Relative volatility of dilute solutions of Rb-Cs system

International Nuclear Information System (INIS)

Gromov, P.B.; Izotov, V.P.; Nisel'son, L.A.

1984-01-01

Relative volatility of diluted solutions Rb-Cs in the temperature range 650-820 K and pressures 13-200 gPa has been studied. The system Rb-Cs in the range of diluted solutions obeys the Henry law. It is shown, that liquid-vapour equilibrium in diluted solutions of cesium in rubidium is characterized by negative deviation from perfection

Light scattering from polymer solutions and nanoparticle dispersions

CERN Document Server

Schärtl, Wolfgang; Janca, Josef

2007-01-01

Light scattering is a very powerful method to characterize the structure of polymers and nanoparticles in solution. Recent technical developments have strongly enhanced the possible applications of this technique, overcoming previous limitations like sample turbidity or insufficient experimental time scales. However, despite their importance, these new developments have not yet been presented in a comprehensive form. In addition, and maybe even more important to the broad audience, there lacks a simple-to-read textbook for students and non-experts interested in the basic principles and fundamental techniques of light scattering. As part of the Springer Laboratory series, this book tries not only to provide such a simple-to-read and illustrative textbook about the seemingly very complicated topic of light scattering from polymers and nanoparticles in dilute solution, but also intends to cover some of the newest technical developments in experimental light scattering.

Bridging the Gap between Polymer Melts and Solutions in Extensional Rheology

DEFF Research Database (Denmark)

Huang, Qian; Hengeller, Ludovica; Alvarez, Nicolas J.

2015-01-01

Since its inception, the tube model of polymer dynamics has undergone several modifications to account for observed experimental trends. One trend that has yet to be captured by a modified version of the tube model is the observed experimental difference between concentrated polymer solutions...... per chain and are diluted in the same solvent (oligomeric styrene). We show that the difference in nonlinear rheological behavior between polystyrene melts reported by Bach et al.1 and polystyrene solutions reported by Bhattacharjee et al.2 and Sridhar et al.3 can be bridged by changing...... the polystyrene concentration. The results presented represent a unique benchmark for all future modifications to the tube model....

Photoinduced partial charge transfer between conjugated polymer and fullerene in solutions

International Nuclear Information System (INIS)

Lin Hongzhen; Weng Yufeng; Huang Hongmin; He Qingguo; Zheng Min; Bai Fenglian

2004-01-01

Photoinduced charge transfer between a conjugated polymer and C 60 and the related processes were investigated in dilute solutions. The substantial fluorescence quenching is correlated with the efficient exciton diffusion within the polymer chains, according to which a sphere-of-action mechanism is proposed. An emissive exciplex was found formed between the conjugated polymer and fullerene in a nonpolar solvent, indicating the occurrence of a photoinduced partial charge transfer process. The low-energy sites in the polymer are believed to play a crucial role in the partial charge transfer. The asymmetry of the exciplex provides a method for evaluating the tendency of photoinduced charge separation between the donor and the acceptor. This method allows screening candidates for photovoltaic applications

Measurement of infinite dilution activity coefficient and application of modified ASOG model for solvent-polymer systems

Energy Technology Data Exchange (ETDEWEB)

Choi, B.; Choi, J. [Kwangwoon University, Seoul (Korea, Republic of); Tochigi, K.; Kojima, K. [Nihon University, Tokyo (Japan)

1996-04-20

A gas chromatographic method was used in order to measure vapor-liquid equilibria for solvent (1)-polymer (2) systems in which the polymers were polystyrene, poly(a-methyl) styrene and the advents were benzene toluene cyclohexane methylisobutylketone, ethylacetate, and vinylacetate. The activity coefficients of solvents for solvent (1)-polymer (2) systems were measured at infinite dilution and the modified ASOG (Analytical Solution of Group) model was suggested to describe vapor-liquid equilibria of those systems within a range of temperatures 423.15K through 498.15K. The model consists of the original ASOG and the free volume term. An external degree of freedom in the free volume term empirically became to a C1={alpha}+{beta}/T as a function of temperature. Each tern in the modified ASOG model is based on the weight fraction. The external degree of freedom in the model was estimated by experimental data within a range of temperatures. As a result of doing it the infinite dilution activity coefficients calculated were agreed with the experimental data within an error of 0.1%. 27 refs., 3 figs., 7 tabs.

Communication: Polarizable polymer chain under external electric field in a dilute polymer solution.

Science.gov (United States)

Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

2015-11-28

We study the conformational behavior of polarizable polymer chain under an external homogeneous electric field within the Flory type self-consistent field theory. We consider the influence of electric field on the polymer coil as well as on the polymer globule. We show that when the polymer chain conformation is a coil, application of external electric field leads to its additional swelling. However, when the polymer conformation is a globule, a sufficiently strong field can induce a globule-coil transition. We show that such "field-induced" globule-coil transition at the sufficiently small monomer polarizabilities goes quite smoothly. On the contrary, when the monomer polarizability exceeds a certain threshold value, the globule-coil transition occurs as a dramatic expansion in the regime of first-order phase transition. The developed theoretical model can be applied to predicting polymer globule density change under external electric field in order to provide more efficient processes of polymer functionalization, such as sorption, dyeing, and chemical modification.

Measurements of mass-fraction activity coefficient at infinite dilution of aliphatic and aromatic hydrocarbons, thiophene, alcohols, water, ethers, and ketones in hyperbranched polymer, Boltorn H2004, using inverse gas chromatography

International Nuclear Information System (INIS)

Domanska, Urszula; Zolek-Tryznowska, Zuzanna

2010-01-01

Thermodynamic properties of the hyperbranched polymer, Boltorn H2004 (B-H2004), were investigated by inverse gas chromatography with 42 different solvents: n-alkanes (C 5 -C 10 ), cycloalkanes (C 5 -C 8 ), alkenes (C 5 -C 8 ), alkynes (C 5 -C 8 ), aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-, m-, p-xylene, thiophene), alcohols (C 1 -C 5 ), water, ethers (tetrahydrofuran (THF), methyl-tert-butylether (MTBE), diethyl-, di-n-propyl-, di-n-butyl ether), and ketones (acetone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclopentanone) at the temperatures from (308.15 to 348.15) K using the inverse gas chromatography (IGC). The density and thermophysical properties of polymer were described. The specific retention volume (V g ), the mass-fraction activity coefficient at infinite dilution (Ω 13 ∞ ), the Flory-Huggins interaction parameter (χ 13 ∞ ), the molar enthalpy of sorption in the polymer (Δ s H), the partial molar excess enthalpy at infinite dilution (ΔH 1 E,∞ ), the molar enthalpy of vaporization to the ideal-gas state for the pure solutes (Δ vap H 0 ), the partial molar Gibbs excess energy at infinite dilution (ΔG 1 E,∞ ), and the solubility parameter of the polymer (δ 3 ), were calculated. The UNIFAC-FV model was used to predict the mass-fraction activity coefficient at infinite dilution for different solutes in the B-H2004 polymer.

Multiresolution Modeling of Semidilute Polymer Solutions: Coarse-Graining Using Wavelet-Accelerated Monte Carlo

Directory of Open Access Journals (Sweden)

Animesh Agarwal

2017-09-01

Full Text Available We present a hierarchical coarse-graining framework for modeling semidilute polymer solutions, based on the wavelet-accelerated Monte Carlo (WAMC method. This framework forms a hierarchy of resolutions to model polymers at length scales that cannot be reached via atomistic or even standard coarse-grained simulations. Previously, it was applied to simulations examining the structure of individual polymer chains in solution using up to four levels of coarse-graining (Ismail et al., J. Chem. Phys., 2005, 122, 234901 and Ismail et al., J. Chem. Phys., 2005, 122, 234902, recovering the correct scaling behavior in the coarse-grained representation. In the present work, we extend this method to the study of polymer solutions, deriving the bonded and non-bonded potentials between coarse-grained superatoms from the single chain statistics. A universal scaling function is obtained, which does not require recalculation of the potentials as the scale of the system is changed. To model semi-dilute polymer solutions, we assume the intermolecular potential between the coarse-grained beads to be equal to the non-bonded potential, which is a reasonable approximation in the case of semidilute systems. Thus, a minimal input of microscopic data is required for simulating the systems at the mesoscopic scale. We show that coarse-grained polymer solutions can reproduce results obtained from the more detailed atomistic system without a significant loss of accuracy.

Constant force extensional rheometry of polymer solutions

DEFF Research Database (Denmark)

Szabo, Peter; McKinley, Gareth H.; Clasen, Christian

2012-01-01

We revisit the rapid stretching of a liquid filament under the action of a constant imposed tensile force, a problem which was first considered by Matta and Tytus [J. Non-Newton. Fluid Mech. 35 (1990) 215–229]. A liquid bridge formed from a viscous Newtonian fluid or from a dilute polymer solution...... is first established between two cylindrical disks. The upper disk is held fixed and may be connected to a force transducer while the lower cylinder falls due to gravity. By varying the mass of the falling cylinder and measuring its resulting acceleration, the viscoelastic nature of the elongating fluid...... filament can be probed. In particular, we show that with this constant force pull (CFP) technique it is possible to readily impose very large material strains and strain rates so that the maximum extensibility of the polymer molecules may be quantified. This unique characteristic of the experiment...

Generalized Langevin Theory Of The Brownian Motion And The Dynamics Of Polymers In Solution

International Nuclear Information System (INIS)

Tothova, J.; Lisy, V.

2015-01-01

The review deals with a generalization of the Rouse and Zimm bead-spring models of the dynamics of flexible polymers in dilute solutions. As distinct from these popular theories, the memory in the polymer motion is taken into account. The memory naturally arises as a consequence of the fluid and bead inertia within the linearized Navier-Stokes hydrodynamics. We begin with a generalization of the classical theory of the Brownian motion, which forms the basis of any theory of the polymer dynamics. The random force driving the Brownian particles is not the white one as in the Langevin theory, but “colored”, i.e., statistically correlated in time, and the friction force on the particles depends on the history of their motion. An efficient method of solving the resulting generalized Langevin equations is presented and applied to the solution of the equations of motion of polymer beads. The memory effects lead to several peculiarities in the time correlation functions used to describe the dynamics of polymer chains. So, the mean square displacement of the polymer coils contains algebraic long-time tails and at short times it is ballistic. It is shown how these features reveal in the experimentally observable quantities, such as the dynamic structure factors of the scattering or the viscosity of polymer solutions. A phenomenological theory is also presented that describes the dependence of these quantities on the polymer concentration in solution. (author)

Carbon Nanotube Dispersion in Solvents and Polymer Solutions: Mechanisms, Assembly, and Preferences.

Science.gov (United States)

Pramanik, Chandrani; Gissinger, Jacob R; Kumar, Satish; Heinz, Hendrik

2017-12-26

Debundling and dispersion of carbon nanotubes (CNTs) in polymer solutions play a major role in the preparation of carbon nanofibers due to early effects on interfacial ordering and mechanical properties. A roadblock toward ultrastrong fibers is the difficulty to achieve homogeneous dispersions of CNTs in polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) precursor solutions in solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). In this contribution, molecular dynamics simulations with accurate interatomic potentials for graphitic materials that include virtual π electrons are reported to analyze the interaction of pristine single wall CNTs with the solvents and polymer solutions at 25 °C. The results explain the barriers toward dispersion of SWCNTs and quantify CNT-solvent, polymer-solvent, as well as CNT-polymer interactions in atomic detail. Debundling of CNTs is overall endothermic and unfavorable with dispersion energies of +20 to +30 mJ/m 2 in the pure solvents, + 20 to +40 mJ/m 2 in PAN solutions, and +20 to +60 mJ/m 2 in PMMA solutions. Differences arise due to molecular geometry, polar, van der Waals, and CH-π interactions. Among the pure solvents, DMF restricts CNT dispersion less due to the planar geometry and stronger van der Waals interactions. PAN and PMMA interact favorably with the pure solvents with dissolution energies of -0.7 to -1.1 kcal per mole monomer and -1.5 to -2.2 kcal per mole monomer, respectively. Adsorption of PMMA onto CNTs is stronger than that of PAN in all solvents as the molecular geometry enables more van der Waals contacts between alkyl groups and the CNT surface. Polar side groups in both polymers prefer interactions with the polar solvents. Higher polymer concentrations in solution lead to polymer aggregation via alkyl groups and reduce adsorption onto CNTs. PAN and PMMA solutions in DMSO and dilute solutions in DMF support CNT dispersion more than other

Neutron scattering study of dilute supercritical solutions

International Nuclear Information System (INIS)

Cochran, H.D.; Wignall, G.D.; Shah, V.M.; Londono, J.D.; Bienkowski, P.R.

1994-01-01

Dilute solutions in supercritical solvents exhibit interesting microstructures that are related to their dramatic macroscopic behavior. In typical attractive solutions, solutes are believed to be surrounded by clusters of solvent molecules, and solute molecules are believed to congregate in the vicinity of one another. Repulsive solutions, on the other hand, exhibit a local region of reduced solvent density around the solute with solute-solute congregation. Such microstructures influence solubility, partial molar volume, reaction kinetics, and many other properties. We have undertaken to observe these interesting microstructures directly by neutron scattering experiments on dilute noble gas systems including Ar. The three partial structure factors for such systems and the corresponding pair correlation functions can be determined by using the isotope substitution technique. The systems studied are uniquely suited for our objectives because of the large coherent neutron scattering length of the isotope 36 Ar and because of the accurate potential energy functions that are available for use in molecular simulations and theoretical calculations to be compared with the scattering results. We will describe our experiment, the unique apparatus we have built for it, and the neutron scattering results from our initial allocations of beam time. We will also describe planned scattering experiments to follow those with noble gases, including study of long-chain molecules in supercritical solvents. Such studies will involve hydrocarbon mixtures with and without deuteration to provide contrast

A Study on the Stability of Diluted Bee Venom Solution

Directory of Open Access Journals (Sweden)

Mi-Suk Kang

2003-06-01

Full Text Available Objective : The purpose of this study was to investigate the stability of bee venom according to the keeping method and period. Method : The author observed microbial contamination of bee venom in nutrient agar, broth, YPD agar and YPD media and antibacterial activity for S. aureus, E. coli manufactured 12, 6 and 3 months ago as the two type of room temperature and 4℃ cold storage. Result : 1. 1:3,000 and 1:4,000 diluted bee venom solution did not show microbial contamination both room temperature and cold storage within twelve months. 2. There was antibacterial activity of diluted bee venom for S. aureus in cold storage within twelve months and there was no antibacterial activity of diluted bee venom for S. aureus in twelve months, room temperature storage. 3. We could not observe the zone of inhibition around paper disc of all for E.coli. in 1:3,000, 1:30,000 and 1:3,000,000 diluted bee venom solution, respectively. According to results, we expect that diluted bee venom solution is stable both cold and room temperature storage within twelve months.

Electrochemical reduction of nickel ions from dilute solutions

NARCIS (Netherlands)

Njau, K.N.; Janssen, L.J.J.

1995-01-01

Electrochemical reduction of nickel ions in dilute solution using a divided GBC-cell is of interest for purification of waste waters. A typical solution to be treated is the effluent from steel etching processes which contain low quantities of nickel, chromate and chromium ions. Reduction of

Dilution Confusion: Conventions for Defining a Dilution

Science.gov (United States)

Fishel, Laurence A.

2010-01-01

Two conventions for preparing dilutions are used in clinical laboratories. The first convention defines an "a:b" dilution as "a" volumes of solution A plus "b" volumes of solution B. The second convention defines an "a:b" dilution as "a" volumes of solution A diluted into a final volume of "b". Use of the incorrect dilution convention could affect…

Phase Equilibria for Complex Polymer Solutions

DEFF Research Database (Denmark)

Lindvig, Thomas; Hestkjær, L. L.; Hansen, A. F.

2002-01-01

the content of organic solvents. This work presents an investigation of the three polymer models Entropic-FV (EFV). UNIFAC-FV (UFV) and GC-Flory (GCF) for their capability of predicting solvent activity coefficients in binary systems containing complex polymers. It is possible to obtain good predictions...... at finite concentrations and satisfactory predictions at infinite dilution, particularly with the EFV model. The investigation shows that EFV is the most robust and stable of the models, which indicates that it is the most well suited model for further development of methods for predicting the miscibility...

Electrostatics of polymer translocation events in electrolyte solutions.

Science.gov (United States)

Buyukdagli, Sahin; Ala-Nissila, T

2016-07-07

We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ≈10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.

Photoluminescence Spectroscopy of Rhodamine 800 Aqueous Solution and Dye-Doped Polymer Thin-Film: Concentration and Solvent Effects

Science.gov (United States)

Le, Khai Q.; Dang, Ngo Hai

2018-05-01

This paper investigates solvent and concentration effects on photoluminescence (PL) or fluorescence properties of Rhodamine 800 (Rho800) dyes formed in aqueous solution and polymer thin-film. Various commonly used organic solvents including ethanol, methanol and cyclopentanol were studied at a constant dye concentration. There were small changes in the PL spectra for the different solvents in terms of PL intensity and peak wavelength. The highest PL intensity was observed for cyclopentanol and the lowest for ethanol. The longest peak wavelength was found in cyclopentanol (716 nm) and the shortest in methanol (708 nm). Dissolving the dye powder in the methanol solvent and varying the dye concentration in aqueous solution from the high concentrated solution to highly dilute states, the wavelength tunability was observed between about 700 nm in the dilute state and 730 nm at high concentration. Such a large shift may be attributed to the formation of dye aggregates. Rho800 dye-doped polyvinyl alcohol (PVA) polymer thin-film was further investigated. The PL intensity of the dye in the form of thin-film is lower than that of the aqueous solution form whereas the peak wavelength is redshifted due to the presence of PVA. This paper, to our best knowledge, reports the first study of spectroscopic properties of Rho800 dyes in various forms and provides useful guidelines for production of controllable organic luminescence sources.

Continuous deionization of a dilute nickel solution

NARCIS (Netherlands)

Spoor, P.B.; Koene, L.; Veen, ter W.R.; Janssen, L.J.J.

2002-01-01

This paper describes the continuous removal of nickel ions from a dilute solution using a hybrid ion-exchange/electrodialysis process. Emphasis was placed on the ionic state of the bed during the process, and the mass balance of ions in the system. Much of this information was obtained by analysing

Foaming behaviour of polymer-surfactant solutions

International Nuclear Information System (INIS)

Cervantes-MartInez, Alfredo; Maldonado, Amir

2007-01-01

We study the effect of a non-ionic amphiphilic polymer (PEG-100 stearate also called Myrj 59) on the foaming behaviour of aqueous solutions of an anionic surfactant (sodium dodecyl sulfate or SDS). The SDS concentration was kept fixed while the Myrj 59 concentration was varied. Measurements of foamability, surface tension and electrical conductivity were carried out. The results show two opposite effects depending on the polymer concentration: foamability is higher when the Myrj 59 concentration is low; however, it decreases considerably when the polymer concentration is increased. This behaviour is due to the polymer adsorption at the air/liquid interface at lower polymer concentrations, and to the formation of a polymer-surfactant complex in the bulk at higher concentrations. The results are confirmed by surface tension and electrical conductivity measurements, which are interpreted in terms of the microstructure of the polymer-surfactant solutions. The observed behaviour is due to the amphiphilic nature of the studied polymer. The increased hydrophobicity of Myrj 59, compared to that of water-soluble polymers like PEG or PEO, increases its 'reactivity' towards SDS, i.e. the strength of its interaction with this anionic surfactant. Our results show that hydrophobically modified polymers have potential applications as additives in order to control the foaming properties of surfactant solutions

High-throughput ab-initio dilute solute diffusion database.

Science.gov (United States)

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-07-19

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world.

Calorimetric study of interaction of barium hydroxide with diluted solutions of hydrofluoric acid

International Nuclear Information System (INIS)

Kurbanov, A.R.; Sharipov, D.Sh.

1993-01-01

Present article is devoted to calorimetric study of interaction of barium hydroxide with diluted solutions of hydrofluoric acid. The calorimetric study of interaction of barium hydroxide with diluted solutions of hydrofluoric acid was carried out in order to determine the thermal effects of reactions. The results of interaction of Ba(OH) 4 ·8H 2 O with 5, 10, and 20% solution of hydrofluoric acid were considered.

Rheology of Biopolymer Solutions and Gels

Directory of Open Access Journals (Sweden)

David R. Picout

2003-01-01

Full Text Available Rheological techniques and methods have been employed for many decades in the characterization of polymers. Originally developed and used on synthetic polymers, rheology has then found much interest in the field of natural (bio polymers. This review concentrates on introducing the fundamentals of rheology and on discussing the rheological aspects and properties of the two major classes of biopolymers: polysaccharides and proteins. An overview of both their solution properties (dilute to semi-dilute and gel properties is described.

Scaling Behavior of Dilute Polymer Solutions Confined between Parallel Plates

NARCIS (Netherlands)

Vliet, J.H. van; Luyten, M.C.; Brinke, G. ten

1992-01-01

The average size and shape of a polymer coil confined in a slit between two parallel plates depends on the distance L between the plates. On the basis of numerical results, four different regimes can be distingubhed. For large values of L the coil is essentially unconfined. For intermediate values

A new scaling for the rotational diffusion of molecular probes in polymer solutions.

Science.gov (United States)

Qing, Jing; Chen, Anpu; Zhao, Nanrong

2017-12-13

In the present work, we propose a new scaling form for the rotational diffusion coefficient of molecular probes in semi-dilute polymer solutions, based on a theoretical study. The mean-field theory for depletion effect and semi-empirical scaling equation for the macroscopic viscosity of polymer solutions are properly incorporated to specify the space-dependent concentration and viscosity profiles in the vicinity of the probe surface. Following the scheme of classical fluid mechanics, we numerically evaluate the shear torque exerted on the probes, which then allows us to further calculate the rotational diffusion coefficient D r . Particular attention is given to the scaling behavior of the retardation factor R rot ≡ D/D r with D being the diffusion coefficient in pure solvent. We find that R rot has little relevance to the macroscopic viscosity of the polymer solution, while it can be well featured by the characteristic length scale r h /δ, i.e. the ratio between the hydrodynamic radius of the probe r h and the depletion thickness δ. Correspondingly, we obtain a novel scaling form for the rotational retardation factor, following R rot = exp[a(r h /δ) b ] with rather robust parameters of a ≃ 0.51 and b ≃ 0.56. We apply the theory to an extensive calculation for various probes in specific polymer solutions of poly(ethylene glycol) (PEG) and dextran. Our theoretical results show good agreements with the experimental data, and clearly demonstrate the validity of the new scaling form. In addition, the difference of the scaling behavior between translational and rotational diffusions is clarified, from which we conclude that the depletion effect plays a more significant role on the local rotational diffusion rather than the long-range translation diffusion.

Dielectric relaxation studies of dilute solutions of amides

Energy Technology Data Exchange (ETDEWEB)

Malathi, M.; Sabesan, R.; Krishnan, S

2003-11-15

The dielectric constants and dielectric losses of formamide, acetamide, N-methyl acetamide, acetanilide and N,N-dimethyl acetamide in dilute solutions of 1,4-dioxan/benzene have been measured at 308 K using 9.37 GHz, dielectric relaxation set up. The relaxation time for the over all rotation {tau}{sub (1)} and that for the group rotation {tau}{sub (2)} of (the molecules were determined using Higasi's method. The activation energies for the processes of dielectric relaxation and viscous flow were determined by using Eyring's rate theory. From relaxation time behaviour of amides in non-polar solvent, solute-solvent and solute-solute type of molecular association is proposed.

A theoretical framework for modeling dilution enhancement of non-reactive solutes in heterogeneous porous media.

Science.gov (United States)

de Barros, F P J; Fiori, A; Boso, F; Bellin, A

2015-01-01

Spatial heterogeneity of the hydraulic properties of geological porous formations leads to erratically shaped solute clouds, thus increasing the edge area of the solute body and augmenting the dilution rate. In this study, we provide a theoretical framework to quantify dilution of a non-reactive solute within a steady state flow as affected by the spatial variability of the hydraulic conductivity. Embracing the Lagrangian concentration framework, we obtain explicit semi-analytical expressions for the dilution index as a function of the structural parameters of the random hydraulic conductivity field, under the assumptions of uniform-in-the-average flow, small injection source and weak-to-mild heterogeneity. Results show how the dilution enhancement of the solute cloud is strongly dependent on both the statistical anisotropy ratio and the heterogeneity level of the porous medium. The explicit semi-analytical solution also captures the temporal evolution of the dilution rate; for the early- and late-time limits, the proposed solution recovers previous results from the literature, while at intermediate times it reflects the increasing interplay between large-scale advection and local-scale dispersion. The performance of the theoretical framework is verified with high resolution numerical results and successfully tested against the Cape Cod field data. Copyright © 2015 Elsevier B.V. All rights reserved.

Method of preparing Ru-immobilized polymer-supported catalyst for hydrogen generation from NaBH{sub 4} solution

Energy Technology Data Exchange (ETDEWEB)

Chen, Ching-Wen; Chen, Chuh-Yung; Huang, Yao-Hui [Department of Chemical Engineering, National Cheng Kung University, No.1, University Road, Tainan City 70101 (China)

2009-03-15

A method of preparing a polymer-supported catalyst for hydrogen generation is introduced in this article. This polymer-supported catalyst is the structure of ruthenium (Ru) nanoparticle immobilized on a monodisperse polystyrene (PSt) microsphere. The diameter of the Ru nanoparticle is around 16 nm, and the diameter of the PSt microsphere is 2.65 um. This preparation method is accomplished by two unique techniques: one is sodium lauryl sulfate/sodium formaldehyde sulfoxylate (SLS/SFS) interface-initiated system, the other is 2-methacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester (GMA-IDA) chelating monomer. By taking advantage of these two techniques, Ru{sup 3+} ion will be chelated and then reduced to Ru{sup (0)} nanoparticle over PSt surface predominantly. The hydrolysis of alkaline sodium borohydride (NaBH{sub 4}) solution catalyzed by this Ru-immobilized polymer-supported catalyst is also examined in this article. It reveals that the hydrogen generation rate is 215.9 ml/min g-cat. in a diluted solution containing 1 wt.% NaBH{sub 4} and 1 wt.% NaOH, and this Ru-immobilized polymer-supported catalyst could be recycled during the reaction. (author)

Segment-based Eyring-Wilson viscosity model for polymer solutions

International Nuclear Information System (INIS)

Sadeghi, Rahmat

2005-01-01

A theory-based model is presented for correlating viscosity of polymer solutions and is based on the segment-based Eyring mixture viscosity model as well as the segment-based Wilson model for describing deviations from ideality. The model has been applied to several polymer solutions and the results show that it is reliable both for correlation and prediction of the viscosity of polymer solutions at different molar masses and temperature of the polymer

Procedures for accurately diluting and dispensing radioactive solutions

International Nuclear Information System (INIS)

1975-01-01

The technique currently used by various laboratories participating in international comparisons of radioactivity measurements are surveyed and recommendations for good laboratory practice established. Thus one describes, for instance, the preparation of solutions, dilution techniques, the use of 'pycnometers', weighing procedures (including buyoancy correction), etc. It should be possible to keep random and systematic uncertainties below 0.1% of the final result

Superhydrophobic and polymer drag reduction in turbulent Taylor-Couette flow

Science.gov (United States)

Rajappan, Anoop; McKinley, Gareth H.

