ZDDP. Follow-on research is needed for further development and optimization of IL chemistry and oil formulation to fully meet ILSAC GF-5 specifications and further enhance the automotive engine efficiency and durability.« less
A Compact Microwave Microfluidic Sensor Using a Re-Entrant Cavity.

PubMed

Hamzah, Hayder; Abduljabar, Ali; Lees, Jonathan; Porch, Adrian

2018-03-19

A miniaturized 2.4 GHz re-entrant cavity has been designed, manufactured and tested as a sensor for microfluidic compositional analysis. It has been fully evaluated experimentally with water and common solvents, namely methanol, ethanol, and chloroform, with excellent agreement with the expected behaviour predicted by the Debye model. The sensor's performance has also been assessed for analysis of segmented flow using water and oil. The samples' interaction with the electric field in the gap region has been maximized by aligning the sample tube parallel to the electric field in this region, and the small width of the gap (typically 1 mm) result in a highly localised complex permittivity measurement. The re-entrant cavity has simple mechanical geometry, small size, high quality factor, and due to the high concentration of electric field in the gap region, a very small mode volume. These factors combine to result in a highly sensitive, compact sensor for both pure liquids and liquid mixtures in capillary or microfluidic environments.
Efficient room-temperature source of polarized single photons

DOEpatents

Lukishova, Svetlana G.; Boyd, Robert W.; Stroud, Carlos R.

2007-08-07

An efficient technique for producing deterministically polarized single photons uses liquid-crystal hosts of either monomeric or oligomeric/polymeric form to preferentially align the single emitters for maximum excitation efficiency. Deterministic molecular alignment also provides deterministically polarized output photons; using planar-aligned cholesteric liquid crystal hosts as 1-D photonic-band-gap microcavities tunable to the emitter fluorescence band to increase source efficiency, using liquid crystal technology to prevent emitter bleaching. Emitters comprise soluble dyes, inorganic nanocrystals or trivalent rare-earth chelates.
Spark channel propagation in a microbubble liquid

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

Panov, V. A.; Vasilyak, L. M., E-mail: vasilyak@ihed.ras.ru; Vetchinin, S. P.

Experimental study on the development of the spark channel from the anode needle under pulsed electrical breakdown of isopropyl alcohol solution in water with air microbubbles has been performed. The presence of the microbubbles increases the velocity of the spark channel propagation and increases the current in the discharge gap circuit. The observed rate of spark channel propagation in microbubble liquid ranges from 4 to 12 m/s, indicating the thermal mechanism of the spark channel development in a microbubble liquid.
Role of medium heterogeneity and viscosity contrast in miscible flow regimes and mixing zone growth: A computational pore-scale approach

NASA Astrophysics Data System (ADS)

Afshari, Saied; Hejazi, S. Hossein; Kantzas, Apostolos

2018-05-01

Miscible displacement of fluids in porous media is often characterized by the scaling of the mixing zone length with displacement time. Depending on the viscosity contrast of fluids, the scaling law varies between the square root relationship, a sign for dispersive transport regime during stable displacement, and the linear relationship, which represents the viscous fingering regime during an unstable displacement. The presence of heterogeneities in a porous medium significantly affects the scaling behavior of the mixing length as it interacts with the viscosity contrast to control the mixing of fluids in the pore space. In this study, the dynamics of the flow and transport during both unit and adverse viscosity ratio miscible displacements are investigated in heterogeneous packings of circular grains using pore-scale numerical simulations. The pore-scale heterogeneity level is characterized by the variations of the grain diameter and velocity field. The growth of mixing length is employed to identify the nature of the miscible transport regime at different viscosity ratios and heterogeneity levels. It is shown that as the viscosity ratio increases to higher adverse values, the scaling law of mixing length gradually shifts from dispersive to fingering nature up to a certain viscosity ratio and remains almost the same afterwards. In heterogeneous media, the mixing length scaling law is observed to be generally governed by the variations of the velocity field rather than the grain size. Furthermore, the normalization of mixing length temporal plots with respect to the governing parameters of viscosity ratio, heterogeneity, medium length, and medium aspect ratio is performed. The results indicate that mixing length scales exponentially with log-viscosity ratio and grain size standard deviation while the impact of aspect ratio is insignificant. For stable flows, mixing length scales with the square root of medium length, whereas it changes linearly with length during unstable flows. This scaling procedure allows us to describe the temporal variation of mixing length using a generalized curve for various combinations of the flow conditions and porous medium properties.
Phase separation of comb polymer nanocomposite melts.