2017-11-01

We use a custom-built Taylor-Couette apparatus (radius ratio η = 0.75) to study frictional drag reduction by dilute polymer solutions and superhydrophobic (SH) surfaces in turbulent flows for 15000 analysis. We also investigate drag reduction by dilute polymer solutions, and show that natural biopolymers from plant mucilage can be an inexpensive and effective alternative to synthetic polymers in drag reduction applications, approaching the same maximum drag reduction asymptote. Finally we explore combinations of the two methods - one arising from wall slip and the other due to changes in turbulence dynamics in the bulk flow - and find that the two effects are not additive; interestingly, the effectiveness of polymer drag reduction is drastically reduced in the presence of an SH coating on the wall. This study was financially supported by the Office of Naval Research (ONR) through Contract No. 3002453814.

Modeling of the (liquid + liquid) equilibrium of polydisperse hyperbranched polymer solutions by lattice-cluster theory

International Nuclear Information System (INIS)

Enders, Sabine; Browarzik, Dieter

2014-01-01

Graphical abstract: - Highlights: • Calculation of the (liquid + liquid) equilibrium of hyperbranched polymer solutions. • Description of branching effects by the lattice-cluster theory. • Consideration of self- and cross association by chemical association models. • Treatment of the molar-mass polydispersity by the use of continuous thermodynamics. • Improvement of the theoretical results by the incorporation of polydispersity. - Abstract: The (liquid + liquid) equilibrium of solutions of hyperbranched polymers of the Boltorn type is modeled in the framework of lattice-cluster theory. The association effects are described by the chemical association models CALM (for self association) and ECALM (for cross association). For the first time the molar mass polydispersity of the hyperbranched polymers is taken into account. For this purpose continuous thermodynamics is applied. Because the segment-molar excess Gibbs free energy depends on the number average of the segment number of the polymer the treatment is more general than in previous papers on continuous thermodynamics. The polydispersity is described by a generalized Schulz–Flory distribution. The calculation of the cloud-point curve reduces to two equations that have to be numerically solved. Conditions for the calculation of the spinodal curve and of the critical point are derived. The calculated results are compared to experimental data taken from the literature. For Boltorn solutions in non-polar solvents the polydispersity influence is small. In all other of the considered cases polydispersity influences the (liquid + liquid) equilibrium considerably. However, association and polydispersity influence phase equilibrium in a complex manner. Taking polydispersity into account the accuracy of the calculations is improved, especially, in the diluted region

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

Science.gov (United States)

Raut, Ashlesha S; Kalonia, Devendra S

2015-04-01

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

Flory-type theories of polymer chains under different external stimuli

Science.gov (United States)

Budkov, Yu A.; Kiselev, M. G.

2018-01-01

In this Review, we present a critical analysis of various applications of the Flory-type theories to a theoretical description of the conformational behavior of single polymer chains in dilute polymer solutions under a few external stimuli. Different theoretical models of flexible polymer chains in the supercritical fluid are discussed and analysed. Different points of view on the conformational behavior of the polymer chain near the liquid-gas transition critical point of the solvent are presented. A theoretical description of the co-solvent-induced coil-globule transitions within the implicit-solvent-explicit-co-solvent models is discussed. Several explicit-solvent-explicit-co-solvent theoretical models of the coil-to-globule-to-coil transition of the polymer chain in a mixture of good solvents (co-nonsolvency) are analysed and compared with each other. Finally, a new theoretical model of the conformational behavior of the dielectric polymer chain under the external constant electric field in the dilute polymer solution with an explicit account for the many-body dipole correlations is discussed. The polymer chain collapse induced by many-body dipole correlations of monomers in the context of statistical thermodynamics of dielectric polymers is analysed.

SANS studies of polymers

International Nuclear Information System (INIS)

Wignall, G.D.

1984-10-01

Before small-angle neutron scattering (SANS), chain conformation studies were limited to light and small angle x-ray scattering techniques, usually in dilute solution. SANS from blends of normal and labeled molecules could give direct information on chain conformation in bulk polymers. Water-soluble polymers may be examined in H 2 O/D 2 O mixtures using contrast variation methods to provide further information on polymer structure. This paper reviews some of the information provided by this technique using examples of experiments performed at the National Center for Small-Angle Scattering Research (NCSASR)

Aspects récents de la thermodynamique des solutions de polymères Recent Aspects of the Thermodynamics of Polymer Solutions

Directory of Open Access Journals (Sweden)

Dayantis J.

2006-11-01

Full Text Available On examine dans cet article différentes approches de la thermodynamique des solutions de polymères placées dans leur contexte historique. On rappelle d'abord le modèle du réseau de Flory-Huggins et on en souligne les déficiences. On traite ensuite brièvement de la mécanique statistique des solutions de polymères introduite par Prigogine en 1957 et on montre qu'elle constitue un progrès qualitatif par rapport à la théorie du réseau, mais qu'elle ne prévoit cependant pas de manière quantitative les propriétés de ces solutions. On montre ensuite que le concept de volume libre, qui permet un traitement simplifié de certaines quantités, permet également d'expliquer tout naturellement l'existence d'une deuxième température de séparation en phase lorsque l'on élève la température, propriété qui différencie les solutions de polymères des mélanges de liquidés simples. Enfin, dans une dernière partie, on mentionne brièvement les travaux récents de l'École de Paris, qui traite les solutions de polymères par analogie avec les transitions magnétiques. This article examines différent approaches ta the thermodynamics of polymer solutions set in their historical context. First of all, the Flory-Huggins network model is described and ifs deficiencies are pointed out. Then attention is briefly drawn to the statistical mechanics of polymer solutions as introduced by Prigogine in 1957, and this mechanics is shown to be a qualitative advance compared with the network theory, but it nonetheless does not quantitatively predict the properties of such solutions. It is then shown that the concept of free volume, enabling some quantifies to be treated in a simplified way, also serves to provide a quite natural explanation for the existence of a second phase separation temperature when the temperature is raised, i. e. a property that differentiates polymer solutions from simple liquid mixtures. In the final part, brief mention is made

Electrochemical reduction of dilute chromate solutions on carbon felt electrodes

NARCIS (Netherlands)

Frenzel, Ines; Frenzel, I.; Holdik, Hans; Barmashenko, Vladimir; Stamatialis, Dimitrios; Wessling, Matthias

2006-01-01

Carbon felt is a potential material for electrochemical reduction of chromates. Very dilute solutions may be efficiently treated due to its large specific surface area and high porosity. In this work, the up-scaling of this technology is investigated using a new type of separated cell and

Electrochemical reduction of metal ions in dilute solution using hydrogen

NARCIS (Netherlands)

Portegies Zwart, I.; Wijnbelt, E.C.W.; Janssen, L.J.J.

1995-01-01

Reduction of metal ions in dilute solutions is of great interest for purification of waste waters and process liquids. A new electrochemical cell has been introduced. This cell - a GBC-cell - is a combination of a gasdiffusion electrode in direct contact with a packed bed of carbon particles.

Preliminary tests on the Pu(IV)-polymers

International Nuclear Information System (INIS)

Cauchetier, P.; Guichard, C.

1983-02-01

It is possible to obtain polymeric species from acid solutions of plutonium by water dilution or slow neutralization. In those two processes the heating improves the polymerization. We describe the conditions of these compounds formation when steam injected in low-acid nitric solutions. The soluble Pu(IV)-polymers are not absorbed by cation-exchangers. They have a well-characterized absorbance spectrum different from that of ionic species. They are stable even after the dilution in the same medium. Inversely, the change of medium including the acidification is able to induce the hydroxide precipitation [fr

Optical absorption of dilute solutions of metals in molten salts

Energy Technology Data Exchange (ETDEWEB)

Senatore, G.; Parrinello, M.; Tosi, M.P. (Trieste Univ. (Italy). Ist. di Fisica Teorica; Gruppo Nazionale di Struttura dell material del CNR, Trieste (Italy); International Centre for Theoretical Physics, Trieste (Italy))

1978-12-23

The theory of liquid structure for fluids of charged hard spheres is applied to an evaluation of the F-centre model for valence electrons in metal-molten salt solutions at high dilution. Minimization of the free energy yields the groundstate radius of the elctron bubble and hence the optical excitation energy in a Franck-Condon transition, the shift and broadening of the transition due to fluctuations in the bubble radius, the volume of mixing, and the activity of the salt in the solution.

Polymer filtration: A new technology for selective metals recovery

Energy Technology Data Exchange (ETDEWEB)

Smith, B.F.; Robison, T.W.; Cournoyer, M.E.; Wilson, K.V.; Sauer, N.N.; Mullen, K.I.; Lu, M.T.; Jarvinen, J.J.

1995-04-01

Polymer Filtration (PF) was evaluated for the recovery of electroplating metal ions (zinc and nickel) from rinse waters. Polymer Filtration combines the use of water-soluble metal-binding polymers and ultrafiltration to concentrate metal ions from dilute rinse water solutions. The metal ions are retained by the polymers; the smaller, unbound species freely pass through the ultrafiltration membrane. By using this process the ultrafiltered permeate more than meets EPA discharge limits. The metal ions are recovered from the concentrated polymer solution by pH adjustment using diafiltration and can be recycled to the original electroplating baths with no deleterious effects on the test panels. Metal-ion recovery is accomplished without producing sludge.

"JCE" Classroom Activity #106. Sequestration of Divalent Metal Ion by Superabsorbent Polymer in Diapers

Science.gov (United States)

Chen, Yueh-Huey; Lin, Jia-Ying; Lin, Li-Pin; Liang, Han; Yaung, Jing-Fun

2010-01-01

This activity explores an alternative use of a superabsorbent polymer known as a water absorbing material. A dilute solution of CuCl[subscript 2] is treated with a small piece of unused disposable diaper containing superabsorbent sodium polyacrylates. The polymer is used for the removal of Cu[superscript 2+] ions from the solution. The…

Thermodynamic properties of hyperbranched polymer, Boltorn U3000, using inverse gas chromatography.

Science.gov (United States)

Domańska, Urszula; Zołek-Tryznowska, Zuzanna

2009-11-19

Mass-fraction activity coefficients at infinite dilution (Omega13(infinity)) of alkanes (C5-C10), cycloalkanes (C5-C8), alkenes (C5-C8), alkynes (C5-C8), aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-, m-, p-xylene, thiophene), alcohols (C1-C5), water, ethers (tetrahydrofuran (THF), methyl-tert-butylether (MTBE), diethyl-, di-n-propyl-, di-n-butyl ether), and ketones (propanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclopentanone) in the hyperbranched polymer, Boltorn U3000 (B-U3000), have been determined by inverse gas chromatography (IGC) using the polymer as the stationary phase. The measurements were carried out at different temperatures between 308.15 and 348.15 K. The density and thermophysical properties of polymer were described. The specific retention volume (V(g)), the Flory-Huggins interaction parameter (chi13(infinity)), the molar enthalpy of sorption (the partial molar enthalpies of solute dissolution) (Delta(s)H), the partial molar excess enthalpy at infinite dilution of the solute and polymer (DeltaH1(E,infinity)), the partial molar Gibbs excess energy at infinite dilution (DeltaG1(E,infinity)), and the solubility parameter (delta3) were calculated.

Brushes and soap : grafted polymers and their interactions with nanocolloids

NARCIS (Netherlands)

Currie, E.P.K.

2000-01-01

Layers of polymer chains end-attached to a grafting plane at high densities, so-called brushes, are a curious state of matter. The (average) monomer density within the brush is as high as in a semi-dilute polymer solution, resulting in a high osmotic pressure in the brush. Due to the

Structuring of polymer solutions upon solvent evaporation

NARCIS (Netherlands)

Schaefer, C.; van der Schoot, P.|info:eu-repo/dai/nl/102140618; Michels, J. J.

2015-01-01

The morphology of solution-cast, phase-separated polymers becomes finer with increasing solvent evaporation rate. We address this observation theoretically for a model polymer where demixing is induced by steady solvent evaporation. In contrast to what is the case for a classical, thermal quench

Polymer diffusion in the interphase between surface and solution.

Science.gov (United States)

Weger, Lukas; Weidmann, Monika; Ali, Wael; Hildebrandt, Marcus; Gutmann, Jochen Stefan; Hoffmann-Jacobsen, Kerstin

2018-05-22

Total internal reflection fluorescence correlation spectroscopy (TIR-FCS) is applied to study the self-diffusion of polyethylene glycol solutions in the presence of weakly attractive interfaces. Glass coverslips modified with aminopropyl- and propyl-terminated silanes are used to study the influence of solid surfaces on polymer diffusion. A model of three phases of polymer diffusion allows to describe the experimental fluorescence autocorrelation functions. Besides the two-dimensional diffusion of adsorbed polymer on the substrate and three-dimensional free diffusion in bulk solution, a third diffusion time scale is observed with intermediate diffusion times. This retarded three-dimensional diffusion in solution is assigned to long range effects of solid surfaces on diffusional dynamics of polymers. The respective diffusion constants show Rouse scaling (D~N -1 ) indicating a screening of hydrodynamic interactions by the presence of the surface. Hence, the presented TIR-FCS method proves to be a valuable tool to investigate the effect of surfaces on polymer diffusion beyond the first adsorbed polymer layer on the 100 nm length scale.

Stochastic entangled chain dynamics of dense polymer solutions.

Science.gov (United States)

Kivotides, Demosthenes; Wilkin, S Louise; Theofanous, Theo G

2010-10-14

We propose an adjustable-parameter-free, entangled chain dynamics model of dense polymer solutions. The model includes the self-consistent dynamics of molecular chains and solvent by describing the former via coarse-grained polymer dynamics that incorporate hydrodynamic interaction effects, and the latter via the forced Stokes equation. Real chain elasticity is modeled via the inclusion of a Pincus regime in the polymer's force-extension curve. Excluded volume effects are taken into account via the combined action of coarse-grained intermolecular potentials and explicit geometric tracking of chain entanglements. We demonstrate that entanglements are responsible for a new (compared to phantom chain dynamics), slow relaxation mode whose characteristic time scale agrees very well with experiment. Similarly good agreement between theory and experiment is also obtained for the equilibrium chain size. We develop methods for the solution of the model in periodic flow domains and apply them to the computation of entangled polymer solutions in equilibrium. We show that the number of entanglements Π agrees well with the number of entanglements expected on the basis of tube theory, satisfactorily reproducing the latter's scaling of Π with the polymer volume fraction φ. Our model predicts diminishing chain size with concentration, thus vindicating Flory's suggestion of excluded volume effects screening in dense solutions. The predicted scaling of chain size with φ is consistent with the heuristic, Flory theory based value.

Shock wave emission from laser-induced cavitation bubbles in polymer solutions.

Science.gov (United States)

Brujan, Emil-Alexandru

2008-09-01

The role of extensional viscosity on the acoustic emission from laser-induced cavitation bubbles in polymer solutions and near a rigid boundary is investigated by acoustic measurements. The polymer solutions consist of a 0.5% polyacrylamide (PAM) aqueous solution with a strong elastic component and a 0.5% carboxymethylcellulose (CMC) aqueous solution with a weak elastic component. A reduction of the maximum amplitude of the shock wave pressure and a prolongation of the oscillation period of the bubble were found in the elastic PAM solution. It might be caused by an increased resistance to extensional flow which is conferred upon the liquid by the polymer additive. In both polymer solutions, however, the shock pressure decays proportionally to r(-1) with increasing distance r from the emission centre.

Viscometric studies of interactions between ionic liquid 1-octyl-3-methyl-imidazolium bromide and polyvinyl pyrrolidone in aqueous solutions

International Nuclear Information System (INIS)

Mehrdad, Abbas; Shekaari, Hemayat; Niknam, Zahra

2014-01-01

Highlights: • Viscosities of PVP in aqueous solution of IL are measured. • The flow activation energies are calculated. • The flow activation energies are correlated in terms of polymer concentration. • Intrinsic viscosity of PVP is decreased by increasing temperature. - Abstract: Ionic liquids are investigated as solvents for polymerization processes, as plasticizers of various kinds of polymers and as components of the polymeric matrixes. In this research, viscosity of polyvinyl pyrrolidone in aqueous solution of ionic liquid, 1-octyl-3-methyl imidazolium bromide are measured at various temperatures. The flow activation energies are calculated and correlated in terms of polymer concentration. From sign of the initial slope of the activation energy versus polymer concentration at zero concentration, it is concluded that thermodynamic quality of ionic liquid aqueous solutions are reduced by increasing temperature. The value of the intrinsic viscosity of polyvinyl pyrrolidone was determined using Huggins equation and thermodynamic parameters of this polymer were calculated on the basis of intrinsic viscosity. Also the effect of ionic liquid, 1-octyl-3-methyl imidazolium bromide on the thermodynamic parameters of dilute aqueous polyvinyl pyrrolidone solutions, such as (polymer + solvent) interaction parameter, theta temperature, the heat of dilution parameter and the entropy of dilution parameter was investigated. Results suggest that the thermodynamic quality of water was increased slightly by the addition of ionic liquid in aqueous solution of polyvinyl pyrrolidone

Influence of complexing on physicochemical properties of polymer-salt solutions

International Nuclear Information System (INIS)

Ostroushko, A.A.; Yushkova, S.M.; Koridze, N.V.; Skobkoreva, N.V.; Zhuravleva, L.I.; Palitskaya, T.A.; Antropova, S.V.; Ostroushko, I.P.; AN SSSR, Moscow

1993-01-01

Using the methods of spectrophotometry, viscosimetry, conductometry the influence of salt-polymer complexing processes on physicochemical prperties of aqueous solutions of yttrium, barium, copper nitrates and formates with polyvinyl alcohol was studied. Change of dynamic viscosity, specific electric conductivity of solutions in the process of complexing was shown. Thermal effects of salt-polymer interaction were measured. It is shown that decrease of transition temperature of polymer to plastic state in films, temperature and effective activation energy of salt decomposition is also connected with complexing. Effective values of surface tension on the boundary with air are measured. Coefficients of cation diffusion in polymer-salt solutions are estimated

Ion separation from dilute electrolyte solutions by nanofiltration

International Nuclear Information System (INIS)

Garcia, Corazon M.

2000-03-01

Nanofiltration (NF) is a pressure-driven process which is considered potential for the separation of ionic species selectively from solutions containing mixture of electrolyte solutes. The lower operating pressure requirement of NF than reverse osmosis (RO) makes the earlier potentially economical. In the separation of ions, many authors believed that there are membranes with characteristic fixed surface charge and that the mechanism of separation of ions is by the differences in valences of the ions. In this study, experiments involving dilute single-solute and multiple-solute electrolyte solutions were performed using three different NF membranes. Permeate fluxes and ion rejections of the different species of ions in samples of permeate solutions were measured at varied conditions. The mechanism of separation in NF was determined based on the analysis of the trends and behavior of ion rejection relative to the solution temperature, pressure, type of solute, feed concentration and feed solution pH. The results of the experiments show that there is no evidence of the presence of fixed surface charge on the NF membranes. Ion separation was made possible by the combination of sieve effect and ion-hydration effect. Ions having higher hydration numbers showed higher ion rejection than those having lower hydration numbers. A method to determine the effective membrane pore size of NF membranes using hydrodynamic model was proposed. The proposed method is based on the assumptions that the membrane is neutral and that the separation is based on sieving effect. (Author)

Self and collective dynamics of ordered star polymer solutions

CERN Document Server

Stellbrink, J; Monkenbusch, M; Richter, D; Ehlers, G; Schleger, P

2002-01-01

We investigated the dynamics of 18-arm polyisoprene star polymer solutions well above their overlap concentration c sup *. Combining neutron spin echo spectroscopy (NSE) and selective H/D labelling, we were able to separate inter- (collective) and intra-star (self) dynamics. Only at low Q-vectors do self and collective dynamics become discernible. Here, collective dynamics are found to be consistent with a colloidal approach resulting from star-star interactions. The collective short time diffusion coefficient D sub e sub f sub f is well described by the term D sub 0 /S(Q), with D sub 0 the diffusion coefficient at infinite dilution. At Q sub m , the peak position in the structure factor S(Q), no difference is observable between collective and self dynamics. For covering the slowed-down dynamics at Q sub m the time range of NSE was extended for the first time up to 350 ns using long wavelengths, lambda=19 A, at IN15 (ILL, Grenoble). We found that S(Q,t)/S(Q,0) relaxes into a concentration-dependent plateau. T...

Effect of temperature on the dilution enthalpies of α,ω-amino acids in aqueous solutions

International Nuclear Information System (INIS)

Romero, C.M.; Cadena, J.C.; Lamprecht, I.

2011-01-01

Highlights: → The dilution of 3-amino propanoic acid, 4-amino butanoic acid, 5-amino pentanoic acid, and 6-amino hexanoic acid in water is an exothermic process at T = (293.15, 298.15, 303.15, and 308.15) K. → The limiting experimental slopes of the enthalpies of dilution with respect to the molality change Δm, are negative suggesting that the solutes interact with water primarily through their alkyl groups. → The value of the pairwise coefficient is positive at the temperatures considered, and the magnitude increases linearly with the number of methylene groups. → The comparison between the pairwise interaction coefficients for α,ω-amino acids and α-amino acids shows that the change in the enthalpic interaction coefficient is related to the relative position of the polar groups. - Abstract: Dilution enthalpies of aqueous solutions of 3-amino propanoic acid, 4-amino butanoic acid, 5-amino pentanoic acid, and 6-amino hexanoic acid were determined at T = (293.15, 298.15, 303.15, and 308.15) K using an LKB flow microcalorimeter. The homotactic interaction coefficients were obtained according to the McMillan-Mayer theory from the experimental data. For all the systems studied, the dilution of α,ω-amino acids in water is an exothermic process; the pair coefficients have positive values which increases with chain length. The obtained values of the interaction coefficients are interpreted in terms of solute-solvent and solute-solute interactions and are used as indicative of hydrophobic behavior of the amino acid studied.

Homogenization Theory for the Prediction of Obstructed Solute Diffusivity in Macromolecular Solutions.

Science.gov (United States)

Donovan, Preston; Chehreghanianzabi, Yasaman; Rathinam, Muruhan; Zustiak, Silviya Petrova

2016-01-01

The study of diffusion in macromolecular solutions is important in many biomedical applications such as separations, drug delivery, and cell encapsulation, and key for many biological processes such as protein assembly and interstitial transport. Not surprisingly, multiple models for the a-priori prediction of diffusion in macromolecular environments have been proposed. However, most models include parameters that are not readily measurable, are specific to the polymer-solute-solvent system, or are fitted and do not have a physical meaning. Here, for the first time, we develop a homogenization theory framework for the prediction of effective solute diffusivity in macromolecular environments based on physical parameters that are easily measurable and not specific to the macromolecule-solute-solvent system. Homogenization theory is useful for situations where knowledge of fine-scale parameters is used to predict bulk system behavior. As a first approximation, we focus on a model where the solute is subjected to obstructed diffusion via stationary spherical obstacles. We find that the homogenization theory results agree well with computationally more expensive Monte Carlo simulations. Moreover, the homogenization theory agrees with effective diffusivities of a solute in dilute and semi-dilute polymer solutions measured using fluorescence correlation spectroscopy. Lastly, we provide a mathematical formula for the effective diffusivity in terms of a non-dimensional and easily measurable geometric system parameter.

Homogenization Theory for the Prediction of Obstructed Solute Diffusivity in Macromolecular Solutions.

Directory of Open Access Journals (Sweden)

Preston Donovan

Full Text Available The study of diffusion in macromolecular solutions is important in many biomedical applications such as separations, drug delivery, and cell encapsulation, and key for many biological processes such as protein assembly and interstitial transport. Not surprisingly, multiple models for the a-priori prediction of diffusion in macromolecular environments have been proposed. However, most models include parameters that are not readily measurable, are specific to the polymer-solute-solvent system, or are fitted and do not have a physical meaning. Here, for the first time, we develop a homogenization theory framework for the prediction of effective solute diffusivity in macromolecular environments based on physical parameters that are easily measurable and not specific to the macromolecule-solute-solvent system. Homogenization theory is useful for situations where knowledge of fine-scale parameters is used to predict bulk system behavior. As a first approximation, we focus on a model where the solute is subjected to obstructed diffusion via stationary spherical obstacles. We find that the homogenization theory results agree well with computationally more expensive Monte Carlo simulations. Moreover, the homogenization theory agrees with effective diffusivities of a solute in dilute and semi-dilute polymer solutions measured using fluorescence correlation spectroscopy. Lastly, we provide a mathematical formula for the effective diffusivity in terms of a non-dimensional and easily measurable geometric system parameter.

Effect of molecular topology on the transport properties of dendrimers in dilute solution at Θ temperature: A Brownian dynamics study

Science.gov (United States)

Bosko, Jaroslaw T.; Ravi Prakash, J.

2008-01-01

Structure and transport properties of dendrimers in dilute solution are studied with the aid of Brownian dynamics simulations. To investigate the effect of molecular topology on the properties, linear chain, star, and dendrimer molecules of comparable molecular weights are studied. A bead-spring chain model with finitely extensible springs and fluctuating hydrodynamic interactions is used to represent polymer molecules under Θ conditions. Structural properties as well as the diffusivity and zero-shear-rate intrinsic viscosity of polymers with varied degrees of branching are analyzed. Results for the free-draining case are compared to and found in very good agreement with the Rouse model predictions. Translational diffusivity is evaluated and the difference between the short-time and long-time behavior due to dynamic correlations is observed. Incorporation of hydrodynamic interactions is found to be sufficient to reproduce the maximum in the intrinsic viscosity versus molecular weight observed experimentally for dendrimers. Results of the nonequilibrium Brownian dynamics simulations of dendrimers and linear chain polymers subjected to a planar shear flow in a wide range of strain rates are also reported. The flow-induced molecular deformation of molecules is found to decrease hydrodynamic interactions and lead to the appearance of shear thickening. Further, branching is found to suppress flow-induced molecular alignment and deformation.

Ordered alternating binary polymer nanodroplet array by sequential spin dewetting.

Science.gov (United States)

Bhandaru, Nandini; Das, Anuja; Salunke, Namrata; Mukherjee, Rabibrata

2014-12-10

We report a facile technique for fabricating an ordered array of nearly equal-sized mesoscale polymer droplets of two constituent polymers (polystyrene, PS and poly(methyl methacrylate), PMMA) arranged in an alternating manner on a topographically patterned substrate. The self-organized array of binary polymers is realized by sequential spin dewetting. First, a dilute solution of PMMA is spin-dewetted on a patterned substrate, resulting in an array of isolated PMMA droplets arranged along the substrate grooves due to self-organization during spin coating itself. The sample is then silanized with octadecyltrichlorosilane (OTS), and subsequently, a dilute solution of PS is spin-coated on to it, which also undergoes spin dewetting. The spin-dewetted PS drops having a size nearly equal to the pre-existing PMMA droplets position themselves between two adjacent PMMA drops under appropriate conditions, forming an alternating binary polymer droplet array. The alternating array formation takes place for a narrow range of solution concentration for both the polymers and depends on the geometry of the substrate. The size of the droplets depends on the extent of confinement, and droplets as small as 100 nm can be obtained by this method, on a suitable template. The findings open up the possibility of creating novel surfaces having ordered multimaterial domains with a potential multifunctional capability.

Study on radiation-induced deactivation and post-deactivation of some oxidoreductases in dilute aqueous solution and protective effect: Pt. 1

International Nuclear Information System (INIS)

Chen Yiqing; Ha Hongfei

1993-01-01

In this work the radiation-induced deactivation of catalase in dilute aqueous solution was reported. The effects of irradiation atmosphere, temperature and original concentration of catalase in dilute aqueous solutions on the deactivation of catalase were investigated. The protective effect by some additives (CH 3 CH 2 OH, HCOONa and EDTA) to radiation deactivation in dilute aqueous solutions was also studied. Remarkable protective effect by those additives was observed. The mechanism of radiation deactivation and protective effect have been discussed

Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution

KAUST Repository

Rai, Durgesh K.; Beaucage, Gregory; Ratkanthwar, Kedar; Beaucage, Peter; Ramachandran, Ramnath; Hadjichristidis, Nikolaos

2015-01-01

Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.

Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution

KAUST Repository

Rai, Durgesh K.

2015-07-15

Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.

Investigations of model polymers: Dynamics of melts and statics of a long chain in a dilute melt of shorter chains

International Nuclear Information System (INIS)

Bishop, M.; Ceperley, D.; Frisch, H.L.; Kalos, M.H.

1982-01-01

We report additional results on a simple model of polymers, namely the diffusion in concentrated polymer systems and the static properties of one long chain in a dilute melt of shorter chains. It is found, for the polymer sizes and time scales amenable to our computer calculations, that there is as yet no evidence for a ''reptation'' regime in a melt. There is some indication of reptation in the case of a single chain moving through fixed obstacles. No statistically significant effect of the change, from excluded volume behavior of the long chain to ideal behavior as the shorter chains grow, is observed

On the attenuation of x-rays and gamma-rays in dilute solutions

DEFF Research Database (Denmark)

Gerward, Leif

1996-01-01

The theory of X-ray and gamma-ray attenuation in solutions is developed. The rule of mixture for the calculation of mass and linear attenuation coefficients is elaborated in the general case as well as in the limit of extreme dilution. The validity of the latter approximation is illustrated...... by the attenuation of 17.443 keV X-rays in aqueous solutions of NaCl. Copyright (C) 1996 Elsevier Science Ltd...

Reversible Mechanochemistry of a PdII Coordination Polymer

NARCIS (Netherlands)

Paulusse, Jos Marie Johannes; Sijbesma, Rint P.

2004-01-01

Breaking up and making up: The ultrasonic cleavage of high-molecular-weight linear coordination polymers of phosphane telechelic polytetrahydrofuran and palladium dichloride in dilute solution is a reversible process (see picture). Sonication for 1 h led to a decrease in the weight-averaged

Polymer solution phase separation: Microgravity simulation

Science.gov (United States)

Cerny, Lawrence C.; Sutter, James K.

1989-01-01

In many multicomponent systems, a transition from a single phase of uniform composition to a multiphase state with separated regions of different composition can be induced by changes in temperature and shear. The density difference between the phase and thermal and/or shear gradients within the system results in buoyancy driven convection. These differences affect kinetics of the phase separation if the system has a sufficiently low viscosity. This investigation presents more preliminary developments of a theoretical model in order to describe effects of the buoyancy driven convection in phase separation kinetics. Polymer solutions were employed as model systems because of the ease with which density differences can be systematically varied and because of the importance of phase separation in the processing and properties of polymeric materials. The results indicate that the kinetics of the phase separation can be performed viscometrically using laser light scattering as a principle means of following the process quantitatively. Isopycnic polymer solutions were used to determine the viscosity and density difference limits for polymer phase separation.

Reduced viscosity for flagella moving in a solution of long polymer chains

Science.gov (United States)

Zhang, Yuchen; Li, Gaojin; Ardekani, Arezoo M.

2018-02-01

The bacterial flagellum thickness is smaller than the radius of gyration of long polymer chain molecules. The flow velocity gradient over the length of polymer chains can be nonuniform and continuum models of polymeric liquids break in this limit. In this work, we use Brownian dynamics simulations to study a rotating helical flagellum in a polymer solution and overcome this limitation. As the polymer size increases, the viscosity experienced by the flagellum asymptotically reduces to the solvent viscosity. The contribution of polymer molecules to the local viscosity in a solution of long polymer chains decreases with the inverse of polymer size to the power 1/2. The difference in viscosity experienced by the bacterial cell body and flagella can predict the nonmonotonic swimming speed of bacteria in polymer solutions.

Polymer fragmentation in extensional flow

Energy Technology Data Exchange (ETDEWEB)

Maroja, Armando M.; Oliveira, Fernando A.; Ciesla, Michal; Longa, Lech

2001-06-01

In this paper we present an analysis of fragmentation of dilute polymer solutions in extensional flow. The transition rate is investigated both from theoretical and computational approaches, where the existence of a Gaussian distribution for the breaking bonds has been controversial. We give as well an explanation for the low fragmentation frequency found in DNA experiments.

Dynamics of polymers in elongational flow studied by the neutron spin-echo technique

International Nuclear Information System (INIS)

Rheinstaedter, Maikel C.; Sattler, Rainer; Haeussler, Wolfgang; Wagner, Christian

2010-01-01

The nanoscale fluctuation dynamics of semidilute high molecular weight polymer solutions of polyethylenoxide (PEO) in D 2 O under non-equilibrium flow conditions were studied by the neutron spin-echo technique. The sample cell was in contraction flow geometry and provided a pressure driven flow with a high elongational component that stretched the polymers most efficiently. Neutron scattering experiments in dilute polymer solutions are challenging because of the low polymer concentration and corresponding small quasi-elastic signals. A relaxation process with relaxation times of about 10 ps was observed, which shows anisotropic dynamics with applied flow.

Effect of solute segregation on thermal creep in dilute nanocyrstalline Cu alloys

International Nuclear Information System (INIS)

Schäfer, Jonathan; Ashkenazy, Yinon; Albe, Karsten; Averback, Robert S

2012-01-01

Highlights: ► Segregating solutes lower the grain boundary free volume in nanocrystalline Cu. ► Lower free volume leads to reduced atomic mobility and higher creep resistance. ► Increase in creep resistance scales with atomic size of segregating solutes. ► Atomic processes in boundaries are similar to the ones in amorphous material. - Abstract: The effect of solute segregation on thermal creep in dilute nanocrystalline alloys (Cu–Nb, Cu–Fe, Cu–Zr) was studied at elevated temperatures using molecular dynamics simulations. A combined Monte-Carlo and molecular dynamics simulation technique was first used to equilibrate the distribution of segregating solutes. Then the creep rates of the diluted Cu samples were measured as functions of temperature, composition, load and accumulated strain. In Cu–Nb samples, the creep rates were observed to increase initially with strain, but then saturate at a value close to that obtained for alloys prepared by randomly locating the solute in the grain boundaries. This behavior is attributed to an increase in grain boundary volume and energy with added chemical disorder. At high temperatures, the apparent activation energy for creep was anomalously high, 3 eV, but only 0.3 eV at lower temperatures. This temperature dependence is found to correlate with atomic mobilities in bulk Cu–Nb glasses. Calculations of creep in nanocrystalline Cu alloys containing other solutes, Fe and Zr, show that the suppression of creep rate scales with their atomic volumes when dissolved in Cu.

Effective Microporosity for Enhanced Adsorption Capacity of Cr (VI) from Dilute Aqueous Solution: Isotherm and Kinetics

OpenAIRE

Lloyd Mukosha; Maurice S. Onyango; Aoyi Ochieng; John Siame

2017-01-01

The adsorbent pore structure significant to enhanced adsorption capacity of Cr (VI) from dilute aqueous solution is evaluated. As reference, low-cost micro-mesoporous activated carbon (AC) of high basicity, mesoporosity centred about 2.4 nm, and effective microporosity centred about 0.9 nm was tested for removal of Cr (VI) from dilute aqueous solution in batch mode. At pH 2 the low-cost AC exhibited highly improved Langmuir Cr (VI) capacity of 115 mg/g which was competitive to high performanc...

Superfluidity of a dilute 3He-4He solution

International Nuclear Information System (INIS)

Soda, Toshio

1993-01-01

The interaction between two 3 He atoms is calculated by taking into account the backflow effect of 3 He by the 4 He in the 3 He- 4 He mixture. The effect contributes solely to the P wave part of the interaction. The repulsive S wave part of the contact interaction contributes to the exchange interaction between the 3 He atoms, while the direct one phonon exchange interaction contributes both to the S and P wave attractive interactions. The overall contribution to the attractive interaction is dominated by the P wave part and the superfluidity in the P wave is more predominant than in the S wave for the 5 % dilute 3 He- 4 He solution, and vice versa for the 1.3 % solution. (author)

Block copolymer micelle coronas as quasi-two-dimensional dilute or semidilute polymer solutions

DEFF Research Database (Denmark)

Svaneborg, C.; Pedersen, J.S.

2001-01-01

Chain-chain interactions in a corona of polymers tethered to a spherical core under good solvent conditions are studied using Monte Carlo simulations. The total scattering function of the corona as well as different partial contributions are sampled. By combining the different contributions...

Radiolysis of dilute aqueous solutions of cesium iodide

International Nuclear Information System (INIS)

Gorbovitskaya, T.I.; Galinkin, D.L.; Kants, L.K.; Tiliks, Yu.E.; Kotelkin, I.M.; Luzanova, L.M.

1993-01-01

Study of physical-chemical processes in the NPP containment by severe accident is carried out. Radiolysis of reactor cooling water containing iodine and cesium radionuclides penetrated therein in the course of accident is considered as of such processes. Role of ionizing radiation in the process of formation and release of ecologically hazardous volatile forms of radioiodine from reactor water into environment is studied. Experiments on radiolysis of CsI diluted water solutions are carried out. The data obtained were used for clarification of radiolysis mechanism for iodine-containing water system, enabling forecast of iodine behaviour in the course of the accident. 5 refs., 4 figs., 1 tab

Numerical simulation of solute trapping phenomena using phase-field solidification model for dilute binary alloys

Directory of Open Access Journals (Sweden)

Henrique Silva Furtado

2009-09-01

Full Text Available Numerical simulation of solute trapping during solidification, using two phase-field model for dilute binary alloys developed by Kim et al. [Phys. Rev. E, 60, 7186 (1999] and Ramirez et al. [Phys. Rev. E, 69, 05167 (2004] is presented here. The simulations on dilute Cu-Ni alloy are in good agreement with one dimensional analytic solution of sharp interface model. Simulation conducted under small solidification velocity using solid-liquid interface thickness (2λ of 8 nanometers reproduced the solute (Cu equilibrium partition coefficient. The spurious numerical solute trapping in solid phase, due to the interface thickness was negligible. A parameter used in analytical solute trapping model was determined by isothermal phase-field simulation of Ni-Cu alloy. Its application to Si-As and Si-Bi alloys reproduced results that agree reasonably well with experimental data. A comparison between the three models of solute trapping (Aziz, Sobolev and Galenko [Phys. Rev. E, 76, 031606 (2007] was performed. It resulted in large differences in predicting the solidification velocity for partition-less solidification, indicating the necessity for new and more acute experimental data.

Extensional Rheology of Entangled Polystyrene Solutions Suggests Importance of Nematic Interactions

DEFF Research Database (Denmark)

Huang, Qian; Javier Alvarez, Nicolas; Matsumiya, Yumi

2013-01-01

We compare the linear and nonlinear rheological response of three entangled polystyrene solutions with the same concentration of polymer, but diluted using different solvents. The three solutions have exactly the same physical tube model parameters when normalized to the same time scale. Although...

A Polymer "Pollution Solution" Classroom Activity.

Science.gov (United States)

Helser, Terry L.

1996-01-01

Explains an approach to presenting polymer chemistry to nonmajors that employs polystyrene foam, foam peanuts made from water soluble starch, and water soluble plastic bags. Students are presented with a pollution scenario and are guided to the discovery of solutions. (DDR)

SANS structural characterization of fullerenol-derived star polymers in solutions

CERN Document Server

Jeng, U S; Wang, L Y; Chiang, L Y; Ho, D L; Han, C C

2002-01-01

We have studied the chain conformations of fullerenol-derived star polymers in two organic solvents using small-angle neutron scattering (SANS). The SANS results indicate that the six poly(urethane-ether) arms, chemically bonded on the fullerenol of the C sub 6 sub 0 -based star polymer, have a Gaussian chain conformation in toluene. However, these arms exhibit a pronounced excluded-volume effect in dimethylformamide solutions. We use a scattering model, with the polydispersity of the polymer taken into account, and a fractal model to extract the radius of gyration R sub g values and the persistence lengths of the C sub 6 sub 0 -star polymers in these two organic solutions. (orig.)

New polymers containing BF2-benzoylacetonate groups. Synthesis, luminescence, excimer and exciplex formation

International Nuclear Information System (INIS)

Fedorenko, Elena V.; Mirochnik, Anatolii G.; Beloliptsev, Anton Yu.

2017-01-01

In the present study, a new synthetic method for the functionalization of polystyrene (PS) and (styrene-methyl methacrylate) copolymer has been developed. Using the new method, polymers containing BF 2 -benzoylacetonate groups have been obtained through double acylation by acetic anhydride with boron trifluoride. Luminescence of the produced polymers in solutions and films has been studied. Quantum yields of polymer solution luminescence are significantly higher than those of the low-molecular-weight analog – boron difluoride benzoylacetonate. For the polymer, in which styrene fragments are separated by methyl methacrylate groups, at low concentrations of the polymer in solution one observes the monomer luminescence of BF 2 -benzoylacetonate groups, while at high concentrations – the excimer luminescence. In case of PS-based polymers, in which BF 2 -benzoylacetonate groups and phenyl rings are not separated, in diluted solutions one observes the fluorescence of the intramolecular exciplexes, while at the concentration increase – the luminescence of intermolecular exciplexes. The ability of excimer formation is responsible for the increased photostability of the produced polymers. - Highlights: •Polymers containing BF 2 -benzoylacetonate groups have been synthesized. •Luminescence of the produced polymers in solutions and films has been studied. •Formation of excimers and exciplexes in solution has been revealed. •Formation of excimers in films increases their photostability.

Flexible polymers in a nematic medium : a Monte Carlo simulation

NARCIS (Netherlands)

Vliet, J.H. van; Luyten, M.C.; Brinke, G. ten

Monte Carlo simulations of self-avoiding random walks surrounded by aligned rods on a square lattice and a simple cubic lattice were performed to address the topological constraints involved for dilute solutions of flexible polymers in a highly oriented nematic solvent. The nematic constraint

Effect of backbone structure on charge transport along isolated conjugated polymer chains

International Nuclear Information System (INIS)

Siebbeles, Laurens D.A.; Grozema, Ferdinand C.; Haas, Matthijs P. de; Warman, John M.

2005-01-01

Fast charge transport in conjugated polymers is essential for their application in opto-electronic devices. In the present paper, measurements and theoretical modeling of the mobility of excess charges along isolated chains of conjugated polymers in dilute solution are presented. Charge carriers were produced by irradiation of the polymer solution with 3-MeV electrons from a Van de Graaff accelerator. The mobilities of the charges along the polymer chains were obtained from time-resolved microwave conductivity measurements. The mobilities are strongly dependent on the chemical nature of the polymer backbone. Comparison of the experimental data with results from ab initio quantum mechanical calculations shows that the measured mobilities are strongly limited by torsional disorder, chemical defects and chain ends. Improvement of the structure of polymer backbones is therefore expected to significantly enhance the performance of these materials in 'plastic electronics'

Artificial Neural Network Model to Estimate the Viscosity of Polymer Solutions for Enhanced Oil Recovery

Directory of Open Access Journals (Sweden)

Pan-Sang Kang

2016-06-01

Full Text Available Polymer flooding is now considered a technically- and commercially-proven method for enhanced oil recovery (EOR. The viscosity of the injected polymer solution is the key property for successful polymer flooding. Given that the viscosity of a polymer solution has a non-linear relationship with various influential parameters (molecular weight, degree of hydrolysis, polymer concentration, cation concentration of polymer solution, shear rate, temperature and that measurement of viscosity based on these parameters is a time-consuming process, the range of solution samples and the measurement conditions need to be limited and precise. Viscosity estimation of the polymer solution is effective for these purposes. An artificial neural network (ANN was applied to the viscosity estimation of FlopaamTM 3330S, FlopaamTM 3630S and AN-125 solutions, three commonly-used EOR polymers. The viscosities measured and estimated by ANN and the Carreau model using Lee’s correlation, the only method for estimating the viscosity of an EOR polymer solution in unmeasured conditions, were compared. Estimation accuracy was evaluated by the average absolute relative deviation, which has been widely used for accuracy evaluation of the results of ANN models. In all conditions, the accuracy of the ANN model is higher than that of the Carreau model using Lee’s correlation.

Neutron spin echo spectroscopy. Its application to the study of the dynamics of polymers in solution

International Nuclear Information System (INIS)

Papoular, Robert

1992-06-01

This work focuses on Neutron Spin Echo (NSE) spectroscopy and on the NSE spectrometer MESS, which we have built at the L.L.B. (CE Saclay). After analyzing in detail the classical and quantum principles of this type of instrument, and illustrated them with optical analogies, we expound a simple formalism for the interpretation of polarized neutron experiments of the most general type. In a second part, we describe the MESS spectrometer extensively; its characteristics and performances as well as the first results obtained with this instrument. In particular, we include two papers showing how the neutron depolarization, spin rotation and echoes can be used to investigate high-Tc superconductors. The last part deals with the dynamics of Polymer-Polymer-Solvent ternary solutions and demonstrates how the Neutron Spin Echo technique becomes a privileged tool for such physico-chemical studies thanks to the joint use of NSE and contrast variation methods, coupled with the adequate ranges of time and scattering vectors accessible. Finally, we describe the specific case of partially deuterated polydimethyl-siloxane (PDMS) in semi-dilute solution in Toluene. We have experimentally and separately evidenced the cooperative and inter-diffusive diffusion modes predicted by the theory of Akcasu, Benoit, Benmouna et al. These results, obtained at the L.L.B. (CE Saclay) are the subject matter of the last paper included in this work. (author) [fr

Dilute solutions and phase behavior of polydisperse A-b-(A-co-B) diblock copolymers

Czech Academy of Sciences Publication Activity Database

Gromadzki, Daniel; Lokaj, Jan; Šlouf, Miroslav; Štěpánek, Petr

2009-01-01

Roč. 50, č. 11 (2009), s. 2451-2459 ISSN 0032-3861 Institutional research plan: CEZ:AV0Z40500505 Keywords : diblock copolymer * dilute solution properties * microphase separation Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.573, year: 2009

Stabilization of polymer solutions in the presence of oxidizing agents

Energy Technology Data Exchange (ETDEWEB)

Mendez, A; Serino, A; Jenkins, D; Lichaa, P M

1974-01-01

Many investigators in the field of heavy oil recovery techniques have confirmed the recovery efficiency which, in the miscible displacement method, has utilized polymer solutions as additives to the injection fluids. The viscosity increase of the displacing phase has lowered the mobility ratio with a significant improvement in the sweep efficiency. Recently, others have reported a notable improvement in the recovery of heavy crude by this same method of miscible displacement which causes a mobile fluid bank between the crude and the displacing fluid. There is an intervening oxidation reaction, promoting the in situ formation of surface-active agents on the interface of these 2 fluids. This study describes the effect on degradation of polymer solutions by such oxidizing agents as potassium chromate and potassium permanganate. The degradation of any polymer solution with or without additives is increased materially by an increase in temperature. The presence of NaCl brine is not often of any great significance in the time of gelation, especially with polymers of the polysaccharide type. (18 refs.)

Controlling solution-phase polymer aggregation with molecular weight and solvent additives to optimize polymer-fullerene bulk heterojunction solar cells

KAUST Repository

Bartelt, Jonathan A.

2014-03-20

The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well understood. This work determines how M n and solvent additives affect the performance of BHJ solar cells made with the polymer poly(di(2-ethylhexyloxy)benzo[1,2-b:4,5-b\\']dithiophene-co- octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD). Low M n PBDTTPD devices have exceedingly large fullerene-rich domains, which cause extensive charge-carrier recombination. Increasing the M n of PBDTTPD decreases the size of these domains and significantly improves device performance. PBDTTPD aggregation in solution affects the size of the fullerene-rich domains and this effect is linked to the dependency of PBDTTPD solubility on M n. Due to its poor solubility high M n PBDTTPD quickly forms a fibrillar polymer network during spin-casting and this network acts as a template that prevents large-scale phase separation. Furthermore, processing low M n PBDTTPD devices with a solvent additive improves device performance by inducing polymer aggregation in solution and preventing large fullerene-rich domains from forming. These findings highlight that polymer aggregation in solution plays a significant role in determining the morphology and performance of BHJ solar cells. The performance of poly(di(2-ethylhexyloxy) benzo[1,2-b:4,5-b\\']dithiophene-co-octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) bulk heterojunction solar cells strongly depends on the polymer molecular weight, and processing these bulk heterojunctions with a solvent additive preferentially improves the performance of low molecular weight devices. It is demonstrated that polymer aggregation in solution significantly impacts the thin-film bulk heterojunction morphology and is vital for high device performance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of the van der Waals equation of state to polymers .4. Correlation and prediction of lower critical solution temperatures for polymer solutions

DEFF Research Database (Denmark)

Goncalves, Ana Saraiva; Kontogeorgis, Georgios; Harismiadis, Vassilis I.

1996-01-01

The van der Waals equation of state is used for the correlation and the prediction of the lower critical solution behavior or mixtures including a solvent and a polymer. The equation of state parameters for the polymer are estimated from experimental volumetric data at low pressures. The equation...

Theoretical-experimental study of the solvation enthalpy of acetone in dilute aqueous solution

International Nuclear Information System (INIS)

Arroyo, S. Tolosa; Martin, J.A. Sanson; Garcia, A. Hidalgo

2005-01-01

The present paper describes molecular dynamics simulations of aqueous solutions at infinite dilution with acetone as solute. Lennard-Jones with electrostatic term (12-6-1 potentials) were employed to describe the solute-solvent interactions. The Morokuma decomposition scheme of ab initio interaction energies at the SCF level and the ESIE charges on the solute atoms were used to reproduce the exchange and Coulomb electrostatic contributions of the solute-water interaction potential. Some extensions, such as including the dispersion component evaluated at MP2 level, were added to the traditional calculation procedures in order to improve the results of the solvation enthalpy. The results obtained with the EX-DIS-ES model were compared with the experimental calorimetry values, the observed agreement being acceptable

New polymers containing BF{sub 2}-benzoylacetonate groups. Synthesis, luminescence, excimer and exciplex formation

Energy Technology Data Exchange (ETDEWEB)

Fedorenko, Elena V., E-mail: gev@ich.dvo.ru [Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, 159, Prosp. 100 letiya Vladivostoka, Vladivostok 690022 (Russian Federation); Mirochnik, Anatolii G.; Beloliptsev, Anton Yu. [Institute of Chemistry, Far Eastern Branch of the Russian Academy of Sciences, 159, Prosp. 100 letiya Vladivostoka, Vladivostok 690022 (Russian Federation)

2017-05-15

In the present study, a new synthetic method for the functionalization of polystyrene (PS) and (styrene-methyl methacrylate) copolymer has been developed. Using the new method, polymers containing BF{sub 2}-benzoylacetonate groups have been obtained through double acylation by acetic anhydride with boron trifluoride. Luminescence of the produced polymers in solutions and films has been studied. Quantum yields of polymer solution luminescence are significantly higher than those of the low-molecular-weight analog – boron difluoride benzoylacetonate. For the polymer, in which styrene fragments are separated by methyl methacrylate groups, at low concentrations of the polymer in solution one observes the monomer luminescence of BF{sub 2}-benzoylacetonate groups, while at high concentrations – the excimer luminescence. In case of PS-based polymers, in which BF{sub 2}-benzoylacetonate groups and phenyl rings are not separated, in diluted solutions one observes the fluorescence of the intramolecular exciplexes, while at the concentration increase – the luminescence of intermolecular exciplexes. The ability of excimer formation is responsible for the increased photostability of the produced polymers. - Highlights: •Polymers containing BF{sub 2}-benzoylacetonate groups have been synthesized. •Luminescence of the produced polymers in solutions and films has been studied. •Formation of excimers and exciplexes in solution has been revealed. •Formation of excimers in films increases their photostability.

Mechanical Degradation Onset of Polyethylene Oxide Used as a Hydrosoluble Model Polymer for Enhanced Oil Recovery Seuil de dégradation mécanique de solutions de polymères utilisés en récupération assistée des hydrocarbures

Directory of Open Access Journals (Sweden)

Dupas A.

2013-02-01

Full Text Available Water soluble polymers such as polyacrylamide are used in polymer flooding, which is an advanced technique of Enhanced Oil Recovery (EOR. It aims at improving crude oil displacement in reservoir by pushing it with a viscous injected fluid. Polymer flood is challenged by mechanical degradation of long macromolecules during intense flows. Many studies reported that above a critical extensional rate hbox{$varepsilon^{mathrm{cdot }}_{mathrm{c}}$} ε c · , polymer chains can break and lose their rheological properties. The molecular weight (M dependence of hbox{$varepsilon^{mathrm{cdot }}_{mathrm{c}}$} ε c · for dilute solutions in laminar flows was shown to follow a power law: hbox{$varepsilon^{mathrm{cdot }}_{mathrm{c}}$} ε c · ≈ Mw–k. An experimental study has been performed to investigate the onset of mechanical degradation in both laminar and turbulent flows and for both dilute and semi dilute polyethylene oxide aqueous solutions. It reveals that the exponent k strongly depends on the concentration and flow regimes and also on solvent quality. Results show that mechanical degradation mainly affects long chains, that it is favoured at high concentrations, under poor solvent conditions. They also evidence that the extensional viscosity at low strain rates decreases to the same extent as shear viscosities due to mechanical degradation. However, the decrease of the extensional viscous properties at high strain rates is much more pronounced. Les polymères hydrosolubles comme les polyacrylamides peuvent être utilisés en récupération assistée des hydrocarbures (Enhanced Oil Recovery (EOR par injection de polymère. Cette technique vise à augmenter la production de brut en le poussant du réservoir vers un puits producteur à l’aide d’une solution de polymère suffisamment visqueuse. Les polymères utilisés à cet effet ont des masses moléculaires supérieures à 106 g/mol, ce qui les rend sensibles à la dégradation. En raison

Numerical solution of the polymer system

Energy Technology Data Exchange (ETDEWEB)

Haugse, V.; Karlsen, K.H.; Lie, K.-A.; Natvig, J.R.