PubMed

Xu, Qinzhi; Feng, Yancong; Chen, Lan

2016-02-07

In this work, the spinodal phase demixing of branched comb polymer nanocomposite (PNC) melts is systematically investigated using the polymer reference interaction site model (PRISM) theory. To verify the reliability of the present method in characterizing the phase behavior of comb PNCs, the intermolecular correlation functions of the system for nonzero particle volume fractions are compared with our molecular dynamics simulation data. After verifying the model and discussing the structure of the comb PNCs in the dilute nanoparticle limit, the interference among the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions between the comb polymer and nanoparticles in spinodal demixing curves is analyzed and discussed in detail. The results predict two kinds of distinct phase separation behaviors. One is called classic fluid phase boundary, which is mediated by the entropic depletion attraction and contact aggregation of nanoparticles at relatively low nanoparticle-monomer attraction strength. The second demixing transition occurs at relatively high attraction strength and involves the formation of an equilibrium physical network phase with local bridging of nanoparticles. The phase boundaries are found to be sensitive to the side chain number, side chain length, nanoparticle-monomer size ratio and attractive interactions. As the side chain length is fixed, the side chain number has a large effect on the phase behavior of comb PNCs; with increasing side chain number, the miscibility window first widens and then shrinks. When the side chain number is lower than a threshold value, the phase boundaries undergo a process from enlarging the miscibility window to narrowing as side chain length increases. Once the side chain number overtakes this threshold value, the phase boundary shifts towards less miscibility. With increasing nanoparticle-monomer size ratio, a crossover of particle size occurs, above which the phase separation is consistent with that of chain PNCs. The miscibility window for this condition gradually narrows while the other parameters of the PNCs system are held constant. These results indicate that the present PRISM theory can give molecular-level details of the underlying mechanisms of the comb PNCs. It is hoped that the results can be used to provide useful guidance for the future design control of novel, thermodynamically stable comb PNCs.
Miscibility, chain packing, and hydration of 1-palmitoyl-2-oleoyl phosphatidylcholine and other lipids in surface phases.

PubMed

Smaby, J M; Brockman, H L

1985-11-01

The miscibility of 1-palmitoyl-2-oleoyl phosphatidylcholine with triolein, 1,2-diolein, 1,3-diolein, 1(3)-monoolein, oleyl alcohol, methyl oleate, oleic acid, and oleyl cyanide (18:1 lipids) was studied at the argon-water interface. The isothermal phase diagrams for the mixtures at 24 degrees were characterized by two compositional regions. At the limit of miscibility with lower mol fractions of 18:1 lipid, the surface pressure was composition-independent, but above a mixture-specific stoichiometry, surface pressure at the limit of miscibility was composition-dependent. From the two-dimensional phase rule, it was determined that at low mol fractions of 18:1 lipids, the surface consisted of phospholipid and a preferred packing array or complex of phospholipid and 18:1 lipid, whereas, above the stoichiometry of the complex, the surface phase consisted of complex and excess 18:1 lipids. In both regions of the phase diagram, mixing along the phase boundary was apparently ideal allowing application of an equation of state described earlier (J. M. Smaby and H. L. Brockman, 1984, Biochemistry, 23:3312-3316). From such analysis, apparent partial molecular areas and hydrations for phospholipid, complex, and 18:1 lipid were obtained. Comparison of these calculated parameters for the complexed and uncomplexed states shows that the aliphatic moieties behave independently of polar head group. The transition of each 18:1 chain to the complexed state involves the loss of about one interfacial water molecule and its corresponding area. For 18:1 lipids with more than one chain another two water molecules per additional chain are present in both states but contribute little to molecular area. In contrast to 18:1 lipids, the phospholipid area and hydration change little upon complexation. The uniformity of chain packing and hydration behavior among 18:1 lipid species contrasts with complex stoichiometries that vary from 0.04 to 0.65. This suggests that the stoichiometry of the preferred packing array is determined by interactions involving the more polar moieties of the 18:1 lipids and the phospholipid.
Theoretical and experimental investigation of drug-polymer interaction and miscibility and its impact on drug supersaturation in aqueous medium.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2016-10-01

Amorphous solid dispersions (ASDs) have the potential to offer higher apparent solubility and bioavailability of BCS class II drugs. Knowledge of the solid state drug-polymer solubility/miscibility and their mutual interaction are fundamental requirements for the effective design and development of such systems. To this end, we have carried out a comprehensive investigation of various ASD systems of dipyridamole and cinnarizine in polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) at different drug loadings. Theoretical and experimental examinations (by implementing binary and ternary Flory-Huggins (F-H) theory) related to drug-polymer interaction/miscibility including solubility parameter approach, melting point depression method, phase diagram, drug-polymer interaction in the presence of moisture and the effect of drug loading on interaction parameter were performed. The information obtained from this study was used to predict the stability of ASDs at different drug loadings and under different thermal and moisture conditions. Thermal and moisture sorption analysis not only provided the composition-dependent interaction parameter but also predicted the composition dependent miscibility. DPM-PVP, DPM-PAA and CNZ-PAA systems have shown molecular level mixing over the complete range of drug loading. For CNZ-PVP, the presence of a single Tg at lower drug loadings (10, 20 and 35%w/w) indicates the formation of solid solution. However, drug recrystallization was observed for samples with higher drug weight fractions (50 and 65%w/w). Finally, the role of polymer in maintaining drug supersaturation has also been explored. It has been found that drug-polymer combinations capable of hydrogen-bonding in the solution state (DPM-PVP, DPM-PAA and CNZ-PAA) are more effective in preventing drug crystallization compared to the drug-polymer systems without such interaction (CNZ-PVP). The DPM-PAA system outperformed all other ASDs in various stability conditions (dry-state, in the presence of moisture and in solution state), which was attributed to the drug's low crystallization tendency, the strong DPM-PAA interaction, the robustness of this interaction against moisture or water and the ability of PAA in maintaining DPM supersaturation. Copyright © 2016 Elsevier B.V. All rights reserved.
Effect of surface viscosity, anchoring energy, and cell gap on the response time of nematic liquid crystals

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

Souza, R.F. de; Yang, D.-Ke; Lenzi, E.K.

2014-07-15

An analytical expression for the relaxation time of a nematic liquid crystal is obtained for the first time by considering the influence of surface viscosity, anchoring energy strength and cell gap, validated numerically by using the so-called relaxation method. This general equation for the molecular response time (τ{sub 0}) was derived for a vertical aligned cell and by solving an eigenvalue equation coming from the usual balance of torque equation in the Derzhanskii and Petrov formulation, recovering the usual equations in the appropriate limit. The results show that τ∼d{sup b}, where b=2 is observed only for strongly anchored cells, whilemore » for moderate to weak anchored cells, the exponent lies between 1 and 2, depending on both, surface viscosity and anchoring strength. We found that the surface viscosity is important when calculating the response time, specially for thin cells, critical for liquid crystal devices. The surface viscosity’s effect on the optical response time with pretilt is also explored. Our results bring new insights about the role of surface viscosity and its effects in applied physics. - Highlights: • The relaxation of nematic liquid crystals is calculated by taking the surface viscosity into account. • An analytical expression for the relaxation time depending on surface viscosity, anchoring strength and cell gap is obtained. • The results are numerically verified. • Surface viscosity is crucial for thin and weak anchored cells. • The effect on optical time and pretilt angle is also studied.« less
Ga/1-x/Al/x/As LED structures grown on GaP substrates.

NASA Technical Reports Server (NTRS)

Woodall, J. M.; Potemski, R. M.; Blum, S. E.; Lynch, R.

1972-01-01

Ga(1-x)Al(x)As light-emitting diode structures have been grown on GaP substrates by the liquid-phase-epitaxial method. In spite of the large differences in lattice constants and thermal-expansion coefficients, room-temperature efficiencies up to 5.5% in air have been observed for a peak emission of 8500 A. Using undoped GaP substrates, which are transparent to the infrared and red portions of the spectrum, thin structures of Ga(1-x)Al(x)As with large external efficiencies can now be made.
Capillary rise in a textured channel

NASA Astrophysics Data System (ADS)

Beilharz, Daniel; Clanet, Christophe; Quere, David

2016-11-01

A wetting liquid can invade a textured material, for example a forest of micropillars. The driving and the viscous forces of this motion are determined by the texture parameters and the influence of shape, height and spacing of posts has been widely studied for the last decade. In this work, we build a channel with textured walls. Brought into contact with a reservoir of wetting liquid, we observe in some cases two advancing fronts. A first one ahead invading the forest of micropillars, and a second one behind filling the remaining gap. We study and model the conditions of existence and the dynamics of these two fronts as a function of the characteristics of both microstructure and gap of this elementary porous medium.
Research study on materials processing in space experiment number M512. [adhesion-cohesion properties of liquid metals under weightlessness conditions in Skylab

NASA Technical Reports Server (NTRS)

Tobin, J. M.; Kossowsky, R.

1973-01-01

Adhesion of the melted metals to the adjacent solid metals, and cohesion of the liquid metal to itself appeared to be equally as strong in zero gravity as on earth. Similar cut edge bead periodicity in cut thin plate, and similar periodic chevron patterns in full penetration welds were seen. The most significant practical result is that the design of braze joints for near zero gravity can be very tolerant of dimensional gaps in the joint. This conclusion is based on a comparison of narrow, wide and variable gap widths. Brazing is very practical as a joining or repairing technique for metal structures at zero gravity. The operation of the hardware developed to locate successive small (0.6 cm) diameter cylinders in the focus of the battery powered EB unit, melt the various metal specimens and deploy some liquid metal drops to drift in space, was generally successful. However, the sphericity and surface roughness were far from those of ball bearings.
High-temperature compatibility between liquid metal as PWR fuel gap filler and stainless steel and high-density concrete

NASA Astrophysics Data System (ADS)

Wongsawaeng, Doonyapong; Jumpee, Chayanit; Jitpukdee, Manit

2014-08-01

In conventional nuclear fuel rods for light-water reactors, a helium-filled as-fabricated gap between the fuel and the cladding inner surface accommodates fuel swelling and cladding creep down. Because helium exhibits a very low thermal conductivity, it results in a large temperature rise in the gap. Liquid metal (LM; 1/3 weight portion each of lead, tin, and bismuth) has been proposed to be a gap filler because of its high thermal conductivity (∼100 times that of He), low melting point (∼100 °C), and lack of chemical reactivity with UO2 and water. With the presence of LM, the temperature drop across the gap is virtually eliminated and the fuel is operated at a lower temperature at the same power output, resulting in safer fuel, delayed fission gas release and prevention of massive secondary hydriding. During normal reactor operation, should an LM-bonded fuel rod failure occurs resulting in a discharge of liquid metal into the bottom of the reactor pressure vessel, it should not corrode stainless steel. An experiment was conducted to confirm that at 315 °C, LM in contact with 304 stainless steel in the PWR water chemistry environment for up to 30 days resulted in no observable corrosion. Moreover, during a hypothetical core-melt accident assuming that the liquid metal with elevated temperature between 1000 and 1600 °C is spread on a high-density concrete basement of the power plant, a small-scale experiment was performed to demonstrate that the LM-concrete interaction at 1000 °C for as long as 12 h resulted in no penetration. At 1200 °C for 5 h, the LM penetrated a distance of ∼1.3 cm, but the penetration appeared to stop. At 1400 °C the penetration rate was ∼0.7 cm/h. At 1600 °C, the penetration rate was ∼17 cm/h. No corrosion based on chemical reactions with high-density concrete occurred, and, hence, the only physical interaction between high-temperature LM and high-density concrete was from tiny cracks generated from thermal stress. Moreover, for as high as 1600 °C, the non-reactive LM was experimentally confirmed not to show any chemical reaction with air or moisture in the air. This experimental work confirmed the excellent compatibility behaviors between the LM as a PWR fuel gap filler and stainless steel and high-density concrete in the high-temperature regime.
Development of an inter-atomic potential for the Pd-H binary system.