1999-05-01

The paper describes the application of front tracking to the polymer system, an example of a nonstrictly hyperbolic system. Front tracking computes piecewise constant approximations based on approximate Remain solutions and exact tracking of waves. It is well known that the front tracking method may introduce a blow-up of the initial total variation for initial data along the curve where the two eigenvalues of the hyperbolic system are identical. It is demonstrated by numerical examples that the method converges to the correct solution after a finite time that decreases with the discretization parameter. For multidimensional problems, front tracking is combined with dimensional splitting and numerical experiments indicate that large splitting steps can be used without loss of accuracy. Typical CFL numbers are in the range of 10 to 20 and comparisons with the Riemann free, high-resolution method confirm the high efficiency of front tracking. The polymer system, coupled with an elliptic pressure equation, models two-phase, tree-component polymer flooding in an oil reservoir. Two examples are presented where this model is solved by a sequential time stepping procedure. Because of the approximate Riemann solver, the method is non-conservative and CFL members must be chosen only moderately larger than unity to avoid substantial material balance errors generated in near-well regions after water breakthrough. Moreover, it is demonstrated that dimensional splitting may introduce severe grid orientation effects for unstable displacements that are accentuated for decreasing discretization parameters. 9 figs., 2 tabs., 26 refs.

Spin coating of an evaporating polymer solution

KAUST Repository

Münch, Andreas; Please, Colin P.; Wagner, Barbara

2011-01-01

and centrifugal forces and evaporation of the solvent. In the model both the diffusivity of the solvent in the polymer and the viscosity of the mixture are very rapidly varying functions of the solvent mass fraction. Guided by numerical solutions an asymptotic

Reverse osmosis performance of cellulose acetate membranes in the separation of uranium from dilute solutions

International Nuclear Information System (INIS)

Sastri, V.S.; Ashbrook, A.W.

1976-01-01

Batch 316-type cellulose acetate membranes were characterized in terms of pure water permeability constant, solute transport parameter, and mass transfer coefficient with a reference system of aqueous sodium chloride solution. These membranes were used in the determination of reverse osmosis characteristics such as product rate and solute separation in the case of uranium sulfate solutions of different concentrations (100 to 8000 ppM) in the feed solutions. A long-term test extending over a week has been carried out with dilute uranium solutions. Reverse osmosis treatment of synthetic mine water sample showed satisfactory performance of the membranes in the separation of metal ions

Diluting ferric carboxymaltose in sodium chloride infusion solution (0.9% w/v) in polypropylene bottles and bags: effects on chemical stability.

Science.gov (United States)

Philipp, Erik; Braitsch, Michaela; Bichsel, Tobias; Mühlebach, Stefan

2016-01-01

This study was designed to assess the physicochemical stability of colloidal ferric carboxymaltose solution (Ferinject) when diluted and stored in polypropylene (PP) bottles and bags for infusion. Two batches of ferric carboxymaltose solution (Ferinject) were diluted (500 mg, 200 mg and 100 mg iron in 100 mL saline) in PP bottles or bags under aseptic conditions. The diluted solutions were stored at 30°C and 75%±5% relative humidity (rH) for 72 h, and samples were withdrawn aseptically at preparation and after 24 h, 48 h and 72 h. Multiple parameters were used to test stability-related measures (pH, total iron and iron (II) content, molecular weight range determination, microbial contamination and particles count ≥10 μm). Overall, Ferinject diluted in 0.9% (w/v) NaCl solution and stored in PP bottles and bags was stable within the specifications for the complex and the acceptability limits set for all assays. In both containers, total iron content remained stable, within 10% of the theoretical iron content, and levels of iron (II) remained far below the threshold of acceptability. All preparations were free from sediments, particle numbers were acceptable and there was no microbial contamination. The molecular weight distribution and polydispersity index were also acceptable. Under the tested experimental conditions, colloidal ferric carboxymaltose solution (Ferinject) diluted in saline in PP infusion bottles or bags demonstrated physical and chemical stability for up to 72 h at 30°C and 75% rH. Because of the lack of additional clinical data, when using ferric carboxymaltose, physicians/pharmacists should refer to the dilution and storing recommendations given in the product's summary of product characteristics.

Osmotic pressure of ring polymer solutions : A Monte Carlo study

NARCIS (Netherlands)

Flikkema, Edwin; Brinke, Gerrit ten

2000-01-01

Using the wall theorem, the osmotic pressure of ring polymers in solution has been determined using an off-lattice topology conserving Monte Carlo algorithm. The ring polymers are modeled as freely-jointed chains with point-like beads, i.e., under conditions corresponding to θ-conditions for the

Drag reduction behavior of hydrolyzed polyacrylamide/xanthan gum mixed polymer solutions

Institute of Scientific and Technical Information of China (English)

Mehdi Habibpour; Peter E.Clark

2017-01-01

Partially hydrolyzed polyacrylamide (HPAM) as the main component of slickwater fracturing fluid is a shear-sensitive polymer,which suffers from mechanical degradation at turbulent flow rates.Five different concentrations of HPAM as well as mixtures of polyacrylamide/xanthan gum were prepared to investigate the possibility of improving shear stability of HPAM.Drag reduction (DR)measurements were performed in a closed flow loop.For HPAM solutions,the extent of DR increased from 30％ to 67％ with increasing HPAM concentration from 100 to 1000 wppm.All the HPAM solutions suffered from mechanical degradation and loss of DR efficiency over the shearing period.Results indicated that the resistance to shear degradation increased with increasing polymer concentration.DR efficiency of 600 wppm xanthan gum (XG)was 38％,indicating that XG was not as good a drag reducer as HPAM.But with only 6％ DR decline,XG solution exhibited a better shear stability compared to HPAM solutions.Mixed HPAM/XG solutions initially exhibited greater DR (40％ and 55％) compared to XG,but due to shear degradation,DR％ dropped for HPAM/XG solutions.Compared to 200 wppm HPAM solution,addition of XG did not improve the drag reduction efficiency of HPAM/XG mixed solutions though XG slightly improved the resistance against mechanical degradation in HPAM/XG mixed polymer solutions.

Gamma-radiolysis of some glycoproteins in dilute aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Nagrani, S

1981-01-01

A study has been made of the radiation-induced damage of some glycoproteins in dilute aqueous solutions. By use of specific radical scavengers, the roles of the individual free radicals, formed by ..gamma..-radiolysis, in causing damage has been assessed. The most effective radical in causing damage to human and porcine glycopolypeptide is the OH radical. The structure of the different blood group glycopolypeptides determines the sensitivity towards the free radical attack. The glycopolypeptide shows depolymerization and a characteristic absorption at approximately 270 nm due to the formation of additional products on irradiation. Chemical changes of the irradiated glycopolypeptide solutions revealed significant damage to the oligosaccharide chain and the polypeptide core of the glycopolypeptide. The radiation-induced inactivation of another glycoprotein, external yeast invertase, due to different radical species at pH 7.0 decreases in the following order: ea-barq > OH radical > (SCN) radical/sub 2//sup -/ > Br radical/sub 2//sup -/. The structure of this enzyme, accounts for the mechanism of enzyme inactivation and the relative damage of carbohydrate and amino acid residues. The irradiated enzyme solutions show significant changes in their electrophoretic behaviour on cellogel electrophoresis due to the formation of radiolysis products, which also show characteristic absorption maxima at approximately 275 nm. (author).

L'infiltration d'une dilution ideale des solutions avec epineph rine au ...

African Journals Online (AJOL)

L'auteur rapporte un procédé simplifié de dilution d'une solution anesthésique avec épinéphrine passant d'une concentration de 1/100 000 à 1/800 000 pour rechercher une hémostase locale effective sans compromettre dans l'immédiat la vitalité de la vascularisation périphérique des lambeaux cutanés levés. The author ...

Selective removal/recovery of RCRA metals from waste and process solutions using polymer filtration trademark technology

International Nuclear Information System (INIS)

Smith, B.F.

1997-01-01

Resource Conservation and Recovery Act (RCRA) metals are found in a number of process and waste streams at many DOE, U.S. Department of Defense, and industrial facilities. RCRA metals consist principally of chromium, mercury, cadmium, lead, and silver. Arsenic and selenium, which form oxyanions, are also considered RCRA elements. Discharge limits for each of these metals are based on toxicity and dictated by state and federal regulations (e.g., drinking water, RCRA, etc.). RCRA metals are used in many current operations, are generated in decontamination and decommissioning (D ampersand D) operations, and are also present in old process wastes that require treatment and stabilization. These metals can exist in solutions, as part of sludges, or as contaminants on soils or solid surfaces, as individual metals or as mixtures with other metals, mixtures with radioactive metals such as actinides (defined as mixed waste), or as mixtures with a variety of inert metals such as calcium and sodium. The authors have successfully completed a preliminary proof-of-principle evaluation of Polymer Filtration trademark (PF) technology for the dissolution of metallic mercury and have also shown that they can remove and concentrate RCRA metals from dilute solutions for a variety of aqueous solution types using PF technology. Another application successfully demonstrated is the dilute metal removal of americium and plutonium from process streams. This application was used to remove the total alpha contamination to below 30 pCi/L for the wastewater treatment plant at TA-50 at Los Alamos National Laboratory (LANL) and from nitric acid distillate in the acid recovery process at TA-55, the Plutonium Facility at LANL (ESP-CP TTP AL16C322). This project will develop and optimize the PF technology for specific DOE process streams containing RCRA metals and coordinate it with the needs of the commercial sector to ensure that technology transfer occurs

Selective removal/recovery of RCRA metals from waste and process solutions using polymer filtration{trademark} technology

Energy Technology Data Exchange (ETDEWEB)

Smith, B.F. [Los Alamos National Lab., NM (United States)

1997-10-01

Resource Conservation and Recovery Act (RCRA) metals are found in a number of process and waste streams at many DOE, U.S. Department of Defense, and industrial facilities. RCRA metals consist principally of chromium, mercury, cadmium, lead, and silver. Arsenic and selenium, which form oxyanions, are also considered RCRA elements. Discharge limits for each of these metals are based on toxicity and dictated by state and federal regulations (e.g., drinking water, RCRA, etc.). RCRA metals are used in many current operations, are generated in decontamination and decommissioning (D&D) operations, and are also present in old process wastes that require treatment and stabilization. These metals can exist in solutions, as part of sludges, or as contaminants on soils or solid surfaces, as individual metals or as mixtures with other metals, mixtures with radioactive metals such as actinides (defined as mixed waste), or as mixtures with a variety of inert metals such as calcium and sodium. The authors have successfully completed a preliminary proof-of-principle evaluation of Polymer Filtration{trademark} (PF) technology for the dissolution of metallic mercury and have also shown that they can remove and concentrate RCRA metals from dilute solutions for a variety of aqueous solution types using PF technology. Another application successfully demonstrated is the dilute metal removal of americium and plutonium from process streams. This application was used to remove the total alpha contamination to below 30 pCi/L for the wastewater treatment plant at TA-50 at Los Alamos National Laboratory (LANL) and from nitric acid distillate in the acid recovery process at TA-55, the Plutonium Facility at LANL (ESP-CP TTP AL16C322). This project will develop and optimize the PF technology for specific DOE process streams containing RCRA metals and coordinate it with the needs of the commercial sector to ensure that technology transfer occurs.

Role of Molecular Interactions for Synergistic Precipitation Inhibition of Poorly Soluble Drug in Supersaturated Drug-Polymer-Polymer Ternary Solution.

Science.gov (United States)

Prasad, Dev; Chauhan, Harsh; Atef, Eman

2016-03-07

We are reporting a synergistic effect of combined Eudragit E100 and PVP K90 in precipitation inhibition of indomethacin (IND) in solutions at low polymer concentration, a phenomenon that has significant implications on the usefulness of developing novel ternary solid dispersion of poorly soluble drugs. The IND supersaturation was created by cosolvent technique, and the precipitation studies were performed in the absence and the presence of individual and combined PVP K90 and Eudragit E100. The studies were also done with PEG 8000 as a noninteracting control polymer. A continuous UV recording of the IND absorption was used to observe changes in the drug concentration over time. The polymorphic form and morphology of precipitated IND were characterized by Raman spectroscopy and scanning electron microscopy. The change in the chemical shift in solution (1)H NMR was used as novel approach to probe IND-polymer interactions. Molecular modeling was used for calculating binding energy between IND-polymer as another indication of IND-polymer interaction. Spontaneous IND precipitation was observed in the absence of polymers. Eudragit E100 showed significant inhibitory effect on nuclei formation due to stronger interaction as reflected in higher binding energy and greater change in chemical shift by NMR. PVP K90 led to significant crystal growth inhibition due to adsorption on growing IND crystals as confirmed by modified crystal habit of precipitate in the presence of PVP K90. Combination of polymers resulted in a synergistic precipitation inhibition and extended supersaturation. The NMR confirmed interaction between IND-Eudragit E100 and IND-PVP K90 in solution. The combination of polymers showed similar peak shift albeit using lower polymer concentration indicating stronger interactions. The results established the significant synergistic precipitation inhibition effect upon combining Eudragit E100 and PVP K90 due to drug-polymer interaction.

Brushes and soap : grafted polymers and their interactions with nanocolloids

OpenAIRE

Currie, E.P.K.

2000-01-01

Layers of polymer chains end-attached to a grafting plane at high densities, so-called brushes, are a curious state of matter. The (average) monomer density within the brush is as high as in a semi-dilute polymer solution, resulting in a high osmotic pressure in the brush. Due to the grafting, however, this isotropic osmotic pressure results in an anisotropic stretching of the chains normal to the surface. This degree of stretching can be quite extensive; in this thesis PEO-chains of...

Investigation of the in-solution relaxation of polymer optical fibre Bragg gratings

DEFF Research Database (Denmark)

Fasano, Andrea; Woyessa, Getinet; Janting, Jakob

2016-01-01

We investigate the response of PMMA microstructured polymer optical fibre Bragg gratings whenimmersed in methanol/water solutions. Overall we observe a permanent blue-shift in Bragg gratingwavelength after solvent evaporation. The main contribution in the resonance wavelength shift probably...... arisesfrom a permanent change in the size of the fibre, as already reported for high-temperature annealing ofpolymer optical fibres. As a consequence of the solution concentration dependence of the glass transitiontemperature of polymers, different methanol/water solutions lead to various degrees of frozen...

Enthalpy of dilution and volumetric properties of N-glycylglycine in aqueous xylitol solutions at T = 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Liu Min, E-mail: panpanliumin@163.co [College of Chemistry and Chemical Engineering, Liao Cheng University, Liaocheng, Shandong 252059 (China); Wang Lili; Li Guangqian; Dong Lina; Sun Dezhi [College of Chemistry and Chemical Engineering, Liao Cheng University, Liaocheng, Shandong 252059 (China); Zhu Lanying [College of Life Science and Bioengineering, Liao Cheng University, Liaocheng, Shandong 252059 (China); Di Youying [College of Chemistry and Chemical Engineering, Liao Cheng University, Liaocheng, Shandong 252059 (China)

2011-06-15

Highlights: Enthalpies of dilution of N-glycylglycine in aqueous xylitol solutions were determined at 298.15 K. The homogeneous enthalpic interaction coefficients were calculated. Apparent molar volumes of the ternary systems were calculated from the data of densities. Limiting partial molar volumes and limiting partial molar volumes of transfer were deduced. - Abstract: The enthalpy of dilution of N-glycylglycine ({Delta}{sub dil}H{sub m}) in aqueous xylitol solutions has been determined by means of flow-mix isothermal microcalorimetry at the temperature of 298.15 K. The homogeneous enthalpic interaction coefficients (h{sub 2}, h{sub 3}, and h{sub 4}) which characterize the interactions of examined N-glycylglycine in aqueous xylitol solutions have been calculated according to the excess enthalpy concept based on the values of dilution enthalpy. It has been found that the enthalpic pair interaction coefficients (h{sub 2}) in the systems investigated are negative and become less negative as the molality of xylitol increases. Values of the density ({rho}) of the ternary homogeneous systems were also measured with a quartz vibrating-tube densimeter at the temperature of 298.15 K. The values of the apparent molar volume (V{sub {phi}}) of the ternary systems were calculated from the data of density, which have been used to deduce limiting partial molar volumes of N-glycylglycine (V{sub {phi}}{sup o}) and limiting partial molar volumes of transfer ({Delta}{sub trs}V{sub {phi}}{sup o}) from water to aqueous xylitol solutions at different concentrations. The results have been discussed based on solute-solute interactions and solvation effects.

Enthalpy of dilution and volumetric properties of N-glycylglycine in aqueous xylitol solutions at T = 298.15 K

International Nuclear Information System (INIS)

Liu Min; Wang Lili; Li Guangqian; Dong Lina; Sun Dezhi; Zhu Lanying; Di Youying

2011-01-01

Highlights: → Enthalpies of dilution of N-glycylglycine in aqueous xylitol solutions were determined at 298.15 K. → The homogeneous enthalpic interaction coefficients were calculated. → Apparent molar volumes of the ternary systems were calculated from the data of densities. → Limiting partial molar volumes and limiting partial molar volumes of transfer were deduced. - Abstract: The enthalpy of dilution of N-glycylglycine (Δ dil H m ) in aqueous xylitol solutions has been determined by means of flow-mix isothermal microcalorimetry at the temperature of 298.15 K. The homogeneous enthalpic interaction coefficients (h 2 , h 3 , and h 4 ) which characterize the interactions of examined N-glycylglycine in aqueous xylitol solutions have been calculated according to the excess enthalpy concept based on the values of dilution enthalpy. It has been found that the enthalpic pair interaction coefficients (h 2 ) in the systems investigated are negative and become less negative as the molality of xylitol increases. Values of the density (ρ) of the ternary homogeneous systems were also measured with a quartz vibrating-tube densimeter at the temperature of 298.15 K. The values of the apparent molar volume (V φ ) of the ternary systems were calculated from the data of density, which have been used to deduce limiting partial molar volumes of N-glycylglycine (V φ o ) and limiting partial molar volumes of transfer (Δ trs V φ o ) from water to aqueous xylitol solutions at different concentrations. The results have been discussed based on solute-solute interactions and solvation effects.

Stern potential and Debye length measurements in dilute ionic solutions with electrostatic force microscopy.

Science.gov (United States)

Kumar, Bharat; Crittenden, Scott R

2013-11-01

We demonstrate the ability to measure Stern potential and Debye length in dilute ionic solution with atomic force microscopy. We develop an analytic expression for the second harmonic force component of the capacitive force in an ionic solution from the linearized Poisson-Boltzmann equation. This allows us to calibrate the AFM tip potential and, further, obtain the Stern potential of sample surfaces. In addition, the measured capacitive force is independent of van der Waals and double layer forces, thus providing a more accurate measure of Debye length.

Suppressive effects of a polymer sodium silicate solution on ...

African Journals Online (AJOL)

Sodium silicate was dissolved in water in either a monomer form or polymer form; the effects of both forms of sodium silicate aqueous solution on rose powdery mildew and root rot diseases of miniature rose were examined. Both forms of sodium silicate aqueous solution were applied to the roots of the miniature rose.

Crossover to entangled dynamics in polymer solutions and melts

International Nuclear Information System (INIS)

Schweizer, K.S.; Szamel, G.

1995-01-01

A statistical dynamical theory of the crossover from unentangled Rouse dynamics to entangled behavior is constructed for chain polymer solutions and melts. Both time and spatial crossovers in long chain fluids, and the degree of polymerization crossover for short polymers, are treated. The analysis is based on a microscopic theory of the perturbative dynamical corrections to Rouse theory arising from chain connectivity and intermolecular excluded volume forces. The dependence of crossover properties such as the plateau shear modulus and entanglement time and length scale on solution density, solvent quality, and chain statistical segment length are derived by combining the dynamical theory with equilibrium liquid state integral equation methods. Scaling relations are obtained which appear to be in general accord with most experiments on both solutions and melts. The physical origin of the predicted scaling behaviors is the fractional power law temporal decay of the entanglement friction memory function on intermediate time scales, and power law reduced density dependence of the equilibrium force correlations. The theory is also applied to compute the dependence of the chain normal mode relaxation times on polymer density and chain length. Favorable qualitative comparisons with recent neutron spin echo experiments are made. copyright 1995 American Institute of Physics

Extension of the segment-based Wilson and NRTL models for correlation of excess molar enthalpies of polymer solutions

International Nuclear Information System (INIS)

Sadeghi, Rahmat

2005-01-01

The polymer Wilson model and the polymer NRTL model have been extended for the representation of the excess enthalpy of multicomponent polymer solutions. Applicability of obtained equations in the correlation of the excess enthalpies of polymer solutions has been examined. It is found that the both models are suitable models in representing the published excess enthalpy data for the tested polymer solutions

Se of polymers to control clay swelling

Energy Technology Data Exchange (ETDEWEB)

Slobod, R L; Beiswanger, J P.G.

1968-01-01

The injection of water to displace oil is one of the main methods used to increase oil recovery. High injection rates are generally desired, and in some cases the flood will not be economic unless high rates are maintained. The presence of clays which swell in the presence of water offers a complication to the problem of maintaining adequate injectivity. In the course of this study it was observed that certain polymers, when present in dilute concentrations in the water, had the ability to reduce the response of these clays to fresh water. Two polymers, one an anionic and the other nonionic, were found to be very effective in controlling the clays present in Berea cores. Successful control of clay swelling was obtained by use of solutions containing as little as 1.0 ppM of polymer, but at this low concentration appreciable volumes of treating solution were required. These results suggest that some minimum amount of polymer must be adsorbed to prevent clay swelling. In Berea sandstone this minimum amount appeared to be of the order of 0.03 mg per cc of pore space. A series of tests made using 10.0 ppM polymer showed that the polymer could be made through the porous system in which 0.066 per mg of polymer was adsorbed per cc of pore space.

Studies of Electrolytic Conductivity of Some Polyelectrolyte Solutions: Importance of the Dielectric Friction Effect at High Dilution

Directory of Open Access Journals (Sweden)

Anis Ghazouani

2013-01-01

Full Text Available We present a general description of conductivity behavior of highly charged strong polyelectrolytes in dilute aqueous solutions taking into account the translational dielectric friction on the moving polyions modeled as chains of charged spheres successively bounded and surrounded by solvent molecules. A general formal limiting expression of the equivalent conductivity of these polyelectrolytes is presented in order to distinguish between two concentration regimes and to evaluate the relative interdependence between the ionic condensation effect and the dielectric friction effect, in the range of very dilute solutions for which the stretched conformation is favored. This approach is illustrated by the limiting behaviors of three polyelectrolytes (sodium heparinate, sodium chondroitin sulfate, and sodium polystyrene sulphonate characterized by different chain lengths and by different discontinuous charge distributions.

Dermal absorption of a dilute aqueous solution of malathion

Directory of Open Access Journals (Sweden)

Scharf John

2008-01-01

Full Text Available Malathion is an organophosphate pesticide commonly used on field crops, fruit trees, livestock, agriculture, and for mosquito and medfly control. Aerial applications can result in solubilized malathion in swimming pools and other recreational waters that may come into contact with human skin. To evaluate the human skin absorption of malathion for the assessment of risk associated with human exposures to aqueous solutions, human volunteers were selected and exposed to aqueous solutions of malathion. Participants submerged their arms and hands in twenty liters of dilute malathion solution in either a stagnant or stirred state. The "disappearance method" was applied by measuring malathion concentrations in the water before and after human exposure for various periods of time. No measurable skin absorption was detected in 42% of the participants; the remaining 58% of participants measured minimal absorbed doses of malathion. Analyzing these results through the Hazard Index model for recreational swimmer and bather exposure levels typically measured in contaminated swimming pools and surface waters after bait application indicated that these exposures are an order of magnitude less than a minimal dose known to result in a measurable change in acetylcholinesterase activity. It is concluded that exposure to aqueous malathion in recreational waters following aerial bait applications is not appreciably absorbed, does not result in an effective dose, and therefore is not a public health hazard.

A study of SEC chromatograms on the basis of polymer structure properties

DEFF Research Database (Denmark)

Size Exclusion Chromatography (SEC), widely used in polymer laboratories, provides a convenient method for the determination of full molecular weight distribution (MWD) of polymers. For linear homogeneous polymer samples, the procedure to estimate the true MWD based on the elution curve of SEC has...... already been well established, while for nonlinear polymer samples and mixtures of linear and nonlinear polymers, the measured SEC data are often used just qualitatively. The SEC separation process is rather complicated, and a detailed study using finite element method and/or Brownian Dynamics simulation...... technique is rather difficult without oversimplifying the problem dramatically. However, it has been known for long that SEC separates polymer molecules according to their size in dilute solutions, and experimental studies with well-defined linear and nonlinear polymer samples have shown that a universal...

A Study of SEC Chromatograms on the basis of Polymer Structure Calculations

DEFF Research Database (Denmark)

Hassager, Ole; Wang, Yanwei

2007-01-01

Size Exclusion Chromatography (SEC), widely used in polymer laboratories, provides a convenient method for the determination of full molecular weight distribution (MWD) of polymers. For linear homogeneous polymer samples, the procedure to estimate the true MWD based on the elution curve of SEC has...... already been well established, while for nonlinear polymer samples and mixtures of linear and nonlinear polymers, the measured SEC data are often used just qualitatively. The SEC separation process is rather complicated, and a detailed study using finite element method and/or Brownian Dynamics simulation...... technique is rather difficult without oversimplifying the problem dramatically. However, it has been known for long that SEC separates polymer molecules according to their size in dilute solutions, and experimental studies with well-defined linear and nonlinear polymer samples have shown that a universal...