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

Zimmerman, Jonathan A.; Hoyt, Jeffrey John; Leonard, Francois Leonard

2007-09-01

Ongoing research at Sandia National Laboratories has been in the area of developing models and simulation methods that can be used to uncover and illuminate the material defects created during He bubble growth in aging bulk metal tritides. Previous efforts have used molecular dynamics calculations to examine the physical mechanisms by which growing He bubbles in a Pd metal lattice create material defects. However, these efforts focused only on the growth of He bubbles in pure Pd and not on bubble growth in the material of interest, palladium tritide (PdT), or its non-radioactive isotope palladium hydride (PdH). The reason formore » this is that existing inter-atomic potentials do not adequately describe the thermodynamics of the Pd-H system, which includes a miscibility gap that leads to phase separation of the dilute (alpha) and concentrated (beta) alloys of H in Pd at room temperature. This document will report the results of research to either find or develop inter-atomic potentials for the Pd-H and Pd-T systems, including our efforts to use experimental data and density functional theory calculations to create an inter-atomic potential for this unique metal alloy system.« less
Designing Quantum Spin-Orbital Liquids in Artificial Mott Insulators

DOE PAGES

Dou, Xu; Kotov, Valeri N.; Uchoa, Bruno

2016-08-24

Quantum spin-orbital liquids are elusive strongly correlated states of matter that emerge from quantum frustration between spin and orbital degrees of freedom. A promising route towards the observation of those states is the creation of artificial Mott insulators where antiferromagnetic correlations between spins and orbitals can be designed. We show that Coulomb impurity lattices on the surface of gapped honeycomb substrates, such as graphene on SiC, can be used to simulate SU(4) symmetric spin-orbital lattice models. We exploit the property that massive Dirac fermions form mid-gap bound states with spin and valley degeneracies in the vicinity of a Coulomb impurity.more » Due to electronic repulsion, the antiferromagnetic correlations of the impurity lattice are driven by a super-exchange interaction with SU(4) symmetry, which emerges from the bound states degeneracy at quarter filling. We propose that quantum spin-orbital liquids can be engineered in artificially designed solid-state systems at vastly higher temperatures than achievable in optical lattices with cold atoms. Lastly, we discuss the experimental setup and possible scenarios for candidate quantum spin-liquids in Coulomb impurity lattices of various geometries.« less
Remote Field Eddy Curent Signal Modeling for the Gap Measurement of Neighboring Tubes

NASA Astrophysics Data System (ADS)

Jung, H. K.; Lee, D. H.; Lee, Y. S.

2005-04-01

The fuel channels in the Canadian Deuterium Uranium (CANDU) reactor consist of the coaxial pressure tube (PT) and the calandria tube (CT). The Liquid injection nozzle (LIN) is cross aligned with the fuel channel to control the reactor by injecting poison. For a safe operation, the gap between the LIN and CT should be maintained in order to prevent a contact of the neighboring tubes. The remote field eddy current (RFEC) method was applied to measure the gap between a nonmagnetic Zircaloy-2 liquid injection nozzle (LIN) and a Zircaloy-2 calandria tube. Under the condition of inserting the RFEC probe into the coaxial tubes and of crossing a LIN above or under the CT, the modeling of a LIN signal is needed to check the possibility of a gap measurement. The Volume Integral Code S/W which covers the axi-symmetric 3D configuration has been very rarely applied to obtain a LIN signal. This problem was solved by assuming a LIN as a flaw which can be described as a complete 3D object. This simulated LIN signal was verified by performing the laboratory experiment. The gap between the LIN and CT can be correlated with the amplitude of the LIN signals in the voltage plane. Typical noises in the fuel channel were the relative constriction, the change in the pressure tube diameter (fill-factor), thickness variation, and so on. These noise signals were simulated by using the modeling and were analyzed by considering their dependency on the phase angle and amplitude of the voltage plane in order to separate the gap signal from them. It could be concluded that the voltage plane analysis of the simulated RFEC signals were effective for obtaining the gap measurement of the neighboring tube.
Notes: Water Flow and Chemical Retardation in Soils: A Simple Effective Laboratory Demonstration.

ERIC Educational Resources Information Center

Bowman, R. S.; And Others

1988-01-01

Describes a laboratory demonstration that illustrates principles of miscible displacement and chemical retardation in soils. Discusses how the experimental apparatus can be constructed from readily available materials. (TW)
How the flow affects the phase behaviour and microstructure of polymer nanocomposites.

PubMed

Stephanou, Pavlos S

2015-02-14

We address the issue of flow effects on the phase behaviour of polymer nanocomposite melts by making use of a recently reported Hamiltonian set of evolution equations developed on principles of non-equilibrium thermodynamics. To this end, we calculate the spinodal curve, by computing values for the nanoparticle radius as a function of the polymer radius-of-gyration for which the second derivative of the generalized free energy of the system becomes zero. Under equilibrium conditions, we recover the phase diagram predicted by Mackay et al. [Science 311, 1740 (2006)]. Under non-equilibrium conditions, we account for the extra terms in the free energy due to changes in the conformations of polymer chains by the shear flow. Overall, our model predicts that flow enhances miscibility, since the corresponding miscibility window opens up for non-zero shear rate values.