Radiation processing of biodegradable polymer hydrogel from cellulose derivatives

International Nuclear Information System (INIS)

Wach, Radoslaw A.; Mitomo, Hiroshi; Yoshii, Fumio; Kume, Tamikazu

2001-01-01

The effects of high-energy radiation on ethers of cellulose: carboxymethyl-, hydroxypropyl- and hydroxyethylcellulose have been investigated. Polymers were irradiated in solid state and aqueous solution at various concentrations. Degree of substitution (DS), the concentration in the solution and irradiation conditions had a significant impact on the obtained products. Irradiation of polymers in solid and in diluted solution resulted in their degradation. A novel hydrogels of such natural polymers were synthesized, without using any additives, by irradiation at high concentration. It was found that high DS of CMC promoted crosslinking and, for all of the ethers, the gel formation occurred easier for more concentrated solutions. Paste-like form of the initial material, when water plasticised the bulk of polymer mass, along with the high dose rate and preventing oxygen accessibility to the sample during irradiation were favorable for hydrogel preparation. Up to 95% of gel fraction was obtained from 50 and 60% CMC solutions irradiated by gamma rays or by a beam of accelerated electrons (EB). The other polymers were more sensitive to the dose rate and formed gels with higher gel fraction while processed by EB. Moreover, polymers (except CMC) treated by gamma rays were susceptible to degradation after application of a dose over 50-100 kGy. The presence of oxygen in the system during irradiation limited a gel content and was prone to easier degradation of already formed gel. Produced hydrogels swelled markedly by absorption when paced in the solvent. Crosslinked polymers showed susceptibility to degradation by cellulase enzyme and by the action of microorganisms in compost or under natural conditions in soil thus could be included into the group of biodegradable materials. (author)

Radiation processing of biodegradable polymer hydrogel from cellulose derivatives

Energy Technology Data Exchange (ETDEWEB)

Wach, Radoslaw A.; Mitomo, Hiroshi [Gunma Univ., Faculty of Engineering, Department of Biological and Chemical Engineering, Kiryu, Gunma (Japan); Yoshii, Fumio; Kume, Tamikazu [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

2001-03-01

The effects of high-energy radiation on ethers of cellulose: carboxymethyl-, hydroxypropyl- and hydroxyethylcellulose have been investigated. Polymers were irradiated in solid state and aqueous solution at various concentrations. Degree of substitution (DS), the concentration in the solution and irradiation conditions had a significant impact on the obtained products. Irradiation of polymers in solid and in diluted solution resulted in their degradation. A novel hydrogels of such natural polymers were synthesized, without using any additives, by irradiation at high concentration. It was found that high DS of CMC promoted crosslinking and, for all of the ethers, the gel formation occurred easier for more concentrated solutions. Paste-like form of the initial material, when water plasticised the bulk of polymer mass, along with the high dose rate and preventing oxygen accessibility to the sample during irradiation were favorable for hydrogel preparation. Up to 95% of gel fraction was obtained from 50 and 60% CMC solutions irradiated by gamma rays or by a beam of accelerated electrons (EB). The other polymers were more sensitive to the dose rate and formed gels with higher gel fraction while processed by EB. Moreover, polymers (except CMC) treated by gamma rays were susceptible to degradation after application of a dose over 50-100 kGy. The presence of oxygen in the system during irradiation limited a gel content and was prone to easier degradation of already formed gel. Produced hydrogels swelled markedly by absorption when paced in the solvent. Crosslinked polymers showed susceptibility to degradation by cellulase enzyme and by the action of microorganisms in compost or under natural conditions in soil thus could be included into the group of biodegradable materials. (author)

Stern potential and Debye length measurements in dilute ionic solutions with electrostatic force microscopy

International Nuclear Information System (INIS)

Kumar, Bharat; Crittenden, Scott R

2013-01-01

We demonstrate the ability to measure Stern potential and Debye length in dilute ionic solution with atomic force microscopy. We develop an analytic expression for the second harmonic force component of the capacitive force in an ionic solution from the linearized Poisson–Boltzmann equation. This allows us to calibrate the AFM tip potential and, further, obtain the Stern potential of sample surfaces. In addition, the measured capacitive force is independent of van der Waals and double layer forces, thus providing a more accurate measure of Debye length. (paper)

Prediction of activity coefficients at infinite dilution for organic solutes in ionic liquids by artificial neural network

Energy Technology Data Exchange (ETDEWEB)

Nami, Faezeh [Department of Chemistry, Shahid Beheshti University, G.C., Evin-Tehran 1983963113 (Iran, Islamic Republic of); Deyhimi, Farzad, E-mail: f-deyhimi@sbu.ac.i [Department of Chemistry, Shahid Beheshti University, G.C., Evin-Tehran 1983963113 (Iran, Islamic Republic of)

2011-01-15

To our knowledge, this work illustrates for the first time the ability of artificial neural network (ANN) to predict activity coefficients at infinite dilution for organic solutes in ionic liquids (ILs). Activity coefficient at infinite dilution ({gamma}{sup {infinity}}) is a useful parameter which can be used for the selection of effective solvent in the separation processes. Using a multi-layer feed-forward network with Levenberg-Marquardt optimization algorithm, the resulting ANN model generated activity coefficient at infinite dilution data over a temperature range of 298 to 363 K. The unavailable input data concerning softness (S) of organic compounds (solutes) and dipole moment ({mu}) of ionic liquids were calculated using GAMESS suites of quantum chemistry programs. The resulting ANN model and its validation are based on the investigation of up to 24 structurally different organic compounds (alkanes, alkenes, alkynes, cycloalkanes, aromatics, and alcohols) in 16 common imidazolium-based ionic liquids, at different temperatures within the range of 298 to 363 K (i.e. a total number of 914 {gamma}{sub Solute}{sup {infinity}}for each IL data point). The results show a satisfactory agreement between the predicted ANN and experimental data, where, the root mean square error (RMSE) and the determination coefficient (R{sup 2}) of the designed neural network were found to be 0.103, 0.996 for training data and 0.128, 0.994 for testing data, respectively.

Prediction of activity coefficients at infinite dilution for organic solutes in ionic liquids by artificial neural network

International Nuclear Information System (INIS)

Nami, Faezeh; Deyhimi, Farzad

2011-01-01

To our knowledge, this work illustrates for the first time the ability of artificial neural network (ANN) to predict activity coefficients at infinite dilution for organic solutes in ionic liquids (ILs). Activity coefficient at infinite dilution (γ ∞ ) is a useful parameter which can be used for the selection of effective solvent in the separation processes. Using a multi-layer feed-forward network with Levenberg-Marquardt optimization algorithm, the resulting ANN model generated activity coefficient at infinite dilution data over a temperature range of 298 to 363 K. The unavailable input data concerning softness (S) of organic compounds (solutes) and dipole moment (μ) of ionic liquids were calculated using GAMESS suites of quantum chemistry programs. The resulting ANN model and its validation are based on the investigation of up to 24 structurally different organic compounds (alkanes, alkenes, alkynes, cycloalkanes, aromatics, and alcohols) in 16 common imidazolium-based ionic liquids, at different temperatures within the range of 298 to 363 K (i.e. a total number of 914 γ Solute ∞ for each IL data point). The results show a satisfactory agreement between the predicted ANN and experimental data, where, the root mean square error (RMSE) and the determination coefficient (R 2 ) of the designed neural network were found to be 0.103, 0.996 for training data and 0.128, 0.994 for testing data, respectively.

Scaling Behavior of Dendritic Nanoparticle Mobility in Semidilute Polymer Solutions

NARCIS (Netherlands)

Kort, de D.W.; Rombouts, W.H.; Hoeben, F.J.M.; Janssen, H.M.; As, van H.; Duynhoven, van J.P.M.

2015-01-01

In our studies on particle mobility in polymer solutions, we have investigated and determined self-diffusion coefficients of nanoparticles in semidilute solutions of poly(ethylene glycol) (PEG, Mw = 6, 20, 35, and 100 kDa). Specially designed PEGylated dendrimers with well-defined sizes (dh =

Controlling solution-phase polymer aggregation with molecular weight and solvent additives to optimize polymer-fullerene bulk heterojunction solar cells

KAUST Repository

Bartelt, Jonathan A.; Douglas, Jessica D.; Mateker, William R.; El Labban, Abdulrahman; Tassone, Christopher J.; Toney, Michael F.; Fré chet, Jean Mj J; Beaujuge, Pierre; McGehee, Michael D.

2014-01-01

The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well

Separation of glycols from dilute aqueous solutions via complexation with boronic acids

Energy Technology Data Exchange (ETDEWEB)

Randel, L.A.; King, C.J.

1991-07-01

This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

Gelation of Photonic Microdomain Structures Formed in Semi-Dilute Solutions of Ultra-High-Molecular-Weight Polystyrene-b-Polybutadiene with Various Polybutadiene Contents

International Nuclear Information System (INIS)

Okamoto, S; Ito, S; Ando, K; Mouri, M; Ikeda, A; Hasegawa, H; Koshikawa, N

2010-01-01

Well-ordered microdomain structures were obtained in semi-dilute solutions and successfully stabilized by gelation. We used polystyrene-b-polybutadiene (PS-b-PB) diblock copolymer with the weight-averaged molecular weight varying from several hundred thousands to millions g/mol. The solutions had iridescent colors because the domain spacing is on the order of the wavelength of visible light. As the structures are susceptible to distortion by flow or vibration, structural fixation was carried out by gelation. The polybutadiene used has the microstructure of 1,2-linkage and hence the chains can be cross-linkable. The Small-Angle X-ray Scattering and the UV-vis spectroscopic measurements showed that in the case of PS-b-PBs with the PB volume fraction, φ PB , greater than about 50 vol % the microdomain structures were successfully fixed by gelation, while largely distorted in the case of those with φ PB < ca. 50 vol %. The SAXS scattering intensities were quantitatively analyzed by the scattering functions numerically calculated based on the one- and two-dimensional paracrystal theories and on the concentration fluctuation between the polymers and the solvent molecules.

Increase in Ice Nucleation Efficiency of Feldspars, Kaolinite and Mica in Dilute NH3 and NH4+-containing Solutions

Science.gov (United States)

Kumar, A.; Marcolli, C.; Luo, B.; Krieger, U. K.; Peter, T.

2017-12-01

Semivolatile species present in the atmosphere are prone to adhere to mineral dust particle surfaces during long range transport, and could potentially change the particle surface properties and its ice nucleation (IN) efficiency. Immersion freezing experiments were performed with microcline (K-feldspar), known to be highly IN active, suspended in aqueous solutions of ammonia, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl to investigate the effect of solutes on the IN efficiency. Freezing of emulsified droplets investigated with a differential scanning calorimeter (DSC) showed that the heterogeneous ice nucleation temperatures deviate from the water activity-based IN theory, describing heterogeneous ice nucleation temperatures as a function of solution water activity by a constant offset with respect to the ice melting point curve (Zobrist et al. 2008). IN temperatures enhanced up to 4.5 K were observed for very dilute NH3 and NH4+-containing solutions while a decrease was observed as the concentration was further increased. For all solutes with cations other than NH4+, the IN efficiency decreased. An increase of the IN efficiency in very dilute NH3 and NH4+-containing solutions followed by a decrease with increasing concentration was also observed for sanidine (K-feldspar) and andesine (Na/Ca-feldspar). This is an important indication towards specific chemical interactions between solutes and the feldspar surface which is not captured by the water activity-based IN theory. A similar trend is present but less pronounced in case of kaolinite and mica, while quartz is barely affected. We hypothesize that the hydrogen bonding of NH3 molecules with surface -OH groups could be the reason for the enhanced freezing temperatures in dilute ammonia and ammonium containing solutions as they could form an ice-like overlayer providing hydrogen bonding groups for ice to nucleate on top of it. This implies to possibilities of enhanced IN efficiency, especially

Viscoelasticity and nonlinear simple shear flow behavior of an entangled asymmetric exact comb polymer solution

KAUST Repository

Snijkers, F.; Kirkwood, K. M.; Vlassopoulos, D.; Leal, L. G.; Nikopoulou, A.; Hadjichristidis, Nikolaos; Coppola, S.

2016-01-01

We report upon the characterization of the steady-state shear stresses and first normal stress differences as a function of shear rate using mechanical rheometry (both with a standard cone and plate and with a cone partitioned plate) and optical rheometry (with a flow-birefringence setup) of an entangled solution of asymmetric exact combs. The combs are polybutadienes (1,4-addition) consisting of an H-skeleton with an additional off-center branch on the backbone. We chose to investigate a solution in order to obtain reliable nonlinear shear data in overlapping dynamic regions with the two different techniques. The transient measurements obtained by cone partitioned plate indicated the appearance of overshoots in both the shear stress and the first normal stress difference during start-up shear flow. Interestingly, the overshoots in the start-up normal stress difference started to occur only at rates above the inverse stretch time of the backbone, when the stretch time of the backbone was estimated in analogy with linear chains including the effects of dynamic dilution of the branches but neglecting the effects of branch point friction, in excellent agreement with the situation for linear polymers. Flow-birefringence measurements were performed in a Couette geometry, and the extracted steady-state shear and first normal stress differences were found to agree well with the mechanical data, but were limited to relatively low rates below the inverse stretch time of the backbone. Finally, the steady-state properties were found to be in good agreement with model predictions based on a nonlinear multimode tube model developed for linear polymers when the branches are treated as solvent.

Viscoelasticity and nonlinear simple shear flow behavior of an entangled asymmetric exact comb polymer solution

KAUST Repository

Snijkers, F.

2016-03-31

We report upon the characterization of the steady-state shear stresses and first normal stress differences as a function of shear rate using mechanical rheometry (both with a standard cone and plate and with a cone partitioned plate) and optical rheometry (with a flow-birefringence setup) of an entangled solution of asymmetric exact combs. The combs are polybutadienes (1,4-addition) consisting of an H-skeleton with an additional off-center branch on the backbone. We chose to investigate a solution in order to obtain reliable nonlinear shear data in overlapping dynamic regions with the two different techniques. The transient measurements obtained by cone partitioned plate indicated the appearance of overshoots in both the shear stress and the first normal stress difference during start-up shear flow. Interestingly, the overshoots in the start-up normal stress difference started to occur only at rates above the inverse stretch time of the backbone, when the stretch time of the backbone was estimated in analogy with linear chains including the effects of dynamic dilution of the branches but neglecting the effects of branch point friction, in excellent agreement with the situation for linear polymers. Flow-birefringence measurements were performed in a Couette geometry, and the extracted steady-state shear and first normal stress differences were found to agree well with the mechanical data, but were limited to relatively low rates below the inverse stretch time of the backbone. Finally, the steady-state properties were found to be in good agreement with model predictions based on a nonlinear multimode tube model developed for linear polymers when the branches are treated as solvent.

Sorption of ochratoxin A from aqueous solutions using β-cyclodextrin-polyurethane polymer.

Science.gov (United States)

Appell, Michael; Jackson, Michael A

2012-02-01

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1-10 μg·L(-1). These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples.

[Effect of 60Co gamma-irradiation on dilute aqueous solutions of surfactants].

Science.gov (United States)

Sawai, T; Shimokowa, T; Miki, Y; Oseko, K; Sawai, T

1978-01-01

Present work deals with the effects of gamma irradiation from 60Co gamma-ray source upon aqueous solutions of three kinds of surfactants. When dilute aqueous solutions of sodium dodecyl sulfate (SDS, anionic), cethyl trimethyl ammonium chloride (CTAC, cationic), and polyoxyethylene lauryl ether (POE, non-ionic) were irradiated with gamma-rays at a room remperature, the residual concentration, products, surface tension, and forming power were examined by colorimetric method, IR spectrophotometric method, gaschromatography, Ross-Miles method, and Traube's stalagnometer etc.. These surfactants were decomposed by the irradiation and thus the surface tension increased and the forming power, on the contrary, decreased with dose. Radiation chemical yields (G-value) of the degradation were about 1 for the solutions of SDS and CTAC, and about 0.3 for the POE solution. From the experimental results, it was found that following chemical reactions seem to occur followed by the radiolysis of water; a) bond cleavage of ester for SDS, of CN for CTAC, and of oxyethylene for POE, b) hydrogen abstraction from the surfactants, c) production of CO bond in the presence of dissolved oxygen.

Synthesis of new water-soluble metal-binding polymers: Combinatorial chemistry approach. 1997 mid-year progress report

International Nuclear Information System (INIS)

Smith, B.F.

1997-01-01

'The first objective of this research is to develop rapid discovery and optimization approaches to new water-soluble chelating polymers. A byproduct of the development approach will be the new, selective, and efficient metal-binding agents. The second objective is to evaluate the concept of using water and organic soluble polymers as new solid supports for combinatorial synthesis. The technology under development, Polymer Filtration (PF), is a technique to selectively remove or recover hazardous and valuable metal ions and radionuclides from various dilute aqueous streams. Not only can this technology be used to remediate contaminated soils and solid surfaces and treat aqueous wastes, it can also be incorporated into facilities as a pollution prevention and waste minimization technology. Polymer Filtration uses water-soluble metal-binding polymers to sequester metal ions in dilute solution. The water-soluble polymers have a sufficiently large molecular size that they can be separated and concentrated using commercial ultrafiltration technology. Water, small organic molecules, and unbound metals pass freely through the ultrafiltration membrane while concentrating the metal-binding polymer. The polymers can then be reused by changing the solution conditions to release the metal ions. The metal-ions are recovered in concentrated form for recycle or disposal using a diafiltration process. The water-soluble polymer can be recycled for further aqueous-stream processing. To advance Polymer Filtration technology to the selectivity levels required for DOE needs. fixture directions in Polymer Filtration must include rapid development, testing, and characterization of new metal-binding polymers. The development of new chelating molecules can be equated to the process of new drugs or new materials discovery. Thus, the authors want to build upon and adapt the combinatorial chemistry approaches developed for rapid molecule generation for the drug industry to the rapid

Formation and thermodynamic stability of (polymer + porphyrin) supramolecular structures in aqueous solutions

International Nuclear Information System (INIS)

Costa, Viviana C.P. da; Hwang, Barrington J.; Eggen, Spencer E.; Wallace, Megan J.; Annunziata, Onofrio

2014-01-01

Highlights: • Thermodynamic stability of a (polymer + porphyrin) supramolecular structure was characterized. • Isothermal titration calorimetry provided two ways to determine reaction enthalpies. • Exothermic (polymer + porphyrin) binding competes with porphyrin self-association. • (Polymer + porphyrin) binding is entropically favored with respect to porphyrin self-association. • Spectral shifts show importance of porphyrin central hydrogens in polymer binding. - Abstract: Optical properties of porphyrins can be tuned through (polymer + porphyrin) (host + guest) binding in solution. This gives rise to the formation of supramolecular structures. In this paper, the formation, thermodynamic stability and spectroscopic properties of (polymer + porphyrin) supramolecular structures and their competition with porphyrin self-association were investigated by both isothermal titration calorimetry (ITC) and absorption spectroscopy. Specifically, reaction enthalpies and equilibrium constants were measured for meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) self-association and TPPS binding to the polymer poly(vinylpyrrolidone) (PVP, 40 kg/mol) in aqueous solutions at pH 7 and three different temperatures (12, 25 and 37 °C). ITC, compared to spectroscopic techniques, provides two independent means to determine reaction enthalpies: direct measurements and Van’t Hoff plot. This was used as a criterion to assess that (1) self-association of TPPS is limited to the formation of dimers and (2) TPPS binds to PVP in its monomeric state only. The formation of TPPS dimers and (PVP + TPPS) supramolecular structures are both enthalpically driven. However, (polymer + porphyrin) binding was found to be entropically favored compared to dimerization. Furthermore, the reaction enthalpies of these two processes significantly depend on temperature. This behavior was attributed to hydrophobic interactions. Finally, the limiting absorption spectra of monomeric, dimeric and polymer

Dynamic structurization in solutions of hydrodynamically active polymers

International Nuclear Information System (INIS)

Pogrebnyak, V.G.; Tverdokhleb, S.V.; Naumchuk, N.V.

1993-01-01

The processes of ordering and self-regulation in nonlinear systems have attracted great attention because understanding the principles of self-regulation and its thermodynamics can become a clue to many physical phenomena. In this work, it is experimentally established that, under the condition of elongational flows, dynamic structurization and periodic processes may originate in the solutions of flexible, hydrodynamically-active polymers due to self-regulation in these systems. The hydrodynamic elongational field was created using the flow of a Newtonian liquid (water, acetone, dioxane) converging to a small opening. The hydrodynamically-active polymers were polyethylene oxide or hydrolyzed polyacrylamide

Universal aspects of macromolecules in polymer blends, solutions, and supercritical mixtures

International Nuclear Information System (INIS)

Melnichenko, Y.B.; Wignall, G.D.; Schwahn, D.

2002-01-01

We demonstrate that macromolecules in miscible polymer blends may behave as good, Θ, and poor polymeric solvents for each other. We construct a conceptual phase diagram, delineating the range of validity of the random-phase approximation, outside of which polymers contract or expand beyond their unperturbed dimensions, contrary to common assumptions. Remarkably, the correlation length for polymer blends, solutions, and supercritical mixtures collapses onto a master curve, reflecting universal behavior for macromolecules in polymeric and small-molecule Θ solvents

Osmotic pressure and virial coefficients of star and comb polymer solutions: dissipative particle dynamics.

Science.gov (United States)

Wang, Tzu-Yu; Fang, Che-Ming; Sheng, Yu-Jane; Tsao, Heng-Kwong

2009-03-28

The effects of macromolecular architecture on the osmotic pressure pi and virial coefficients (B(2) and B(3)) of star and comb polymers in good solvents are studied by dissipative particle dynamics simulations for both dilute and semiconcentrated regimes. The dependence of the osmotic pressure on polymer concentration is directly calculated by considering two reservoirs separated by a semipermeable, fictitious membrane. Our simulation results show that the ratios A(n+1) identical with B(n+1)/R(g)(3n) are essentially constant and A(2) and A(3) are arm number (f) dependent, where R(g) is zero-density radius of gyration. The value of dimensionless virial ratio g = A(3)/A(2)(2) increases with arm number of stars whereas it is essentially arm number independent for comb polymers. In semiconcentrated regime the scaling relation between osmotic pressure and volume fraction, pi proportional to phi(lambda), still holds for both star and comb polymers. For comb polymers, the exponent lambda is close to lambda(*) (approximately = 2.73 for linear chains) and is independent of the arm number. However, for star polymers, the exponent lambda deviates from lambda(*) and actually grows with increasing the arm number. This may be attributed to the significant ternary interactions near the star core in the many-arm systems.

Activity coefficients at infinite dilution of organic solutes in 1-hexyl-3-methylimidazolium trifluoroacetate and influence of interfacial adsorption using gas–liquid chromatography

International Nuclear Information System (INIS)

Jiang, Lin-Kun; Wang, Li-Sheng; Du, Chao-Jun; Wang, Xue-Yuan

2014-01-01

Highlights: • Activity coefficients at infinite dilution of organic solutes in [HMIM][TFA] were determined. • The contribution of interfacial adsorption to the retention mechanism was estimated. • The partial molar excess enthalpies and the solubility parameters of [HMIM][TFA] were calculated. -- Abstract: Activity coefficients at infinite dilution for a series of organic solutes in the ionic liquid 1-hexyl-3-methylimidazolium trifluoroacetate ([HMIM][TFA]) have been determined by gas–liquid chromatography at the temperature range from (303.15 to 363.15) K. The contribution of interfacial adsorption to the retention mechanism was estimated by changing the loading of ionic liquid in stationary phase. The partial molar excess enthalpies at infinite dilution and the solubility parameters of ionic liquid were also calculated from the experimental values of activity coefficients at infinite dilution

Activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate

International Nuclear Information System (INIS)

Domanska, Urszula; Krolikowska, Marta; Acree, William E.; Baker, Gary A.

2011-01-01

Research highlights: → Measurements of activity coefficients at infinite dilution using GLC. → 36 organic solvents and water in the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate, [EMIM][TCB]. → Possible entrainer for different separation processes. → The partial molar excess thermodynamic functions at infinite dilution were calculated. - Abstract: The activity coefficients at infinite dilution, γ 13 ∞ , for 36 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, tetrahydrofuran, ethers, acetone, and water, in the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate, [EMIM][TCB], were determined by gas-liquid chromatography at temperatures from 298.15 K to 358.15 K. These values are compared to those previously published for selected solutes in the same ionic liquid. The values of the partial molar excess Gibbs free energy ΔG 1 E,∞ , enthalpy ΔH 1 E,∞ , and entropy ΔS 1 E,∞ at infinite dilution were calculated from the experimental γ 13 ∞ values obtained over the temperature range. Three gas-liquid partition coefficients, K L were calculated for all solutes and the Abraham solvation parameter model is discussed. The values of the selectivity for different separation problems were calculated from γ 13 ∞ and compared to literature values for N-methyl-2-pyrrolidinone (NMP), sulfolane, 1-decyl-3-methylimidazolium tetracyanoborate, [DMIM][TCB], and additional ionic liquids.

Assessment of Some Synthetic Polymers for the Removal of Pollutants from Waste Solutions

International Nuclear Information System (INIS)

Ayoub, R.; El-Naggar, H.A.; Ezz EL-Din, M.R.; Moussa, A.R.

1999-01-01

The sorption capacity of 134 Cs, 60 Co, 152+154 Eu and Cu (II) by three prepared has been studied using batch and column techniques. The three polymers are polyacrylic acid (PAA), polyacrylamide-acrylic acid (PAM-AA) and polyacrylamide-N-vinyl-2-pyrraldone (PAM-NVP). These polymers were prepared by gamma radiation initiated polymerization of their corresponding monomer solutions. The appropriate value for V/m ratio (volume of solution to mass of polymer) that can result in reasonably high distribution coefficient, Kd, was determined. The variation of the amount sorbed of the isotope per gram polymer (X/m) with concentration of the relevant element was found to follow a Frendlich type isotherm. The distribution coefficient, Kd, of the studied element was found to be affected by the ph of the solution. The desorption of the investigated metal ions is also studied at different ph. For column studies, the percent removed of the radioisotopes 134 Cs, 60 Co, ( 152+154 )Eu in addition to some heavy metals ions such as Pb, Cd, Zn and Cu(II) was determined. More than 95% of these elements were removed when 3 beds column of PAA or PAM-AA was used. From the data obtained we can conclude that the polymer PAA or PAM-AA can considered as an efficient sorbent for metal cations from their aqueous solution

Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

Science.gov (United States)

Schuler, Thomas; Nastar, Maylise

2016-06-01

We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

Conformation of ionizable poly Para phenylene ethynylene in dilute solutions

International Nuclear Information System (INIS)

Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora; Grest, Gary S.

2015-01-01

The conformation of dinonyl poly para phenylene ethynylenes (PPEs) with carboxylate side chains, equilibrated in solvents of different quality is studied using molecular dynamics simulations. PPEs are of interest because of their tunable electro-optical properties, chemical diversity, and functionality which are essential in wide range of applications. The polymer conformation determines the conjugation length and their assembly mode and affects electro-optical properties which are critical in their current and potential uses. The current study investigates the effect of carboxylate fraction on PPEs side chains on the conformation of chains in the dilute limit, in solvents of different quality. The dinonyl PPE chains are modeled atomistically, where the solvents are modeled both implicitly and explicitly. Dinonyl PPEs maintained a stretched out conformation up to a carboxylate fraction f of 0.7 in all solvents studied. The nonyl side chains are extended and oriented away from the PPE backbone in toluene and in implicit good solvent whereas in water and implicit poor solvent, the nonyl side chains are collapsed towards the PPE backbone. Thus, rotation around the aromatic ring is fast and no long range correlations are seen within the backbone

Sorption of Ochratoxin A from aqueous solutions using beta-cyclodextrin-polyurethane polymer

Science.gov (United States)

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions, including wine, was examined by batch rebinding assays and equilibrium sorption isotherms. The results were fit to two parameter models. Freundlich analysis of the sorption isotherm indicates the polyme...

Manufacturing polymer light emitting diode with high luminance efficiency by solution process

Science.gov (United States)

Kim, Miyoung; Jo, SongJin; Yang, Ho Chang; Yoon, Dang Mo; Kwon, Jae-Taek; Lee, Seung-Hyun; Choi, Ju Hwan; Lee, Bum-Joo; Shin, Jin-Koog

2012-06-01

While investigating polymer light emitting diodes (polymer-LEDs) fabricated by solution process, surface roughness influences electro-optical (E-O) characteristics. We expect that E-O characteristics such as luminance and power efficiency related to surface roughness and layer thickness of emitting layer with poly-9-Vinylcarbazole. In this study, we fabricated polymer organic light emitting diodes by solution process which guarantees easy, eco-friendly and low cost manufacturing for flexible display applications. In order to obtain high luminescence efficiency, E-O characteristics of these devices by varying parameters for printing process have been investigated. Therefore, we optimized process condition for polymer-LEDs by adjusting annealing temperatures of emission, thickness of emission layer showing efficiency (10.8 cd/A) at 10 mA/cm2. We also checked wavelength dependent electroluminescence spectrum in order to find the correlation between the variation of efficiency and the thickness of the layer.

A simple relation for the concentration dependence of osmotic pressure and depletion thickness in polymer solutions

NARCIS (Netherlands)

Fleer, G.J.; Skvortsov, A.M.; Tuinier, R.

2007-01-01

We propose simple expressions II/IIo = 1 + and (omega/omega(ex))(3 alpha-1) and (delta(0)/delta)(2) = 1 + (omega/omega(ex))(2 alpha) for the osmotic pressure II and the depletion thickness 6 as a function of the polymer concentration omega. Here, IIo and delta 0 correspond to the dilute limit, and

Polymer-based oral rehydration solution for treating acute watery diarrhoea

Science.gov (United States)

Gregorio, Germana V; Gonzales, Maria Liza M; Dans, Leonila F; Martinez, Elizabeth G

2016-01-01

Background Acute diarrhoea is one of the main causes of morbidity and mortality among children in low-income countries. Glucose-based oral rehydration solution (ORS) helps replace fluid and prevent further dehydration from acute diarrhoea. Since 2004, the World Health Organization (WHO) has recommended the osmolarity of less than 270 mOsm/L (ORS ≤ 270) versus greater than 310 mOsm/L formulation (ORS ≥ 310). Polymer-based ORS (for example, prepared using rice or wheat) slowly releases glucose and may be superior to glucose-based ORS. Objectives To compare polymer-based oral rehydration solution (polymer-based ORS) with glucose-based oral rehydration solution (glucose-based ORS) for treating acute watery diarrhoea. Search methods We searched the following sources up to 5 September 2016: the Cochrane Infectious Diseases Group (CIDG) Specialized Register, the Cochrane Central Register of Controlled Trials (CENTRAL) (the Cochrane Library 2016, Issue 9), MEDLINE (1966 to 5 September 2016), EMBASE (1974 to 5 September 2016), LILACS (1982 to 5 September 2016), and mRCT (2007 to 5 September 2016). We also contacted researchers, organizations, and pharmaceutical companies, and searched reference lists. Selection criteria We included randomized controlled trials (RCTs) of people with acute watery diarrhoea (cholera and non-cholera associated) that compared polymer-based and glucose-based ORS (with identical electrolyte contents). Data collection and analysis Two review authors independently assessed the search results and risk of bias, and extracted data. In multiple-treatment arms with two or more treatment groups, we combined outcomes as appropriate and compared collectively with the control group. Main results Thirty-five trials that included 4284 participants met the inclusion criteria: 28 trials exclusively included children, five included adults, and two included both adults and children. Polymer-based ORS versus glucose-based ORS (osmolarity ≤ 270) Eight trials

Laser synthesis of aluminium nanoparticles in biocompatible polymer solutions

Science.gov (United States)

Singh, Rina; Soni, R. K.

2014-08-01

Pulsed laser ablation of Aluminium (Al) in pure water rapidly forms a thin alumina (Al2O3) layer which drastically modifies surface plasmon resonance (SPR) absorption characteristics in deep-UV region. Initially, pure aluminium nanoparticles (NPs) are generated in water without any stabilizers or surfactants at low laser fluence which gradually transform to stable Al-Al2O3 core-shell nanostructure with increasing either residency time or fluence. The role of laser wavelength and fluence on the SPR properties and oxidation characteristics of Al NPs has been investigated in detail. We also present a one-step in situ synthesis of oxide-free stable Al NPs in biocompatible polymer solutions using laser ablation in liquid method. We have used nonionic polymers (PVP, PVA and PEG) and anionic surfactant (SDS) stabilizer to suppress the Al2O3 formation and studied the effect of polymer functional group, polymeric chain length, polymer concentration and anionic surfactant on the incipient embryonic aluminium particles and their sizes. The different functional groups of polymers resulted in different oxidation states of Al. PVP and PVA polymers resulted in pure Al NPs; however, PEG and SDS resulted in alumina-modified Al NPs. The Al nanoparticles capped with PVP, PVA, and PEG show a good correlation between nanoparticle stability and monomeric length of the polymer chain.

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

Science.gov (United States)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

Evaluation of a cell-biopolymer sorbent for uptake of strontium from dilute solutions

International Nuclear Information System (INIS)

Watson, J.S.; Scott, C.D.; Faison, B.D.

1990-01-01

Immobilization of Micrococcus luteus within beads of bone gelatin results in a material which is able to adsorb significant quantities of strontium from dilute aqueous solutions analogous to some nuclear industry wastewaters. The mechanism appears to be principally an ion-exchange phenomenon. Both the bone gelatin and the microbial cells contribute to strontium removal; the principal contribution from the cells appears to be sorption onto cell wall material. This particular biosorbent may not be an immediate replacement for conventional ion-exchange materials currently used to remove strontium from wastewaters. However, the study does indicate that relatively inexpensive biological materials can be incorporated into particulate forms such as gel beads and used for the removal of dissolved metal ions from aqueous solution

Making Molecular Balloons in Laser-Induced Explosive Boiling of Polymer Solutions

International Nuclear Information System (INIS)

Leveugle, Elodie; Sellinger, Aaron; Fitz-Gerald, James M.; Zhigilei, Leonid V.

2007-01-01

The effect of the dynamic molecular rearrangements leading to compositional segregation is revealed in coarse-grained molecular dynamics simulations of short pulse laser interaction with a polymer solution in a volatile matrix. An internal release of matrix vapor at the onset of the explosive boiling of the overheated liquid is capable of pushing polymer molecules to the outskirts of a transient bubble, forming a polymer-rich surface layer enclosing the volatile matrix material. The results explain unexpected 'deflated balloon' structures observed in films deposited by the matrix-assisted pulsed laser evaporation technique

Non‐diluted seawater enhances nasal ciliary beat frequency and wound repair speed compared to diluted seawater and normal saline

Science.gov (United States)

Bonnomet, Arnaud; Luczka, Emilie; Coraux, Christelle

2016-01-01

Background The regulation of mucociliary clearance is a key part of the defense mechanisms developed by the airway epithelium. If a high aggregate quality of evidence shows the clinical effectiveness of nasal irrigation, there is a lack of studies showing the intrinsic role of the different irrigation solutions allowing such results. This study investigated the impact of solutions with different pH and ionic compositions, eg, normal saline, non‐diluted seawater and diluted seawater, on nasal mucosa functional parameters. Methods For this randomized, controlled, blinded, in vitro study, we used airway epithelial cells obtained from 13 nasal polyps explants to measure ciliary beat frequency (CBF) and epithelial wound repair speed (WRS) in response to 3 isotonic nasal irrigation solutions: (1) normal saline 0.9%; (2) non‐diluted seawater (Physiomer®); and (3) 30% diluted seawater (Stérimar). The results were compared to control (cell culture medium). Results Non‐diluted seawater enhanced the CBF and the WRS when compared to diluted seawater and to normal saline. When compared to the control, it significantly enhanced CBF and slightly, though nonsignificantly, improved the WRS. Interestingly, normal saline markedly reduced the number of epithelial cells and ciliated cells when compared to the control condition. Conclusion Our results suggest that the physicochemical features of the nasal wash solution is important because it determines the optimal conditions to enhance CBF and epithelial WRS thus preserving the respiratory mucosa in pathological conditions. Non‐diluted seawater obtains the best results on CBF and WRS vs normal saline showing a deleterious effect on epithelial cell function. PMID:27101776

Effect of 60Co gamma-ray irradiation on dilute aqueous solutions of surfactants

International Nuclear Information System (INIS)

Sawai, Teruko; Shimokawa, Toshinari; Miki, Yasushi; Oseko, Koichi; Sawai, Takeshi

1978-01-01

Present work deals with the effects of gamma irradiation from 60 Co γ-ray source upon aqueous solutions of three kinds of surfactants. When dilute aqueous solutions of sodium dodecyl sulfate (SDS, anionic), cethyl trimethyl ammonium chloride (CTAC, cationic), and polyoxyethylene lauryl ether (POE, non-ionic) were irradiated with γ-rays at a room temperature, the residual concentration, products, surface tension, and forming power were examined by colorimetric method, IR spectrophotometric method, gaschromatography, Ross-Miles method, and Traube's stalagmometer etc. These surfactants were decomposed by the irradiation and thus the surface tension increased and the forming power, on the contrary, decreased with dose. Radiation chemical yields (G-value) of the degradation were about 1 for the solutions of SDS and CTAC, and about 0.3 for the POE solution. From the experimental results, it was found that following chemical reactions seem to occur followed by the radiolysis of water: a) bond cleavage of ester for SDS, of CN for CTAC, and of oxyethylene for POE, b) hydrogen abstraction from the surfactants, c) production of CO bond in the presence of dissolved oxygen. (auth.)

Degradation of homogeneous polymer solutions in high shear turbulent pipe flow

Science.gov (United States)

Elbing, B. R.; Winkel, E. S.; Solomon, M. J.; Ceccio, S. L.

2009-12-01

This study quantifies degradation of polyethylene oxide (PEO) and polyacrylamide (PAM) polymer solutions in large diameter (2.72 cm) turbulent pipe flow at Reynolds numbers to 3 × 105 and shear rates greater than 105 1/s. The present results support a universal scaling law for polymer chain scission reported by Vanapalli et al. (2006) that predicts the maximum chain drag force to be proportional to Re 3/2, validating this scaling law at higher Reynolds numbers than prior studies. Use of this scaling gives estimated backbone bond strengths from PEO and PAM of 3.2 and 3.8 nN, respectively. Additionally, with the use of synthetic seawater as a solvent the onset of drag reduction occurred at higher shear rates relative to the pure water solvent solutions, but had little influence on the extent of degradation at higher shear rates. These results are significant for large diameter pipe flow applications that use polymers to reduce drag.

Entropy-induced separation of star polymers in porous media

International Nuclear Information System (INIS)

Blavats'ka, V.; Ferber, C. von; Holovatch, Yu.

2006-01-01

We present a quantitative picture of the separation of star polymers in a solution where part of the volume is influenced by a porous medium. To this end, we study the impact of long-range-correlated quenched disorder on the entropy and scaling properties of f-arm star polymers in a good solvent. We assume that the disorder is correlated on the polymer length scale with a power-law decay of the pair correlation function g(r)∼r -a . Applying the field-theoretical renormalization group approach we show in a double expansion in ε=4-d and δ=4-a that there is a range of correlation strengths δ for which the disorder changes the scaling behavior of star polymers. In a second approach we calculate for fixed space dimension d=3 and different values of the correlation parameter a the corresponding scaling exponents γ f that govern entropic effects. We find that γ f -1, the deviation of γ f from its mean field value is amplified by the disorder once we increase δ beyond a threshold. The consequences for a solution of diluted chain and star polymers of equal molecular weight inside a porous medium are that star polymers exert a higher osmotic pressure than chain polymers and in general higher branched star polymers are expelled more strongly from the correlated porous medium. Surprisingly, polymer chains will prefer a stronger correlated medium to a less or uncorrelated medium of the same density while the opposite is the case for star polymers

Synthesis of uranyl ion imprinted polymer and its application in analysis

International Nuclear Information System (INIS)

Xiao Jingshui; Liu Huijun; Xiao Xilin; Huang Shengli

2011-01-01

Uranyl ion imprinted polymer beads were prepared by the copolymerization of styrene monomer and divinyl benzene as crosslinking agent in methanol solution,with the UO 2 2+ -o-dihydroxybenzene-4-vinyl pyridine ternary complex as template, the 2, 2'-azo-bis-isobutyronitrile as initiator and UO 2 2+ as the imprinting ion. The uranyl ions were removed from the polymer beads by treating with 6 mol/L HCl, leaving behind cavities that match uranyl ion in size. The treated polymer beads can preconcentrate uranyl ions from dilute aqueous solutions. The adsorption efficiency can reach 99% or above with good selectivity when pH is in the range of 5-7 and the adsorption time is more than 20 min. The elution rate can reach above 99% under the conditions of concentration of HCl being above 1.0 mol/L, elution time more than 20 min and the elution Janume more than 5 times the Janume of ion imprinted polymer. The uranyl ion imprinted polymer beads have been successfully applied to determine micro-uranium in brine samples. The results are satisfactory compared with NBS method.(authors)

A free-volume modification of GEM-QC to correlate VLE and LLE in polymer solutions

International Nuclear Information System (INIS)

Radfarnia, H.R.; Taghikhani, V.; Ghotbi, C.; Khoshkbarchi, M.K.

2004-01-01

The generalized quasi-chemical (GEM-QC) model proposed by Wang and Vera is modified to correlate better the phase equilibrium and to overcome the shortcoming of the original model to predict the lower critical solution temperature (LCST) of binary polymer solutions. This shortcoming is mainly because the GEM-QC model does not consider the effect of free-volume, which is important in systems containing molecules with large size differences. The proposed modification is based on replacing the combinatorial term of the GEM-QC model by a term proposed by Kontogerogis et al., which includes the effect of the free-volume. The main advantage of the free volume generalized quasi-chemical (GEM-QC-FV) model over the original GEM-QC is its ability to predict the phase behaviour of binary polymer solutions with LCST behaviour. In addition, the free volume UNIQUAC (UNIQUAC-FV) model is used to correlate VLE and LLE experimental data for binary polymer solutions. The comparison of the results obtained from the GEM-QC-FV model and the UNIQUAC-FV model shows the superiority of the GEM-QC-FV model in correlating the VLE and LLE experimental data for binary polymer solutions

Spin coating of an evaporating polymer solution

KAUST Repository

Münch, Andreas

2011-01-01

We consider a mathematical model of spin coating of a single polymer blended in a solvent. The model describes the one-dimensional development of a thin layer of the mixture as the layer thins due to flow created by a balance of viscous forces and centrifugal forces and evaporation of the solvent. In the model both the diffusivity of the solvent in the polymer and the viscosity of the mixture are very rapidly varying functions of the solvent mass fraction. Guided by numerical solutions an asymptotic analysis reveals a number of different possible behaviours of the thinning layer dependent on the nondimensional parameters describing the system. The main practical interest is in controlling the appearance and development of a "skin" on the polymer where the solvent concentration reduces rapidly on the outer surface leaving the bulk of the layer still with high concentrations of solvent. In practice, a fast and uniform drying of the film is required. The critical parameters controlling this behaviour are found to be the ratio of the diffusion to advection time scales ε, the ratio of the evaporation to advection time scales δ and the ratio of the diffusivity of the pure polymer and the initial mixture exp(-1/γ). In particular, our analysis shows that for very small evaporation with δ

Inhibition of the solid state transformation of carbamazepine in aqueous solution: impact of polymeric properties.

Science.gov (United States)

Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison

2017-11-06

The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.

Integration of molecular machines into supramolecular materials: actuation between equilibrium polymers and crystal-like gels.

Science.gov (United States)

Mariani, Giacomo; Goujon, Antoine; Moulin, Emilie; Rawiso, Michel; Giuseppone, Nicolas; Buhler, Eric

2017-11-30

In this article, the dynamic structure of complex supramolecular polymers composed of bistable [c2]daisy chain rotaxanes as molecular machines that are linked by ureidopyrimidinones (Upy) as recognition moieties was studied. pH actuation of the integrated mechanically active rotaxanes controls the contraction/extension of the polymer chains as well as their physical reticulation. Small-angle neutron and X-ray scattering were used to study in-depth the nanostructure of the contracted and extended polymer aggregates in toluene solution. The supramolecular polymers comprising contracted nanomachines were found to be equilibrium polymers with a mass that is concentration dependent in dilute and semidilute regimes. Surprisingly, the extended polymers form a gel network with a crystal-like internal structure that is independent of concentration and reminiscent of a pearl-necklace network.

Non-diluted seawater enhances nasal ciliary beat frequency and wound repair speed compared to diluted seawater and normal saline.

Science.gov (United States)

Bonnomet, Arnaud; Luczka, Emilie; Coraux, Christelle; de Gabory, Ludovic

2016-10-01

The regulation of mucociliary clearance is a key part of the defense mechanisms developed by the airway epithelium. If a high aggregate quality of evidence shows the clinical effectiveness of nasal irrigation, there is a lack of studies showing the intrinsic role of the different irrigation solutions allowing such results. This study investigated the impact of solutions with different pH and ionic compositions, eg, normal saline, non-diluted seawater and diluted seawater, on nasal mucosa functional parameters. For this randomized, controlled, blinded, in vitro study, we used airway epithelial cells obtained from 13 nasal polyps explants to measure ciliary beat frequency (CBF) and epithelial wound repair speed (WRS) in response to 3 isotonic nasal irrigation solutions: (1) normal saline 0.9%; (2) non-diluted seawater (Physiomer®); and (3) 30% diluted seawater (Stérimar). The results were compared to control (cell culture medium). Non-diluted seawater enhanced the CBF and the WRS when compared to diluted seawater and to normal saline. When compared to the control, it significantly enhanced CBF and slightly, though nonsignificantly, improved the WRS. Interestingly, normal saline markedly reduced the number of epithelial cells and ciliated cells when compared to the control condition. Our results suggest that the physicochemical features of the nasal wash solution is important because it determines the optimal conditions to enhance CBF and epithelial WRS thus preserving the respiratory mucosa in pathological conditions. Non-diluted seawater obtains the best results on CBF and WRS vs normal saline showing a deleterious effect on epithelial cell function. © 2016 The Authors International Forum of Allergy & Rhinology, published by ARSAAOA, LLC.

Plutonium determination by isotope dilution

International Nuclear Information System (INIS)

Lucas, M.

1980-01-01

The principle is to add to a known amount of the analysed solution a known amount of a spike solution consisting of plutonium 242. The isotopic composition of the resulting mixture is then determined by surface ionization mass spectrometry, and the plutonium concentration in the solution is deduced, from this measurement. For irradiated fuels neutronic studies or for fissile materials balance measurements, requiring the knowledge of the ratio U/Pu or of concentration both uranium and plutonium, it is better to use the double spike isotope dilution method, with a spike solution of known 233 U- 242 Pu ratio. Using this method, the ratio of uranium to plutonium concentration in the irradiated fuel solution can be determined without any accurate measurement of the mixed amounts of sample and spike solutions. For fissile material balance measurements, the uranium concentration is determined by using single isotope dilution, and the plutonium concentration is deduced from the ratio Pu/U and U concentration. The main advantages of isotope dilution are its selectivity, accuracy and very high sensitivity. The recent improvements made to surface ionization mass spectrometers have considerably increased the precision of the measurements; a relative precision of about 0.2% to 0.3% is obtained currently, but it could be reduced to 0.1%, in the future, with a careful control of the experimental procedures. The detection limite is around 0.1 ppb [fr

Solvent-dependent self-assembly and ordering in slow-drying semi-crystalline conjugated polymer solutions

KAUST Repository

Zhao, Kui

2015-09-07

The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport and optoelectronic properties. Yet, to date the vast majority of studies have focused on the fast solution process itself, with studies of slower intrinsic molecular self-assembly in formulations lagging behind. Here we have investigated molecular self-assembly during spontaneous organization and uncovered how changes in formulation influence the microstructure, morphology and transport properties of conjugated polymer thin films. Our results suggest that the polymer-solvent interaction is the key factor for the molecular self-assembly and changes in macroscopic charge transport, which is in contrast with most solution processes, such as spin-coating and blade coating, where solvent drying kinetics dominates the aggregation and crystallization processes. Energetically favourable interactions between the polymer and its solvent are shown to cause chain expansion, resulting in a large hydrodynamic volume and few chain entanglements in solution. This provides molecular freedom for self-assembly and is shown to greatly enhance the local and long range order of the polymer, intra-chain backbone planarity and crystallite size. These improvements, in turn, are shown to endow the conjugated polymer with high carrier transport, as demonstrated by organic thin film transistors.

Synthesis and Rheological Properties of an Associative Star Polymer in Aqueous Solutions

DEFF Research Database (Denmark)

Hietala, Sami; Mononen, Pekka; Strandman, Satu

2007-01-01

synthesised by atom transfer radical. polymerization (ATRP) was found to fonn hydrogels at room temperature at polymer concentrations. Cp, over 22 gIL due to the interpolymer drophobic association of the PS blocks. Increasing Cp leads to stronger elastic networks at room temperature that show a gel......Rheological properties of aqueous solutions and hydrogels fonned by an amphiphiIic star block copolymer poly(acrylic acid)-blockpolystyrene (PAAS4-b-PS6)4. were investigated as a function of the polymer concentration (Cp), temperature, and added saIt concentration. The water-soluble polymer......-to-solution transition with increasing temperature. Increase of ionic strength decreases the moduli compared with the pure hydrogel but did not affect the gel-sol transition temperature significantly. Small-angle X-ray experiments showed two distinct scattering correlation peaks for samples above the gelling Cp, which...

Chemical effects associated to (n, γ) nuclear reactions in diluted aqueous solutions of liquid or frozen organic halogenides

International Nuclear Information System (INIS)

Bermudez Rodriguez, I.M.

1985-09-01

Chemical effects associated to nuclear transformation 37 Cl (n, γ) 38 Cl or 127 I (n, γ) 128 I in solid or liquid aqueous solutions of ethyl iodide, trichloro-ethylene, thyroxine or DDT irradiated in a nuclear reactor are studied. The retention of radiohalogen under its initial chemical shape decrease with solute concentration in liquid phase but is almost constant with solute dilution in the solid phase. Potential applications in neutron activation analysis evidencing halogenated molecules in irradiated media are discussed. 57 refs [fr

Modification of a Turbulent Boundary Layer within a Homogeneous Concentration of Drag reducing Polymer Solution

Science.gov (United States)

Farsiani, Yasaman; Elbing, Brian

2017-11-01

High molecular weight polymer solutions in wall-bounded flows can reduce the local skin friction by as much as 80%. External flow studies have typical focused on injection of polymer within a developing turbulent boundary layer (TBL), allowing the concentration and drag reduction level to evolve with downstream distance. Modification of the log-law region of the TBL is directly related to drag reduction, but recent results suggest that the exact behavior is dependent on flow and polymer properties. Weissenberg number and the viscosity ratio (ratio of solvent viscosity to the zero-shear viscosity) are concentration dependent, thus the current study uses a polymer ocean (i.e. a homogenous concentration of polymer solution) with a developing TBL to eliminate uncertainty related to polymer properties. The near-wall modified TBL velocity profiles are acquired with particle image velocimetry. In the current presentation the mean velocity profiles and the corresponding flow (Reynolds number) and polymer (Weissenberg number, viscosity ratio, and length ratio) properties are reported. Note that the impact of polymer degradation on molecular weight will also be quantified and accounted for when estimating polymer properties This work was supported by NSF Grant 1604978.

Investigation of the required length for fully developed pipe flow with drag-reducing polymer solutions

Science.gov (United States)

Farsiani, Yasaman; Elbing, Brian

2015-11-01

Adding trace amounts of long chain polymers into a liquid flow is known to reduce skin friction drag by up to 80%. While polymer drag reduction (PDR) has been successfully implemented in internal flows, diffusion and degradation have limited its external flow applications. A weakness in many previous PDR studies is that there was no characterization of the polymer being injected into the turbulent boundary layer, which can be accomplished by testing a sample in a pressure-drop tube. An implicit assumption in polymer characterization is that the flow is fully developed at the differential pressure measurement. While available data in the literature shows that the entry length to achieve fully developed flow increases with polymeric solutions, it is unclear how long is required to achieve fully developed flow for non-Newtonian turbulent flows. In the present study, the pressure-drop is measured across a 1.05 meter length section of a 1.04 cm inner diameter pipe. Differential pressure is measured with a pressure transducer for different entry lengths, flow and polymer solution properties. This presentation will present preliminary data on the required entrance length as well as characterization of polymer solution an estimate of the mean molecular weight.

One-Dimensional Modelling of Polymer Flood Performance. Analytical and Graphical Solutions Modélisation de l'efficacité du déplacement unidimensionnel par injection de polymères. Solutions analytiques et graphiques

Directory of Open Access Journals (Sweden)

Grattoni C. A.

2006-11-01

Full Text Available A graphical method for simulating linear polymer flooding is proposed. The method is based upon the analytical solution of Darcy's law and continuity equation which describe the two-phase, one-dimensional, incompressible flow of oil and polymer solution through the reservoir rock. Continuous polymer injection and polymer slug injection are considered. Several physical mechanisms determining microscopic displacement efficiency are taken into account: resistance factor, residual resistance factor, retention composed by adsorption and mechanical entrapment, and inaccessible pore volume. Other properties are not considered: mixing and dispersion, shear and thermal degradation. This analytical-graphical model closely reproduces linear laboratory oil displacement experiments. Consequently, it can be used by the Field Engineer to rapidly estimate the additional oil recoverable by a linear polymer flood. On propose dans cet article une méthode graphique de simulation de l'injection de polymères dans le cas unidimensionnel. Cette méthode est basée sur la solution analytique de la loi de Darcy et de l'équation de continuité qui décrivent l'écoulement diphasique incompressible unidimen-sionnel d'huile et d'une solution de polymères à travers la roche réservoir. On examine l'injection continue et l'injection de bouchons de polymères. On prend en compte plusieurs mécanismes physiques qui déterminent l'efficacité du déplacement microscopique : facteur de ré-sistance, facteur de résistance résiduel, rétention due à l'adsorption et au piégeage mécanique et, enfin, volume des pores inacessibles. On ne tient pas compte des autres propriétés : mélange et dispersion, dégradation mécanique et thermique. Ce modèle analytique et graphique reproduit très directement les expériences de laboratoire de déplacement d'huile en milieu unidimensionnel. II peut donc être utilisé par l'ingénieur de chantier pour une estimation rapide de l

Synthesis, Characterization and Biological Studies of New Linear Thermally Stable Schiff Base Polymers with Flexible Spacers.

Science.gov (United States)

Qureshi, Farah; Khuhawar, Muhammad Yar; Jahangir, Taj Muhammad; Channar, Abdul Hamid

2016-01-01

Five new linear Schiff base polymers having azomethine structures, ether linkages and extended aliphatic chain lengths with flexible spacers were synthesized by polycondensation of dialdehyde (monomer) with aliphatic and aromatic diamines. The formation yields of monomer and polymers were obtained within 75-92%. The polymers with flexible spacers of n-hexane were somewhat soluble in acetone, chloroform, THF, DMF and DMSO on heating. The monomer and polymers were characterized by melting point, elemental microanalysis, FT-IR, (1)HNMR, UV-Vis spectroscopy, thermogravimetry (TG), differential thermal analysis (DTA), fluorescence emission, scanning electron microscopy (SEM) and viscosities and thermodynamic parameters measurements of their dilute solutions. The studies supported formation of the monomer and polymers and on the basis of these studies their structures have been assigned. The synthesized polymers were tested for their antibacterial and antifungal activities.