Brewster Angle Microscopy Study of Model Stratum Corneum Lipid Monolayers at the Air-Water Interface

NASA Astrophysics Data System (ADS)

Adams, Ellen; Champagne, Alex; William, Joseph; Allen, Heather

2012-04-01

As the first and last barrier in the body, the stratum corneum (SC) is essential to life. Understanding the interactions and organization of lipids within the SC provides insight into essential physiological processes, including water loss prevention and the adsorption of substances from the environment. Langmuir monolayers have long been used to study complex systems, such as biological membranes and marine aerosols, due to their ability to shed light on intermolecular interactions. In this study, lipid mixtures with varying cholesterol and cerebroside ratios were investigated at the air/water interface. Surface tension measurements along with Brewster angle microscopy (BAM) images were used to examine the lipid phase transitions. Results indicate that cholesterol and cerebrosides form miscible monolayers, exhibiting ideal behavior. BAM images of a singular, uniform collapse phase also suggest formation of a miscible monolayer.
Crystallization of D-mannitol in binary mixtures with NaCl: phase diagram and polymorphism.

PubMed

Telang, Chitra; Suryanarayanan, Raj; Yu, Lian

2003-12-01

To study the crystallization, polymorphism, and phase behavior of D-mannitol in binary mixtures with NaCl to better understand their interactions in frozen aqueous solutions. Differential scanning calorimetry, hot-stage microscopy, Raman microscopy, and variable-temperature X-ray diffractometry were used to characterize D-mannitol-NaCl mixtures. NaCl and D-mannitol exhibited significant melt miscibility (up to 7.5% w/w or 0.20 mole fraction of NaCl) and a eutectic phase diagram (eutectic composition 7.5% w/w NaCl; eutectic temperature 150 degrees C for the alpha and beta polymorphs of D-mannitol and 139 degrees C for the delta). The presence of NaCl did not prevent mannitol from crystallizing but, depending on sample size, affected the polymorph crystallized: below 10 mg, delta was obtained; above 100 mg, alpha was obtained. Pure mannitol crystallized under the same conditions first as the delta polymorph and then as the a polymorph, with the latter nucleating on the former. KCl showed similar eutectic points and melt miscibility with D-mannitol as NaCl. LiCl yielded lower eutectic melting points, inhibited the crystallization of D-mannitol during cooling, and enabled the observation of its glass transition. Despite their structural dissimilarity, significant melt miscibility exists between D-mannitol and NaCl. Their phase diagram has been determined and features polymorph-dependent eutectic points. NaCl influences the polymorphic behavior of mannitol, and the effect is linked to the crystallization of mannitol in two polymorphic stages.
Amorphous and Crystalline Particulates: Challenges and Perspectives in Drug Delivery.

PubMed

Al-Obaidi, Hisham; Majumder, Mridul; Bari, Fiza

2017-01-01

Crystalline and amorphous dispersions have been the focus of academic and industrial research due to their potential role in formulating poorly water-soluble drugs. This review looks at the progress made starting with crystalline carriers in the form of eutectics moving towards more complex crystalline mixtures. It also covers using glassy polymers to maintain the drug as amorphous exhibiting higher energy and entropy. However, the amorphous form tends to recrystallize on storage, which limits the benefits of this approach. Specific interactions between the drug and the polymer may retard this spontaneous conversion of the amorphous drug. Some studies have shown that it is possible to maintain the drug in the amorphous form for extended periods of time. For the drug and the polymer to form a stable mixture they have to be miscible on a molecular basis. Another form of solid dispersions is pharmaceutical co-crystals, for which research has focused on understanding the chemistry, crystal engineering and physico-chemical properties. USFDA has issued a guidance in April 2013 suggesting that the co-crystals as a pharmaceutical product may be a reality; but just not yet! While some of the research is still oriented towards application of these carriers, understanding the mechanism by which drug-carrier miscibility occurs is also covered. Within this context is the use of thermodynamic models such as Flory-Huggins model with some examples of studies used to predict miscibility. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.
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.
Calcium Ions as “Miscibility Switch”: Colocalization of Surfactant Protein B with Anionic Lipids under Absolute Calcium Free Conditions

PubMed Central

Saleem, Mohammed; Meyer, Michaela C.; Breitenstein, Daniel; Galla, Hans-Joachim

2009-01-01

Abstract One of the main determinants of lung surfactant function is the complex interplay between its protein and lipid components. The lipid specificity of surfactant protein B (SP-B), however, and the protein's ability to selectively squeeze out lipids, has remained contradictory. In this work we present, for the first time to our knowledge, by means of time-of-flight secondary ion mass spectrometry chemical imaging, a direct evidence for colocalization of SP-B as well as its model peptide KL4 with negatively charged dipalmitoylphosphatidylglycerol under absolute calcium free conditions. Our results prove that protein/lipid localization depends on the miscibility of all surfactant components, which itself is influenced by subphase ionic conditions. In contrast to our earlier studies reporting SP-B/KL4 colocalization with zwitterionic dipalmitoylphosphatidylcholine, in the presence of even the smallest traces of calcium, we finally evidence an apparent reversal of protein/lipid mixing behavior upon calcium removal with ethylene diamine tetraacetic acid. In addition, scanning force microscopy measurements reveal that by depleting the subphase from calcium ions the protrusion formation ability of SP-B or KL4 is not hampered. However, in the case of KL4, distinct differences in protrusion morphology and height are visible. Our results support the idea that calcium ions act as a “miscibility switch” in surfactant model systems and probably are one of the major factors steering lipid/protein mixing behavior as well as influencing the protein's protrusion formation ability. PMID:19619464
Improved Method Of Bending Concentric Pipes

NASA Technical Reports Server (NTRS)

Schroeder, James E.