Dilute solution properties of canary seed (Phalaris canariensis) starch in comparison to wheat starch.

Science.gov (United States)

Irani, Mahdi; Razavi, Seyed M A; Abdel-Aal, El-Sayed M; Hucl, Pierre; Patterson, Carol Ann

2016-06-01

Dilute solution properties of an unknown starch are important to understand its performance and applications in food and non-food industries. In this paper, rheological and molecular properties (intrinsic viscosity, molecular weight, shape factor, voluminosity, conformation and coil overlap parameters) of the starches from two hairless canary seed varieties (CO5041 & CDC Maria) developed for food use were evaluated in the dilute regime (Starch dispersions in DMSO (0.5g/dl)) and compared with wheat starch (WS). The results showed that Higiro model is the best among five applied models for intrinsic viscosity determination of canary seed starch (CSS) and WS on the basis of coefficient of determination (R(2)) and root mean square error (RMSE). WS sample showed higher intrinsic viscosity value (1.670dl/g) in comparison to CSS samples (1.325-1.397dl/g). Berry number and the slope of master curve demonstrated that CSS and WS samples were in dilute domain without entanglement occurrence. The shape factor suggested spherical and ellipsoidal structure for CO5041 starch and ellipsoidal for CDC Maria starch and WS. The molecular weight, coil radius and coil volume of CSSs were smaller than WS. The behavior and molecular characterization of canary seed starch showed its unique properties compared with wheat starch. Copyright © 2016 Elsevier B.V. All rights reserved.

Study on radiation-induced deactivation and post-deactivation of some oxide-reductase in dilute aqueous solutions and protective effects: Pt. 2

International Nuclear Information System (INIS)

Ha Hongfei; Chen Yiqing

1993-01-01

The post-deactivation of irradiated catalase in dilute aqueous solution was found and investigated. Post-deactivation of irradiated catalase means that the catalase in dilute aqueous solution could not only be deactivated during γ-irradiation, but it has also been deactivated continuously for some time after the irradiated samples were taken out of the radiation field. No reports about this phenomenon in literature were searched up to now. The effects of absorbed dose, initial catalase concentration in solutions, atmosphere, temperature and additive on post-deactivation of catalase were investigated. H 2 O 2 produced by water radiolysis may attend the post-deactivation reaction in some way. Oxygen in enzyme samples in necessitous for the post-deactivation. 1 x 10 -4 to 5 x 10 -3 mol/L of CH 3 CH 2 OH, HCOONa and EDTA could control the post-deactivation efficiently

Synthesis of new water-soluble metal-binding polymers: Combinatorial chemistry approach. 1998 annual progress report

International Nuclear Information System (INIS)

Kurth, M.J.; Miller, R.B.; Sawan, S.; Smith, B.F.

1998-01-01

'(1) Develop rapid discovery and optimization approaches to new water-soluble chelating polymers for use in Polymer Filtration (PF) systems, and (2) evaluate the concept of using water and organic soluble polymers as new solid supports for combinatorial synthesis. Polymer Filtration (PF), which uses water-soluble metal-binding polymers to sequester metal ions in dilute solution with ultrafiltration (UF) to separate the polymers, is a new technology to selectively remove or recover hazardous and valuable metal ions. Future directions in PF must include rapid development, testing, and characterization of new metal-binding polymers. Thus, the authors are building upon and adapting the combinatorial chemistry approach developed for rapid molecule generation for the drug industry to the rapid development of new chelating polymers. The authors have focused on four areas including the development of: (1) synthetic procedures, (2) small ultrafiltration equipment compatible with organic- and aqueous-based combinatorial synthesis, (3) rapid assay techniques, and (4) polymer characterization techniques.'

The cathodic reduction of dioxygen on uranium oxide in dilute alkaline aqueous solution

International Nuclear Information System (INIS)

Hocking, W.H.; Betteridge, J.S.; Shoesmith, D.W.

1991-09-01

The cathodic reduction of dioxygen on uranium oxide in dilute alkaline aqueous solutions has been investigated within the context of a program to develop a comprehensive model to predict the behaviour of used CANDU (Canada Deuterium Uranium) nuclear fuel under disposal-vault conditions. Two different kinds of ceramic UO 2 were studied: reactor-grade CANDU fuel with normal p-type electrical conductivity and low-resistance material that exhibits n-type photoelectrochemical behaviour. The transport of electroactive species in solution was controlled by varying the rotation rate of rotating disc electrodes (RDE) and rotating ring-disc electrodes (RRDE). Steady-state polarization measurements were made using the current-interrupt method to compensate for the potential drop caused by ohmic resistance. Any release of peroxide to solution from the UO 2 (disc) surface could be monitored by oxidizing it at the Au ring of an RRDE. The existing theory for the cathodic 0 2 -reduction process as applied to RDE and RRDE experiments has been reviewed as a starting point for the interpretation of the results obtained in our work. (37 figs., 2 tabs., 170 refs.)

Polyketone polymer: a new support for direct enzyme immobilization.

Science.gov (United States)

Agostinelli, E; Belli, F; Tempera, G; Mura, A; Floris, G; Toniolo, L; Vavasori, A; Fabris, S; Momo, F; Stevanato, R

2007-01-20

Polyketone polymer -[-CO-CH(2)-CH(2)-](n)-, obtained by copolymerization of ethene and carbon monoxide, is utilized for immobilization of three different enzymes, one peroxidase from horseradish (HRP) and two amine oxidases, from bovine serum (BSAO) and lentil seedlings (LSAO). The easy immobilization procedure is carried out in diluted buffer, at pH 7.0 and 3 degrees C, gently mixing the proteins with the polymer. No bifunctional reagents and spacer arms are required for the immobilization, which occurs exclusively via a large number of hydrogen bonds between the carbonyl groups of the polymer and the -NH groups of the polypeptidic chain. Experiments demonstrate a high linking capacity of polymer for BSAO and an extraordinary strong linkage for LSAO. Moreover, activity measurements demonstrate that immobilized LSAO totally retains the catalytic characteristics of the free enzyme, where only a limited increase of K(M) value is observed. Finally, the HRP-activated polymer is successfully used as active packed bed of an enzymatic reactor for continuous flow conversion and flow injection analysis of hydrogen peroxide containing solutions.

Polymers for enhanced oil recovery : A paradigm for structure-property relationship in aqueous solution

NARCIS (Netherlands)

Wever, D. A. Z.; Picchioni, F.; Broekhuis, A. A.

Recent developments in the field of water-soluble polymers aimed at enhancing the aqueous solution viscosity are reviewed. Classic and novel associating water-soluble polymers for enhanced oil recovery (EOR) applications are discussed along with their limitations. Particular emphasis is placed on

1H NMR quantification in very dilute toxin solutions: application to anatoxin-a analysis.

Science.gov (United States)

Dagnino, Denise; Schripsema, Jan

2005-08-01

A complete procedure is described for the extraction, detection and quantification of anatoxin-a in biological samples. Anatoxin-a is extracted from biomass by a routine acid base extraction. The extract is analysed by GC-MS, without the need of derivatization, with a detection limit of 0.5 ng. A method was developed for the accurate quantification of anatoxin-a in the standard solution to be used for the calibration of the GC analysis. 1H NMR allowed the accurate quantification of microgram quantities of anatoxin-a. The accurate quantification of compounds in standard solutions is rarely discussed, but for compounds like anatoxin-a (toxins with prices in the range of a million dollar a gram), of which generally only milligram quantities or less are available, this factor in the quantitative analysis is certainly not trivial. The method that was developed can easily be adapted for the accurate quantification of other toxins in very dilute solutions.

Chemical metallization of KMPR photoresist polymer in aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Zeb, Gul [MiQro Innovation Collaborative Centre (C2MI), 45, boul. de l' Aéroport, Bromont, QC, J2L 1S8 (Canada); Mining & Materials Engineering, McGill University, 3610,University Street, Montreal, QC, H3A 0C5 (Canada); Duong, Xuan Truong [Department of Mechanical Engineering, Ecole polytechnique de Montréal, Montréal, QC, H3C 3T5 (Canada); Thai Nguyen University of Technology, 3-2 Street, Thai Nguyen City (Viet Nam); Vu, Ngoc Pi; Phan, Quang The; Nguyen, Duc Tuong; Ly, Viet Anh [Thai Nguyen University of Technology, 3-2 Street, Thai Nguyen City (Viet Nam); Salimy, Siamak [ePeer Review LLC, 145 Pine Haven Shores Rd, Suite 1000-X, Shelburne, VT 05482 (United States); Le, Xuan Tuan, E-mail: xuantuan.le@teledyne.com [MiQro Innovation Collaborative Centre (C2MI), 45, boul. de l' Aéroport, Bromont, QC, J2L 1S8 (Canada); Thai Nguyen University of Technology, 3-2 Street, Thai Nguyen City (Viet Nam)

2017-06-15

Highlights: • Electroless deposition of Ni-B film on KMPR photoresist polymer insulator with excellent adhesion has been achieved. • This metallization has been carried out in aqueous solutions at low temperature. • Polyamine palladium complexes grafts serve as seeds for the electroless plating on KMPR. • This electroless metallization process is simple, industrially feasible, chromium-free and environment-friendly. - Abstract: While conventional methods for preparing thin films of metals and metallic alloys on insulating substrates in the field of microelectromechanical systems (MEMS) include vapor deposition techniques, we demonstrate here that electroless deposition can be considered as an alternate efficient approach to metallize the surface of insulating substrates, such as KMPR epoxy photoresist polymer. In comparison with the physical and chemical vapor deposition methods, which are well-established for metallization of photoresist polymers, our electroless nickel plating requires only immersing the substrates into aqueous solutions in open air at low temperatures. Thin films of nickel alloy have been deposited electrolessly on KMPR surface, through a cost-effective and environmental chromium-free process, mediated through direct grafting of amine palladium complexes in aqueous medium. This covalent organic coating provides excellent adhesion between KMPR and the nickel film and allows better control of the palladium catalyst content. Covalent grafting and characterization of the deposited nickel film have been carried out by means of Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy techniques.

Cementation of the solid radioactive waste with polymer-cement solutions using the method of impregnation

International Nuclear Information System (INIS)

Gorbunova, O.

2015-01-01

Cementation of solid radioactive waste (SRW), i.e. inclusion of solid radioactive waste into cement matrix without cavities - is one of the main technological processes used for conditioning low and intermediate level radioactive waste. At FSUE 'Radon' the industrialized method of impregnation has been developed and since 2003 has been using for cementation of solid radioactive waste. The technology is that the polymer-cement solution, having high penetrating properties, is supplied under pressure through a tube to the bottom of the container in which solid radioactive waste has preliminarily been placed. The polymer-cement solution is evenly moving upwards through the channels between the particles of solid radioactive waste, fills the voids in the bulk volume of the waste and hardens, forming a cement compound, the amount of which is equal to the original volume. The aim of the investigation was a selection of a cement solution suitable for SRW impregnation (including fine particles) without solution depletion and bottom layers stuffing. It has been chosen a polymer: PHMG (polyhexamethylene-guanidine), which is a stabilizing and water-retaining component of the cement solution. The experiments confirm that the polymer increases the permeability of the cement solution by a 2-2.5 factor, the viscosity by a 1.2 factor, the stability of the consistency by a 1.5-1.7 factor, and extends the operating range of the W/C ratio to 0.5-1.1. So it is possible to penetrate a volume of SRW bigger by a 1.5-2.0 factor. It has been proved, that PHMG polymer increases strength and frost-resistance of the final compounds by a 1.8-2.7 factor, and contributes to fast strength development at the beginning of hardening and it decreases Cs-137 leashing rate by a 1.5-2 factor

Physical and chemical stability of reconstituted and diluted dexrazoxane infusion solutions.

Science.gov (United States)

Zhang, Yan-Ping; Myers, Alan L; Trinh, Van A; Kawedia, Jitesh D; Kramer, Mark A; Benjamin, Robert S; Tran, Hai T

2014-02-01

Dexrazoxane is used clinically to prevent anthracycline-associated cardiotoxicity. Hydrolysis of dexrazoxane prior to reaching the cardiac membranes severely hampers its mode of action; therefore, degradation during the preparation and administration of intravenous dexrazoxane admixtures demands special attention. Moreover, the ongoing national shortage of one dexrazoxane formulation in the United States has forced pharmacies to dispense other commercially available dexrazoxane products. However, the manufacturers' limited stability data restrict the flexibility of dexrazoxane usage in clinical practice. The aims of this study are to determine the physical and chemical stability of reconstituted and diluted solutions of two commercially available dexrazoxane formulations. The stability of two dexrazoxane products, brand and generic name, in reconstituted and intravenous solutions stored at room temperature without light protection in polyvinyl chloride bags was determined. The concentrations of dexrazoxane were measured at predetermined time points up to 24 h using a validated reversed phase high-performance liquid chromatography with ultraviolet detection assay. Brand (B-) and generic (G-) dexrazoxane products, reconstituted in either sterile water or 0.167 M sodium lactate (final concentration of 10 mg/mL), were found stable for at least to 8 h. Infusion solutions of B-dexrazoxane, prepared according to each manufacturer's directions, were stable for at least 24 h and 8 h at 1 mg/mL and 3 mg/mL, respectively. Infusion solutions of G-dexrazoxane, prepared in either 5% dextrose or 0.9% sodium chloride following the manufacturer's guidelines, were also stable for at least 24 h and 8 h at 1 mg/mL and 3 mg/mL, respectively. All tested solutions were found physically stable up to 24 h at room temperature. The stability of dexrazoxane infusion solutions reported herein permits advance preparation of dexrazoxane intravenous admixtures, facilitating

Hydrophobically Modified Sulfonated Polyacrylamides for IOR: Correlations between Associative Behavior and Injectivity in the Diluted Regime Polyacrylamides sulfonés modifiés hydrophobes pour la RAH (IOR : corrélations entre le caractère associatif et l’injectivité en régime dilué

Directory of Open Access Journals (Sweden)

Dupuis G.

2013-01-01

Full Text Available We report new experimental correlations between the injectivity through polycarbonate membranes and associative properties of random Hydrophobically Modified Water Soluble Polymers (HMWSP with sulfonated polyacrylamides (SPAM backbones and variable compositions in hydrophobic units. The investigations are focused on both their associative behavior in the diluted and semi-diluted regime and their injectivity under frontal filtration conditions in the diluted regime. Results from viscosimetric and dynamic light scattering measurements indicate the existence of thresholds in terms of amount (≥ 0.5 mol% and mass (≥ C12 of alkyl hydrophobic units above which interchain interactions arise. These interactions are evidenced by the presence of multichain aggregates in diluted solutions and by enhanced thickening abilities in semi- diluted solutions. The filtration study was performed with capillary pore membranes (track-etched in the Darcy regime under constant -flow rate and high Jamming Ratio conditions. Results show that: injection of diluted solutions of HMWSP without interchaininteractions (i.e. with composition in hydrophobic units belowthe above mentioned thresholds does not lead to significantmobility and permeability reductions as compared to theinjection of a reference Water Soluble Polymer (WSP; injection of diluted solutions of HMWSP with interchain interactions leads to significant mobility and permeability reductions; HMWSP-induced mobility and permeability reductions are essentially due to irreversible polymer adsorption on the pore walls and not to the formation of filter-cakes; HMWSP adsorbed layers thicknesses are limited by the effective stress applied by the solution’s flow in the pores. Nous présentons de nouvelles corrélations expérimentales entre l’injectivité dans des membranes de polycarbonate et le caractère associatif de Polymères Hydrosolubles Modifiés Hydrophobes (PHMH ayant des squelettes de polyacrylamide

Static and dynamic light scattering studies on dilute polyrotaxane solutions

International Nuclear Information System (INIS)

Kume, Tetsuya; Sakai, Yasuhiro; Mayumi, Koichi; Kidowaki, Masatoshi; Yokoyama, Hideaki; Ito, Kohzo; Araki, Jun

2009-01-01

Static and dynamic light scattering measurements were performed for dilute polyrotaxane solutions in different types of solvent systems, i.e. dimethylacetamide (DMAc) or dimethylformamide (DMF) containing 1-6 wt% lithium chloride (LiCl), 1 M aqueous sodium hydroxide (NaOH) and dimethylsulfoxide (DMSO). No aggregation of the polyrotaxane in DMF/LiCl was confirmed in the present study. Radius of gyration of the dissolved polyrotaxane was largest in NaOHaq., followed by values in amide solvents/LiCl and that in DMSO, and was probably dominated not by Coulombic repulsion but by the mutual affinity between solvent and polyrotaxane. Ratio of radius of gyration to hydrodynamic radius suggested the flexible random-coiled conformation in DMSO and relatively more extended, semi-flexible ones in amide solvents/LiCl and NaOHaq. The obtained values of second virial coefficient and weight average molecular weight seemed to be affected by a potential change in differential refractive index increments, caused by selective macrocationization or ionization.

Static and dynamic light scattering studies on dilute polyrotaxane solutions

Science.gov (United States)

Kume, Tetsuya; Araki, Jun; Sakai, Yasuhiro; Mayumi, Koichi; Kidowaki, Masatoshi; Yokoyama, Hideaki; Ito, Kohzo

2009-08-01

Static and dynamic light scattering measurements were performed for dilute polyrotaxane solutions in different types of solvent systems, i.e. dimethylacetamide (DMAc) or dimethylformamide (DMF) containing 1-6 wt% lithium chloride (LiCl), 1 M aqueous sodium hydroxide (NaOH) and dimethylsulfoxide (DMSO). No aggregation of the polyrotaxane in DMF/LiCl was confirmed in the present study. Radius of gyration of the dissolved polyrotaxane was largest in NaOHaq., followed by values in amide solvents/LiCl and that in DMSO, and was probably dominated not by Coulombic repulsion but by the mutual affinity between solvent and polyrotaxane. Ratio of radius of gyration to hydrodynamic radius suggested the flexible random-coiled conformation in DMSO and relatively more extended, semi-flexible ones in amide solvents/LiCl and NaOHaq. The obtained values of second virial coefficient and weight average molecular weight seemed to be affected by a potential change in differential refractive index increments, caused by selective macrocationization or ionization.

Fully solution-processing route toward highly transparent polymer solar cells.

Science.gov (United States)

Guo, Fei; Kubis, Peter; Stubhan, Tobias; Li, Ning; Baran, Derya; Przybilla, Thomas; Spiecker, Erdmann; Forberich, Karen; Brabec, Christoph J

2014-10-22

We report highly transparent polymer solar cells using metallic silver nanowires (AgNWs) as both the electron- and hole-collecting electrodes. The entire stack of the devices is processed from solution using a doctor blading technique. A thin layer of zinc oxide nanoparticles is introduced between photoactive layer and top AgNW electrode which plays decisive roles in device functionality: it serves as a mechanical foundation which allows the solution-deposition of top AgNWs, and more importantly it facilitates charge carriers extraction due to the better energy level alignment and the formation of ohmic contacts between the active layer/ZnO and ZnO/AgNWs. The resulting semitransparent polymer:fullerene solar cells showed a power conversion efficiency of 2.9%, which is 72% of the efficiency of an opaque reference device. Moreover, an average transmittance of 41% in the wavelength range of 400-800 nm is achieved, which is of particular interest for applications in transparent architectures.

Mechanisms behind injecting the combination of nano-clay particles and polymer solution for enhanced oil recovery

Science.gov (United States)

Khalili Nezhad, Seyyed Shahram; Cheraghian, Goshtasp

2016-08-01

Laboratory investigations and field applications have proved injection of polymer solution to be an effective means to improve oil recovery for reservoirs of medium oil viscosity. The incremental oil produced in this case is the result of an increase in areal and vertical sweep efficiencies. Biopolymers and synthetic polymers are the major categories used in the petroleum industry for specific reasons. Biopolymers like xanthan are limited in their application as they are more susceptible to biodegradation. Synthetic polymers like Hydrolyzed PolyAcrylaMide (HPAM) have a much wider application as they are less susceptible to biodegradation. Furthermore, development of nanotechnology has successfully provided technical and economical viable alternatives for present materials. The objective of this study is to investigate the effect of combining clay nanoparticles with polymer solution on oil recovery. This paper includes a history match of both one-dimensional and two-dimensional polymer floods using a three-dimensional numerical model for fluid flow and mass transport. Results indicated that the amount of polymer adsorption decreased when clay nanoparticles were added to the PolyAcrylaMide solution; however, mobility ratio improvement is believed to be the main contributor for the proposed method in order to enhance much oil recovery compared to xanthan flood and HPAM flood.

Application of β-cyclodextrin polymers in separation of metal ions

International Nuclear Information System (INIS)

Kozlowski, C.A.; Kozlowska, J.

2006-01-01

In the present work the competitive transport of Cu(II), Co(II), Ni(II) and Zn(II) ions through the plasticized immobilized membranes was studied. β-cyclodextrin (β-CD) polymers have been used as macrocyclic ligands for separation of metal ions from dilute aqueous solutions by ion exchange methods, i.e. transport across polymer inclusion membranes and ion flotation process. β-CD polymers were prepared by cross-linking β-CD with alkenyl (nonenyl) succinic anhydride derivatives, phtalic and 3-nitrophtalic anhydride in anhydrous N,N-dimethylformamide (DMF) resulting in formation of Polymer A, B or C, respectively. In he case of cooper(II) flotation results obtained with the use of nonylphenol polyoxyethyl glycol ether as an non-anionic surfactant and β-CD polymers as complexation agent, show that the removal of metal decreases with higher molecular mass of β-CD polymers linked by phtalic or 3-nitrophtalic anhydrides. For both derivatives with pH increase the copper(II) removed increase. The highest flotation removal, i.e. 93% is observed for β-CD polymers synthesized at 100 o C with molar ratio CD : NaH : 3-nitrophtalic anhydride equal to 1 : 7 : 7

A conductance study of guanidinium chloride, thiocyanate, sulfate, and carbonate in dilute aqueous solutions: ion-association and carbonate hydrolysis effects.

Science.gov (United States)

Hunger, Johannes; Neueder, Roland; Buchner, Richard; Apelblat, Alexander

2013-01-17

We study the conductance of dilute aqueous solutions for a series of guandinium salts at 298.15 K. The experimental molar conductivities were analyzed within the framework of the Quint-Viallard theory in combination with Debye-Hückel activity coefficients. From this analysis, we find no evidence for significant ion association in aqueous solutions of guanidinium chloride (GdmCl) and guanidinium thiocyanate (GdmSCN), and the molar conductivity of these electrolytes can be modeled assuming a complete dissociation. The limiting ionic conductivity of the guanidinium ion (Gdm(+)) is accurately determined to λ(Gdm(+)) = 51.45 ± 0.10 S cm(2) mol(-1). For the bivalent salts guanidinium sulfate (Gdm(2)SO(4)) and guanidinium carbonate (Gdm(2)CO(3)), the molar conductivities show small deviations from ideal (fully dissociated electrolyte) behavior, which are related to weak ion association in solution. Furthermore, for solutions of Gdm(2)CO(3), the hydrolysis of the carbonate anion leads to distinctively increased molar conductivities at high dilutions. The observed ion association is rather weak for all studied electrolytes and cannot explain the different protein denaturing activities of the studied guanidinium salts, as has been proposed previously.

Understanding diffusion of intrinsically disordered proteins in polymer solutions: A disorder plus collapse model

Directory of Open Access Journals (Sweden)

Juan Wang

2017-11-01

Full Text Available Understanding diffusion of intrinsically disordered proteins (IDPs under crowded environments is of ubiquitous importance to modelling related dynamics in biological systems. In the present work, we proposed a theoretical framework to study the diffusion behavior of IDPs in polymer solutions. IDP is modeled as an ensemble of particles with a wide range of gyration radius subject to Flory-Fisk distribution, where the collapse effect which leads to the shrink of IDP due to polymer crowding is included. The diffusion coefficient of IDP is calculated as the average, denoted by 〈D〉, over the values of the particle samples. By properly incorporating the scaling relations for diffusion coefficient of nanoparticle (NP in polymer solutions, we are able to evaluate 〈D〉 straightforwardly and reveal the disorder and collapse effects on IDP’s diffusion in an explicit manner. Particular attentions are paid on comparison between the diffusion coefficient of an IDP and that of a NP. Results demonstrate that both disorder and collapse can enhance IDP diffusion rate. Our analysis shows that the crossover behavior reported by experiments can be actually a general phenomenon, namely, while a NP with smaller size than that of an IDP diffuses faster in simple solutions, the IDP may become the faster one under crowded conditions. We apply our theory to analyze the diffusion of several types of IDP in a few different polymer solutions. Good agreements between the theoretical results and the experimental data are obtained.

Comparison of nanoparticle diffusion using fluorescence correlation spectroscopy and differential dynamic microscopy within concentrated polymer solutions

Science.gov (United States)

Shokeen, Namita; Issa, Christopher; Mukhopadhyay, Ashis

2017-12-01

We studied the diffusion of nanoparticles (NPs) within aqueous entangled solutions of polyethylene oxide (PEO) by using two different optical techniques. Fluorescence correlation spectroscopy, a method widely used to investigate nanoparticle dynamics in polymer solution, was used to measure the long-time diffusion coefficient (D) of 25 nm radius particles within high molecular weight, Mw = 600 kg/mol PEO in water solutions. Differential dynamic microscopy (DDM) was used to determine the wave-vector dependent dynamics of NPs within the same polymer solutions. Our results showed good agreement between the two methods, including demonstration of normal diffusion and almost identical diffusion coefficients obtained by both techniques. The research extends the scope of DDM to study the dynamics and rheological properties of soft matter at a nanoscale. The measured diffusion coefficients followed a scaling theory, which can be explained by the coupling between polymer dynamics and NP motion.

Pattern Formation During Phase Separation of Polymer-Ionic Liquid Co-Solutions

Science.gov (United States)

Meng, Zhiyong; Osuji, Chinedum

2010-03-01

Co-solutions of polystyrene (PS) with a 1-butyl-3-methylimidazolium based ionic liquid (IL) in DMF phase separated into IL-rich and PS-rich domains on solvent evaporation. Over a limited range of polymer molecular weights and substrate temperatures, a variety of striped and cellular or polygonal structures were found on the resulting film surface, as visualized using bright-field and phase-contrast optical microscopy. This effect appears to be due to a Benard-Marangoni instability at the free surface of the liquid film as it undergoes evaporation, setting up convection rolls inside the fluid which become locked in place as the system vitrifies on solvent removal. Differential scanning calorimetry shows that the IL does not significantly plasticize the polymer, suggesting that the viscosity of the polystyrene solution itself controls the formation of this instability.