1995-01-01

Proposed method for bending two concentric pipes simultaneously while maintaining void between them replaces present tedious, messy, and labor-intensive method. Array of rubber tubes inserted in gap between concentric pipes. Tubes then inflated with relatively incompressible liquid to fill gap. Enables bending to be done faster and more cleanly, and amenable to automation of significant portion of bending process on computer numerically controlled (CNC) tube-bending machinery.
Process optimization for microcystin-LR degradation by Response Surface Methodology and mechanism analysis in gas-liquid hybrid discharge system.

PubMed

Zhang, Yi; Wei, Hanyu; Xin, Qing; Wang, Mingang; Wang, Qi; Wang, Qiang; Cong, Yanqing

2016-12-01

A gas-liquid hybrid discharge system was applied to microcystin-LR (MC-LR) degradation. MC-LR degradation was completed after 1 min under a pulsed high voltage of 16 kV, gas-liquid interface gap of 10 mm and oxygen flow rate of 160 L/h. The Box-Behnken Design was proposed in Response Surface Methodology to evaluate the influence of pulsed high voltage, electrode distance and oxygen flow rate on MC-LR removal efficiency. Multiple regression analysis, focused on multivariable factors, was employed and a reduced cubic model was developed. The ANOVA analysis shows that the model is significant and the model prediction on MC-LR removal was also validated with experimental data. The optimum conditions for the process are obtained at pulsed voltage of 16 kV, gas-liquid interface gap of 10 mm and oxygen flow rate of 120 L/h with ta removal efficiency of MC-LR of 96.6%. The addition of catalysts (TiO 2 or Fe 2+ ) in the gas-liquid hybrid discharge system was found to enhance the removal of MC-LR. The intermediates of MC-LR degradation were analyzed by liquid chromatography/mass spectrometry. The degradation pathway proposed envisaged the oxidation of hydroxyl radicals and ozone, and attack of high-energy electrons on the unsaturated double bonds of Adda and Mdha, with MC-LR finally decomposing into small molecular products. Copyright © 2016 Elsevier Ltd. All rights reserved.
GaAs quantum dots in a GaP nanowire photodetector

NASA Astrophysics Data System (ADS)

Kuyanov, P.; McNamee, S. A.; LaPierre, R. R.

2018-03-01

We report the structural, optical and electrical properties of GaAs quantum dots (QDs) embedded along GaP nanowires. The GaP nanowires contained p-i-n junctions with 15 consecutively grown GaAs QDs within the intrinsic region. The nanowires were grown by molecular beam epitaxy using the self-assisted vapor-liquid-solid process. The crystal structure of the NWs alternated between twinned ZB and WZ as the composition along the NW alternated between the GaP barriers and the GaAs QDs, respectively, leading to a polytypic structure with a periodic modulation of the NW sidewall facets. Photodetector devices containing QDs showed absorption beyond the bandgap of GaP in comparison to nanowires without QDs. Voltage-dependent measurements suggested a field emission process of carriers from the QDs.
Probing ionization potential, electron affinity and self-energy effect on the spectral shape and exciton binding energy of quantum liquid water with self-consistent many-body perturbation theory and the Bethe-Salpeter equation.

PubMed

Ziaei, Vafa; Bredow, Thomas

2018-05-31

An accurate theoretical prediction of ionization potential (IP) and electron affinity (EA) is key in understanding complex photochemical processes in aqueous environments. There have been numerous efforts in literature to accurately predict IP and EA of liquid water, however with often conflicting results depending on the level of theory and the underlying water structures. In a recent study based on hybrid-non-self-consistent many-body perturbation theory (MBPT) Gaiduk et al (2018 Nat. Commun. 9 247) predicted an IP of 10.2 eV and EA of 0.2 eV, resulting in an electronic band gap (i.e. electronic gap (IP-EA) as measured by photoelectron spectroscopy) of about 10 eV, redefining the widely cited experimental gap of 8.7 eV in literature. In the present work, we show that GW self-consistency and an implicit vertex correction in MBPT considerably affect recently reported EA values by Gaiduk et al (2018 Nat. Commun. 9 247) by about 1 eV. Furthermore, the choice of pseudo-potential is critical for an accurate determination of the absolute band positions. Consequently, the self-consistent GW approach with an implicit vertex correction based on projector augmented wave (PAW) method on top of quantum water structures predicts an IP of 10.2, an EA of 1.1, a fundamental gap of 9.1 eV and an exciton binding (Eb) energy of 0.9 eV for the first absorption band of liquid water via the Bethe-Salpeter equation (BSE). Only within such a self-consistent approach a simultanously accurate prediction of IP, EA, Eg, Eb is possible.
Probing ionization potential, electron affinity and self-energy effect on the spectral shape and exciton binding energy of quantum liquid water with self-consistent many-body perturbation theory and the Bethe–Salpeter equation

NASA Astrophysics Data System (ADS)

Ziaei, Vafa; Bredow, Thomas

2018-05-01

An accurate theoretical prediction of ionization potential (IP) and electron affinity (EA) is key in understanding complex photochemical processes in aqueous environments. There have been numerous efforts in literature to accurately predict IP and EA of liquid water, however with often conflicting results depending on the level of theory and the underlying water structures. In a recent study based on hybrid-non-self-consistent many-body perturbation theory (MBPT) Gaiduk et al (2018 Nat. Commun. 9 247) predicted an IP of 10.2 eV and EA of 0.2 eV, resulting in an electronic band gap (i.e. electronic gap (IP-EA) as measured by photoelectron spectroscopy) of about 10 eV, redefining the widely cited experimental gap of 8.7 eV in literature. In the present work, we show that GW self-consistency and an implicit vertex correction in MBPT considerably affect recently reported EA values by Gaiduk et al (2018 Nat. Commun. 9 247) by about 1 eV. Furthermore, the choice of pseudo-potential is critical for an accurate determination of the absolute band positions. Consequently, the self-consistent GW approach with an implicit vertex correction based on projector augmented wave (PAW) method on top of quantum water structures predicts an IP of 10.2, an EA of 1.1, a fundamental gap of 9.1 eV and an exciton binding (Eb) energy of 0.9 eV for the first absorption band of liquid water via the Bethe–Salpeter equation (BSE). Only within such a self-consistent approach a simultanously accurate prediction of IP, EA, Eg, Eb is possible.
Electronic energy gap of molecular hydrogen from electrical conductivity measurements at high shock pressures

NASA Technical Reports Server (NTRS)

Nellis, W. J.; Mitchell, A. C.; Mccandless, P. C.; Erskine, D. J.; Weir, S. T.

1992-01-01

Electrical conductivities were measured for liquid D2 and H2 shock compressed to pressures of 10-20 GPa (100-200 kbar), molar volumes near 8 cu cm/mol, and calculated temperatures of 2900-4600 K. The semiconducting energy gap derived from the conductivities is 12 eV, in good agreement with recent quasi-particle calculations and with oscillator frequencies measured in diamond-anvil cells.
Transmission through a potential barrier in Luttinger liquids with a topological spin gap

NASA Astrophysics Data System (ADS)

Kainaris, Nikolaos; Carr, Sam T.; Mirlin, Alexander D.

2018-03-01

We study theoretically the transport of the one-dimensional single-channel interacting electron gas through a strong potential barrier in the parameter regime where the spin sector of the low-energy theory is gapped by interaction (Luther-Emery liquid). There are two distinct phases of this nature, of which one is of particular interest as it exhibits nontrivial interaction-induced topological properties. Focusing on this phase and using bosonization and an expansion in the tunneling strength we calculate the conductance through the barrier as a function of the temperature as well as the local density of states (LDOS) at the barrier. Our main result concerns the mechanism of bound-state-mediated tunneling. The characteristic feature of the topological phase is the emergence of protected zero-energy bound states with fractional spin located at the impurity position. By flipping this fractional spin, single electrons can tunnel across the impurity even though the bulk spectrum for spin excitations is gapped. This results in a finite LDOS below the bulk gap and in a nonmonotonic behavior of the conductance. The system represents an important physical example of an interacting symmetry-protected topological phase, which combines features of a topological spin insulator and a topological charge metal, in which the topology can be probed by measuring transport properties.
Theory of Fermi Liquid with Flat Bands

NASA Astrophysics Data System (ADS)

Khodel, V. A.

2018-04-01

A self-consistent theory of Fermi systems hosting flat bands is developed. Compared with an original model of fermion condensation, its key point consists in proper accounting for mixing between condensate and non-condensate degrees of freedom that leads to formation of a non-BCS gap Υ (p) in the single-particle spectrum. The results obtained explain: (1) the two-gap structure of spectra of single-particle excitations of electron systems of copper oxides, revealed in ARPES studies, (2) the role of violation of the topological stability of the Landau state in the arrangement of the T-x phase diagram of this family of high-T_c superconductors, (3) the topological nature of a metal-insulator transition, discovered in homogeneous two-dimensional low-density electron liquid of MOSFETs more than 20 years ago.
Diagnosis of toxic alcohols: limitations of present methods.

PubMed

Kraut, Jeffrey A

2015-01-01

Methanol, ethylene glycol, diethylene glycol, and propylene glycol intoxications are associated with cellular dysfunction and an increased risk of death. Adverse effects can develop quickly; thus, there is a need for methods for rapidly detecting their presence. To examine the value and limitations of present methods to diagnose patients with possible toxic alcohol exposure. I searched MEDLINE for articles published between 1969 and 2014 using the terms: toxic alcohols, serum osmolality, serum osmol gap, serum anion gap, metabolic acidosis, methanol, ethylene glycol, diethylene glycol, propylene glycol, and fomepizole. Each article was reviewed for additional references. The diagnosis of toxic alcohol exposure is often made on the basis of this history and physical findings along with an increase in the serum osmol and anion gaps. However, an increase in the osmol and/or anion gaps is not always present. Definitive detection in blood requires gas or liquid chromatography, laborious and expensive procedures which are not always available. Newer methods including a qualitative colorimetric test for detection of all alcohols or enzymatic tests for a specific alcohol might allow for more rapid diagnosis. Exposure to toxic alcohols is associated with cellular dysfunction and increased risk of death. Treatment, if initiated early, can markedly improve outcome, but present methods of diagnosis including changes in serum osmol and anion gap, and use of gas or liquid chromatography have important limitations. Development of more rapid and effective tests for detection of these intoxications is essential for optimal care of patients.
Stabilization of a finite slice in miscible displacement in homogeneous porous media

NASA Astrophysics Data System (ADS)

Pramanik, Satyajit; Mishra, Manoranjan

2016-11-01

We numerically studied the miscible displacement of a finite slice of variable viscosity and density. The stability of the finite slice depends on different flow parameters, such as displacement velocity U, mobility ratio R , and the density contrast. Series of numerical simulations corresponding to different ordered pair (R, U) in the parameter space, and a given density contrast reveal six different instability regions. We have shown that independent of the width of the slice, there always exists a region of stable displacement, and below a critical value of the slice width, this stable region increases with decreasing slice width. Further we observe that the viscous fingering (buoyancy-induced instability) at the upper interface induces buoyancy-induced instability (viscous fingering) at the lower interface. Besides the fundamental fluid dynamics understanding, our results can be helpful to model CO2 sequestration and chromatographic separation.
Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR FT-IR) Mapping Coupled with Multivariate Curve Resolution (MCR) for Studying the Miscibility of Chlorobutyl Rubber/Polyamide-12 Blends.

PubMed

Tang, Yongjiao; Jing, Nan; Zhang, Pudun

2015-11-01

A series of chlorobutyl rubber/polyamide-12 (CIIR/PA-12) blends compatibilized by different amounts of maleic anhydride (MAH) grafted polypropylene (PP-g-MAH) were investigated by attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) mapping. Multivariate curve resolution (MCR) was used to process the FT-IR images. Both the spectra of pure components in the blends and their concentration distributions in a micro-region were acquired. Our results demonstrated that the blend with 15 parts per hundred rubber PP-g-MAH showed the best miscibility. An amide interphase and an imide interphase were inferred by analyzing the spectra of MCR component 3 of the blends with and without PP-g-MAH, respectively. Correspondingly, two different compatibilizing mechanisms were proposed for these blends.
Density profiles around A+B→C reaction-diffusion fronts in partially miscible systems: A general classification.

PubMed

Loodts, V; Trevelyan, P M J; Rongy, L; De Wit, A

2016-10-01

Various spatial density profiles can develop in partially miscible stratifications when a phase A dissolves with a finite solubility into a host phase containing a dissolved reactant B. We investigate theoretically the impact of an A+B→C reaction on such density profiles in the host phase and classify them in a parameter space spanned by the ratios of relative contributions to density and diffusion coefficients of the chemical species. While the density profile is either monotonically increasing or decreasing in the nonreactive case, reactions combined with differential diffusivity can create eight different types of density profiles featuring up to two extrema in density, at the reaction front or below it. We use this framework to predict various possible hydrodynamic instability scenarios inducing buoyancy-driven convection around such reaction fronts when they propagate parallel to the gravity field.
Miscibility and crystallization behavior of poly (3-hydroxybutyrate) and poly (ethylene glycol) blends studied by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Abdel-Hady, E. E.; Abdel-Hamed, M. O.; Hammam, A. M.

2011-01-01

Positron annihilation Lifetime (PAL) spectroscopy has been used to study the effect of PEG concentrations on the free volume properties of PHB. The data revealed that the ortho-positronium (o-Ps) lifetime τPs increases with 20% increase in concentration, decrease as the concentration increases to 40%, then rapid increase at 50% concentration of PEG. The o-Ps intensity, I3, shows a linear dependence as the concentration increases with a discontinuity at 20% concentration of PEG. Furthermore, the results presented and discussed in this work show that the PHB and PEG are miscible up to 40% of PEG but greater than 40%, the blend is immiscible. In addition, the mechanical properties of PHB are well improved by the addition of PEG with a low concentration up to 20%, while at higher concentration the blend becomes waxy.
Confinement effects on the miscibility of block copolymer blends.

PubMed

Spencer, Russell K W; Matsen, Mark W

2016-04-01

Thin films of long and short symmetric AB diblock copolymers are examined using self-consistent field theory (SCFT). We focus on hard confining walls with a preference for the A component, such that the lamellar domains orient parallel to the film with an even number ν of monolayers. For neat melts, confinement causes the lamellar period, D, to deviate from its bulk value, Db, in order to be commensurate with the film thickness, i.e., L = νD/2. For blends, however, the melt also has the option of macrophase separating into ν(l) large and ν((s)) small monolayers so as to provide a better fit, where L = ν(l)D(l)/2 + ν(s)D((s))/2. In addition to performing full SCFT calculations of the entire film, we develop a semi-analytical calculation for the coexistence of thick and thin monolayers that helps explain the complicated interplay between miscibility and commensurability.
Polymer collapse in miscible good solvents is a generic phenomenon driven by preferential adsorption

PubMed Central

Mukherji, Debashish; Marques, Carlos M.; Kremer, Kurt

2014-01-01

Water and alcohol, such as methanol or ethanol, are miscible and, individually, good solvents for poly(N-isopropylacrylamide) (PNIPAm), but this polymer precipitates in water–alcohol mixtures. The intriguing behaviour of solvent mixtures that cannot dissolve a given polymer or a given protein, while the same macromolecule dissolves well in each of the cosolvents, is called cononsolvency. It is a widespread phenomenon, relevant for many formulation steps in the physicochemical and pharmaceutical industry, that is usually explained by invoking specific chemical details of the mixtures: as such, it has so far eluded any generic explanation. Here, by using a combination of simulations and theory, we present a simple and universal treatment that requires only the preferential interaction of one of the cosolvents with the polymer. The results show striking quantitative agreement with experiments and chemically specific simulations, opening a new perspective towards an operational understanding of macromolecular solubility. PMID:25216245

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