Influence of complexing on physicochemical properties of polymer-salt solutions. Vliyanie kompleksoobrazovaniya na fiziko-khimicheskie svojstva polimerno-solevykh rastvorov

Energy Technology Data Exchange (ETDEWEB)

Ostroushko, A A; Yushkova, S M; Koridze, N V; Skobkoreva, N V; Zhuravleva, L I; Palitskaya, T A; Antropova, S V; Ostroushko, I P [Ural' skij Gosudarstvennyj Univ., Sverdlovsk (Russian Federation) AN SSSR, Moscow (Russian Federation). Inst. Obshchej i Neorganicheskoj Khimii

1993-06-01

Using the methods of spectrophotometry, viscosimetry, conductometry the influence of salt-polymer complexing processes on physicochemical prperties of aqueous solutions of yttrium, barium, copper nitrates and formates with polyvinyl alcohol was studied. Change of dynamic viscosity, specific electric conductivity of solutions in the process of complexing was shown. Thermal effects of salt-polymer interaction were measured. It is shown that decrease of transition temperature of polymer to plastic state in films, temperature and effective activation energy of salt decomposition is also connected with complexing. Effective values of surface tension on the boundary with air are measured. Coefficients of cation diffusion in polymer-salt solutions are estimated.

Effect of gamma irradiation on viscosity of aqueous solutions of some natural polymers

International Nuclear Information System (INIS)

Nguyen Tan Man; Truong Thi Hanh; Le Quang Luan; Le Hai; Nguyen Quoc Hien

2000-01-01

Effect of gamma irradiation on viscosity of aqueous solution of alginate and carbon xylmethyl cellulose (CMC) irradiated in solid state has been carried out. the viscosity of aqueous solution of alginate and CMC decreased remarkably with increasing dose and the viscosity of 2% solution of above polymers irradiated at 50 kGy was about 100 times lower than the original one. (author)

Chain propagator, mass, and universality in polymer solutions from Brownian relativity

International Nuclear Information System (INIS)

Mezzasalma, Stefano A.

2005-01-01

A Lagrangian theory for single chains in polymer solutions is addressed via a recent Brownian relativity. By employing generalized diffusive coordinates, statements of covariance and diffusivity invariance result into free particle Lagrangians, where mass turns out to rise as a universal spacetime property. It descends from lowering diffusivity (or curving spacetime), so identifying a mechanism which conceptually resemble those ruling macromolecular scaling laws. An extended chain propagator recovers the Gaussian end-to-end distribution and, in the limits of time-like and space-like orbits, the dualism for diffusive paths and polymer random-walks

Ultrasound degradation of xanthan polymer in aqueous solution: Its scission mechanism and the effect of NaCl incorporation.

Science.gov (United States)

Saleh, H M; Annuar, M S M; Simarani, K

2017-11-01

Degradation of xanthan polymer in aqueous solution by ultrasonic irradiation was investigated. The effects of selected variables i.e. sonication intensity, irradiation time, concentration of xanthan gum and molar concentration of NaCl in solution were studied. Combined approach of full factorial design and conventional one-factor-at-a-time was applied to obtain optimum degradation at sonication power intensity of 11.5Wcm -2 , irradiation time 120min and 0.1gL -1 xanthan in a salt-free solution. Molecular weight reduction of xanthan gum under sonication was described by an exponential decay function with higher rate constant for polymer degradation in the salt free solution. The limiting molecular weight where fragments no longer undergo scission was determined from the function. The incorporation of NaCl in xanthan solution resulted in a lower limiting molecular weight. The ultrasound-mediated degradation of aqueous xanthan polymer chain agreed with a random scission model. Side chain of xanthan polymer is proposed to be the primary site of scission action. Copyright © 2017 Elsevier B.V. All rights reserved.

Entanglements in Marginal Solutions: A Means of Tuning Pre-Aggregation of Conjugated Polymers with Positive Implications for Charge Transport

KAUST Repository

Hu, Hanlin

2015-06-17

The solution-processing of conjugated polymers, just like commodity polymers, is subject to solvent and molecular weight-dependent solubility, interactions and chain entanglements within the polymer, all of which can influence the crystallization and microstructure development in semi-crystalline polymers and consequently affect charge transport and optoelectronic properties. Disentanglement of polymer chains in marginal solvents was reported to work via ultrasonication, facilitating the formation of photophysically ordered polymer aggregates. In this contribution, we explore how a wide range of technologically relevant solvents and formulations commonly used in organic electronics influence chain entanglement and the aggregation behaviour of P3HT using a combination of rheological and spectrophotometric measurements. The specific viscosity of the solution offers an excellent indication of the degree of entanglements in the solution, which is found to be related to the solubility of P3HT in a given solvent. Moreover, deliberately disentangling the solution in the presence of solvophobic driving forces, leads consistently to formation of photophysically visible aggregates which is indicative of local and perhaps long range order in the solute. We show for a broad range of solvents and molecular weights that disentanglement ultimately leads to significant ordering of the polymer in the solid state and a commensurate increase in charge transport properties. In doing so we demonstrate a remarkable ability to tune the microstructure which has important implications for transport properties. We discuss its potential implications in the context of organic photovoltaics.

Entanglements in Marginal Solutions: A Means of Tuning Pre-Aggregation of Conjugated Polymers with Positive Implications for Charge Transport

KAUST Repository

Hu, Hanlin; Zhao, Kui; Fernandes, Nikhil J.; Boufflet, Pierre; Bannock, James Henry; Yu, Liyang; de Mello, John C; Stingelin, Natalie; Heeney, Martin; Giannelis, Emmanuel P.; Amassian, Aram

2015-01-01

The solution-processing of conjugated polymers, just like commodity polymers, is subject to solvent and molecular weight-dependent solubility, interactions and chain entanglements within the polymer, all of which can influence the crystallization and microstructure development in semi-crystalline polymers and consequently affect charge transport and optoelectronic properties. Disentanglement of polymer chains in marginal solvents was reported to work via ultrasonication, facilitating the formation of photophysically ordered polymer aggregates. In this contribution, we explore how a wide range of technologically relevant solvents and formulations commonly used in organic electronics influence chain entanglement and the aggregation behaviour of P3HT using a combination of rheological and spectrophotometric measurements. The specific viscosity of the solution offers an excellent indication of the degree of entanglements in the solution, which is found to be related to the solubility of P3HT in a given solvent. Moreover, deliberately disentangling the solution in the presence of solvophobic driving forces, leads consistently to formation of photophysically visible aggregates which is indicative of local and perhaps long range order in the solute. We show for a broad range of solvents and molecular weights that disentanglement ultimately leads to significant ordering of the polymer in the solid state and a commensurate increase in charge transport properties. In doing so we demonstrate a remarkable ability to tune the microstructure which has important implications for transport properties. We discuss its potential implications in the context of organic photovoltaics.

A thermodynamic model for solid solutions and its application to the C-Fe-Co, C-Fe-Ni and Mn-Cr-Pt solid dilutions

International Nuclear Information System (INIS)

Tao, D.P.

2004-01-01

Based on the free volume theory and the lattice model, the partition functions of pure solids and their mixtures were expressed. This resulted in the establishment of a thermodynamic model for solid solutions. The model naturally combines the excess entropy and excess enthalpy of a solution by means of new expressions of the configurational partition functions of solids and their mixtures derived from statistical thermodynamics, which is approximate to real solid solutions, that is S E ≠0 (V E ≠0) and H E ≠0. It can describe the thermodynamic properties of partially miscible systems and predict the thermodynamic properties in a multicomponent solid solution system using only the related binary infinite dilute activity coefficients. The predicted activity coefficients from the model are in good agreement with the experimental data of the ternary solid dilutions. This shows that the prediction effect of the proposed model is of better stability and reliability because it has a good physical basis

Mechanism of pitting corrosion prevention by nitrite in carbon steel exposed to dilute salt solutions. 1998 annual progress report

International Nuclear Information System (INIS)

Zapp, P.E.; Zee, J. van.

1998-01-01

'The overall goal of this project is to develop a fundamental understanding of the role of nitrite in preventing the breakdown of protective oxide(s) on carbon steel and the onset of pitting. Pitting corrosion of carbon steel exposed to dilute alkaline salt solutions can be induced by nitrate, sulfate, and chloride ions and is prevented by sufficient concentration of nitrite. A significant example of this material/electrolyte system is the storage and processing of DOE''s high-level radioactive liquid waste in carbon steel tanks. Added nitrite in the waste has a considerable downstream impact on the immobilization of the waste in a stable glass form. Waste tank integrity and glass production efficiency may benefit from the fundamental understanding of nitrite''s role in preventing pitting. This report summarizes progress after approximately six months of effort in this three-year EMSP project. Initial experimental and theoretical work has focused on the electrochemical behavior of carbon steel in simplified non-radioactive solutions that simulate complex dilute radioactive waste solutions. These solutions contain corrosion-inducing species such as nitrate and chloride and the corrosion-inhibiting nitrite at moderately alkaline pHs. The electrochemical behavior of interest here is that of the open-circuit potential of the steel specimen at equilibrium in the experimental electrolyte and the measures of the steel''s passivity and passivity breakdown.'

Statistical Investigation on Coherent Vortex Structure in Turbulent Drag Reducing Channel Flow with Blown Polymer Solution

International Nuclear Information System (INIS)

Ishitsuka, Shota; Motozawa, Masaaki; Kawaguchi, Yasuo; Iwamoto, Kaoru; Ando, Hirotomo; Senda, Tetsuya

2011-01-01

Coherent vortex structure in turbulent drag-reducing channel flow with blown polymer solution from the wall was investigated. As a statistical analysis, we carried out Galilean decomposition, swirling strength and linear stochastic estimation of the PIV data obtained by the PIV measurement in x – y plane. Reynolds number based on bulk velocity and channel height was set to 40000. As a result, the angle of shear layer that cleared up by using Galilean decomposition becomes small in the drag-reducing flow. Q3 events were observed near the shear layer. In addition, as a result of linear stochastic estimation (LSE) based on swirling strength, we confirmed that the velocity under the vortex core is strong in the water flow. This result shows Q2 (ejection) are dominant in the water flow. However, in the drag-reducing flow with blown polymer solution, the velocity above the vortex core become strong, that is, Q4 (sweep) events are relatively strong around the vortex core. This is the result of Q4 events to come from the channel center region because the polymer solution does not exist in this region. The typical structure like this was observed in the drag -reducing flow with blown polymer solution from the wall.

Volumetric properties of ascorbic acid (vitamin C) and thiamine hydrochloride (vitamin B1) in dilute HCl and in aqueous NaCl solutions at (283.15, 293.15, 298.15, 303.15, 308.15, and 313.15) K

International Nuclear Information System (INIS)

Ayranci, Guler; Sahin, Melike; Ayranci, Erol

2007-01-01

Apparent molar volumes and apparent molar isentropic compressibilities of ascorbic acid (vitamin C) and thiamine hydrochloride (vitamin B 1 ) were determined from accurately measured density and sound velocity data in water and in aqueous NaCl solutions at (283.15, 293.15, 298.15, 303.15, 308.15, and 313.15) K. These volume and compressibility data were extrapolated to zero concentration using suitable empirical or theoretical equations to determine the corresponding infinite dilution values. Apparent molar expansibilities at infinite dilution were determined from slopes of apparent molar volume vs. temperature plots. Ionization of both ascorbic acid and thiamine hydrochloride were suppressed using sufficiently acidic solutions. Apparent molar volumes at infinite dilution for ascorbic acid and thiamine hydrochloride were found to increase with temperature in acidic solutions and in the presence of co-solute, NaCl. Apparent molar expansibility at infinite dilution were found to be constant over the temperature range studied and were all positive, indicating the hydrophilic character of the two vitamins studied in water and in the presence of co-solute, NaCl. Apparent molar isentropic compressibilities of ascorbic acid at infinite dilution were positive in water and in the presence of co-solute, NaCl, at low molalities. Those of thiamine hydrochloride at infinitive dilution were all negative, consistent with its ionic nature. Transfer apparent molar volumes of vitamins at infinite dilution from water solutions to NaCl solutions at various temperatures were determined. The results were interpreted in terms of complex vitamin-water-co-solute (NaCl) interactions

Ion Transport in Confined Geometries below the Nanoscale: Access Resistance Dominates Protein Channel Conductance in Diluted Solutions.

Science.gov (United States)

Alcaraz, Antonio; López, M Lidón; Queralt-Martín, María; Aguilella, Vicente M

2017-10-24

Synthetic nanopores and mesoscopic protein channels have common traits like the importance of electrostatic interactions between the permeating ions and the nanochannel. Ion transport at the nanoscale occurs under confinement conditions so that the usual assumptions made in microfluidics are challenged, among others, by interfacial effects such as access resistance (AR). Here, we show that a sound interpretation of electrophysiological measurements in terms of channel ion selective properties requires the consideration of interfacial effects, up to the point that they dominate protein channel conductance in diluted solutions. We measure AR in a large ion channel, the bacterial porin OmpF, by means of single-channel conductance measurements in electrolyte solutions containing varying concentrations of high molecular weight PEG, sterically excluded from the pore. Comparison of experiments performed in charged and neutral planar membranes shows that lipid surface charges modify the ion distribution and determine the value of AR, indicating that lipid molecules are more than passive scaffolds even in the case of large transmembrane proteins. We also found that AR may reach up to 80% of the total channel conductance in diluted solutions, where electrophysiological recordings register essentially the AR of the system and depend marginally on the pore characteristics. These findings may have implications for several low aspect ratio biological channels that perform their physiological function in a low ionic strength and macromolecule crowded environment, just the two conditions enhancing the AR contribution.

Ionic liquids behave as dilute electrolyte solutions

Science.gov (United States)

Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

2013-01-01

We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

Micellar copolymerization of poly(acrylamide-g-propylene oxide): rheological evaluation and solution characterization; Copolimerizacao micelar de poli(acrilamida-g-oxido de propileno): avaliacao reologica e caracterizacao de suas solucoes

Energy Technology Data Exchange (ETDEWEB)

Sadicoff, Bianca L.; Brandao, Edimir M.; Lucas, Elizabete F. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas]. E-mail: elucas@ima.ufrj.br; Amorim, Marcia C.V. [Universidade Estadual, Rio de Janeiro, RJ (Brazil). Inst. de Quimica

2001-06-01

Graft copolymers of polyacrylamide and poly(propylene oxide) were synthesized by a micellar copolymerization technique. The rheological properties of the copolymers solutions were evaluated and compared with literature data for solutions of the same copolymers, synthesized by solution polymerization. The effect of hydrophobe content, salt addition and surfactant addition on the rheological properties were also investigated. Increasing hydrophobe content resulted in higher solution viscosities in the semi-dilute regime. Upon addition of salts, the hydrophobic groups associated to minimize their exposure to water. In the semi-dilute region, higher contents of surfactant added resulted in lower reduced viscosities of the polymer solutions. The copolymers were qualitatively characterized by infra-red spectrometry. (author)

Perovskite/polymer solar cells prepared using solution process

International Nuclear Information System (INIS)

Rosa, E. S.; Shobih; Nursam, N. M.; Saputri, D. G.

2016-01-01

We report a simple solution-based process to fabricate a perovskite/polymer tandem solar cell using inorganic CH 3 NH 3 PM 3 as an absorber and organic PCBM (6,6 phenyl C61- butyric acid methyl ester) as an electron transport layer. The absorber solution was prepared by mixing the CH 3 NH 3 I (methyl ammonium iodide) with PbI 2 (lead iodide) in DMF (N,N- dimethyl formamide) solvent. The absorber and electron transport layer were deposited by spin coating method. The electrical characteristics generated from the cell under 50 mW/cm 2 at 25 °C comprised of an open circuit voltage of 0. 3 1 V, a short circuit current density of 2.53 mA/cm 2 , and a power conversion efficiency of 0.42%. (paper)

Activity coefficients at infinite dilution of organic solutes in N-alkylpyridinium bis(trifluoromethylsulfonyl)imide ([CnPY][NTf2], n = 2, 4, 5) using gas-liquid chromatography

International Nuclear Information System (INIS)

Yan Peifang; Liu Qingshan; Yang Miao; Liu Xiumei; Tan Zhicheng; Welz-Biermann, Urs

2010-01-01

The activity coefficients at infinite dilution, γ i ∞ for both polar and non-polar solutes in the ionic liquids N-alkylpyridinium bis(trifluoromethylsulfonyl)imide ([C n PY][NTf 2 ], n = 2, 4, 5) have been determined by gas-liquid chromatography using the ionic liquid as the stationary phase. The measurements were carried out at the temperatures from (303 to 353) K. The partial molar excess enthalpies at infinite dilution H i E,∞ of the solutes in the ionic liquids were also derived from the temperature dependence of the γ i ∞ values. The values of the selectivity for the hexane/benzene and cyclohexane/benzene separation problems were calculated from experimental infinite dilution activity coefficient values and compared to the other ionic liquids, taken from the recent literatures.

Electro-Optical Parameters Of Hairy Rod Polymer/Dimethylformamide System

International Nuclear Information System (INIS)

Spasevska, Hristina

2003-01-01

Rigid rod polymers are materials with special features, that is the reason why they have large scientific and technological applications like isotropic-nematic and other types of transition. One of the biggest problems that happen while investigation to these polymers, at molecular level, is their poor solubility in most of the common solvents. Solubility gets better if while synthesize junctions flexible side chains, [1]. Remaining polymers belong on one new class - hairy rod polymers and have big potential for their technological applications. Because of their nonlinear optical properties and opportunity for self-organization in super molecular structures (films and fibers), can be used in electronics and telecommunications industry either at display-technologies [2]. That is the main reason why controlling the remaining polymer features and connection of their microscopic and macroscopic characteristics, like an complete characterization (in solutions and solid state) is from essential scientific interest, actually it is an imperative. The polymer POD-2/that is subject of investigation, bellows to hairy rod polymers and it is synthesized for the first time [3] by giving a support to their characterization. Measures on diluted solutions from the system POD-2/dimethylformamide are made by the method electric birefringence, at three temperatures (25, 40 and 55 o C). For different concentrations on system, from obtained electro-optical signals (EOS), dependence on electric birefringence (Δn) against applied electric field (E 2 ), is determined. By investigation of electro-optical effects, especially studding the way of their maintenance and losing, while applying electric square impulses, relaxation time τ o of polymer molecules is calculated. From these parameters, as presented data for EOS rise and decay too, deformational electro-optical effect has been determined. (Author)

Polymer electronics

CERN Document Server

Hsin-Fei, Meng

2013-01-01

Polymer semiconductor is the only semiconductor that can be processed in solution. Electronics made by these flexible materials have many advantages such as large-area solution process, low cost, and high performance. Researchers and companies are increasingly dedicating time and money in polymer electronics. This book focuses on the fundamental materials and device physics of polymer electronics. It describes polymer light-emitting diodes, polymer field-effect transistors, organic vertical transistors, polymer solar cells, and many applications based on polymer electronics. The book also disc

Dilute acid/metal salt hydrolysis of lignocellulosics

Science.gov (United States)

Nguyen, Quang A.; Tucker, Melvin P.

2002-01-01

A modified dilute acid method of hydrolyzing the cellulose and hemicellulose in lignocellulosic material under conditions to obtain higher overall fermentable sugar yields than is obtainable using dilute acid alone, comprising: impregnating a lignocellulosic feedstock with a mixture of an amount of aqueous solution of a dilute acid catalyst and a metal salt catalyst sufficient to provide higher overall fermentable sugar yields than is obtainable when hydrolyzing with dilute acid alone; loading the impregnated lignocellulosic feedstock into a reactor and heating for a sufficient period of time to hydrolyze substantially all of the hemicellulose and greater than 45% of the cellulose to water soluble sugars; and recovering the water soluble sugars.

Isotope dilution alpha spectrometry for the determination of plutonium concentration in irradiated fuel dissolver solution : IDAS and R-IDAS

International Nuclear Information System (INIS)

Ramaniah, M.V.; Jain, H.C.; Aggarwal, S.K.; Chitambar, S.A.; Kavimandan, V.D.; Almaula, A.I.; Shah, P.M.; Parab, A.R.; Sant, V.L.

1980-01-01

The report presents a new technique, Isotope Dilution Alpha Spectrometry (IDAS) and Reverse Isotope Dilution Alpha Spectrometry (R-IDAS) for determining the concentration of plutonium in the irradiated fuel dissolver solution. The method exploits sup(238)Pu in IDAS and sup(239)Pu in R-IDAS as a spike and provides an alternative method to Isotope Dilution Mass Spectrometry (IDMS) which requires enriched sup(242)Pu as a spike. Depending upon the burn-up of the fuel, sup(238)Pu or sup(239)Pu is used as a spike to change the sup(238)Pu/(sup(239)Pu+sup(240)Pu)α activity ratio in the sample by a factor of 10. This change is determined by α-spectrometry on electrodeposited sources using a solid state silicon surface barrier detector coupled to a multichannel analyser. The validity of a simple method based on the geometric progression (G.P.) decrease for the far tail of the spectrum to correct for the tail contribution of sup(238)Pu peak (5.50 MeV) to the low energy sup(239)Pu + sup(240)Pu peak (5.17 MeV) is established. Results for the plutonium concentration on different irradiated fuel dissolver solutions with burn-uo ranging from J,000 to 100,000 MWD/TU are presented and compared with those obtained by IDMS. The values obtained by IDAS or R-IDAS and IDMS agree within 0.5%. (auth.)

Unraveling the Solution-State Supramolecular Structures of Donor-Acceptor Polymers and their Influence on Solid-State Morphology and Charge-Transport Properties.

Science.gov (United States)

Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Dou, Jin-Hu; Yang, Chi-Yuan; Zou, Lin; Meng, Xiangyi; Ma, Wei; Wang, Jie-Yu; Pei, Jian

2017-11-01

Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequentially solution-processed, nanostructured polymer photovoltaics using selective solvents

KAUST Repository

Kim, Do Hwan; Mei, Jianguo; Ayzner, Alexander L.; Schmidt, Kristin; Giri, Gaurav; Appleton, Anthony L.; Toney, Michael F.; Bao, Zhenan

2014-01-01

We demonstrate high-performance sequentially solution-processed organic photovoltaics (OPVs) with a power conversion efficiency (PCE) of 5% for blend films using a donor polymer based on the isoindigo-bithiophene repeat unit (PII2T-C10C8) and a fullerene derivative [6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM). This has been accomplished by systematically controlling the swelling and intermixing processes of the layer with various processing solvents during deposition of the fullerene. We find that among the solvents used for fullerene deposition that primarily swell but do not re-dissolve the polymer underlayer, there were significant microstructural differences between chloro and o-dichlorobenzene solvents (CB and ODCB, respectively). Specifically, we show that the polymer crystallite orientation distribution in films where ODCB was used to cast the fullerene is broad. This indicates that out-of-plane charge transport through a tortuous transport network is relatively efficient due to a large density of inter-grain connections. In contrast, using CB results in primarily edge-on oriented polymer crystallites, which leads to diminished out-of-plane charge transport. We correlate these microstructural differences with photocurrent measurements, which clearly show that casting the fullerene out of ODCB leads to significantly enhanced power conversion efficiencies. Thus, we believe that tuning the processing solvents used to cast the electron acceptor in sequentially-processed devices is a viable way to controllably tune the blend film microstructure. © 2014 The Royal Society of Chemistry.

Solution-processable ambipolar diketopyrrolopyrrole-selenophene polymer with unprecedentedly high hole and electron mobilities.

Science.gov (United States)

Lee, Junghoon; Han, A-Reum; Kim, Jonggi; Kim, Yiho; Oh, Joon Hak; Yang, Changduk

2012-12-26

There is a fast-growing demand for polymer-based ambipolar thin-film transistors (TFTs), in which both n-type and p-type transistor operations are realized in a single layer, while maintaining simplicity in processing. Research progress toward this end is essentially fueled by molecular engineering of the conjugated backbones of the polymers and the development of process architectures for device fabrication, which has recently led to hole and electron mobilities of more than 1.0 cm(2) V(-1) s(-1). However, ambipolar polymers with even higher performance are still required. By taking into account both the conjugated backbone and side chains of the polymer component, we have developed a dithienyl-diketopyrrolopyrrole (TDPP) and selenophene containing polymer with hybrid siloxane-solubilizing groups (PTDPPSe-Si). A synergistic combination of rational polymer backbone design, side-chain dynamics, and solution processing affords an enormous boost in ambipolar TFT performance, resulting in unprecedentedly high hole and electron mobilities of 3.97 and 2.20 cm(2) V(-1) s(-1), respectively.

Spray-dried HPMC microparticles of Indomethacin: Impact of drug-polymer ratio and viscosity of the polymeric solution on dissolution

International Nuclear Information System (INIS)

Alanazi, Fars K.; El-Badry, M.; Alsarra, Ibrahim A.

2006-01-01

Polymeric microparticles prepared by spray-drying techniques were investigated to enhance the dissolution rate of indomethacin (IM) in comparison with conventional microparticles prepared by co-precipitation solid dispersion method. Drug-polymer ratios and viscosity of polymeric solutions as potential factors were used in order to enhance the dissolution rate of IM. Spray-drying technique was used for preparing of microparticles using aqueous suspension of IM in hydroxypropyl methylcellulose (HPMC) polymer solution. The effect of drug-polymer ratios on dissolution rates of IM was studied in simulating intestinal medium. IM was analyzed spectrophotometrically at λ =320nm. For each drug-polymer ratios, low and high viscosity polymeric solutions were prepared and their impacts on the dissolution of IM were observed. Microparticles were morphologically characterized by optical microscopy. The interaction between IM and HPMC was studied by differential scanning caloremetry (DSC) and x-ray diffractometry (XRD). Spherical fluffy microparticles of IM were obtained using HPMC. It was observed that the prepared spray-dried microparticles significantly increase the dissolution rate of IM. The increase in dissolution rates was achieved with drug: polymer ratios 1: 1 as well as 1:2 and interestingly, the decrease in drug content in ratio exceeding 1:2 resulted in reduction in dissolution rates. Also, with all drug-polymer ratios, the low viscosity polymeric solutions gave the higher dissolution rates. In conclusion, HPMC microparticles loaded with IM were prepared by spray drying-technique and the potential of this technique to enhance the dissolution was studied. The findings indicate that the dissolution profile of IM microparticles prepared by spray -drying technique relied on drug-polymer ratios and viscosity of polymeric solutions. (author)

Solution-processable MoOx nanocrystals enable highly efficient reflective and semitransparent polymer solar cells

KAUST Repository

Jagadamma, Lethy Krishnan

2016-09-09

Solution-manufacturing of organic solar cells with best-in-class power conversion efficiency (PCE) will require all layers to be solution-coated without compromising solar cell performance. To date, the hole transporting layer (HTL) deposited on top of the organic bulk heterojunction layer in the inverted architecture is most commonly an ultrathin (<10 nm) metal oxide layer prepared by vacuum-deposition. Here, we show that an alcohol-based nanocrystalline MoOx suspension with carefully controlled nanocrystal (NC) size can yield state of the art reflective and semitransparent solar cells. Using NCs smaller than the target HTL thickness (∼10 nm) can yield compact, pinhole-free films which result in highly efficient polymer:fullerene bulk heterojunction (BHJ) solar cells with PCE=9.5%. The solution processed HTL is shown to achieve performance parity with vacuum-evaporated HTLs for several polymer:fullerene combinations and is even shown to work as hole injection layer in polymer light emitting diodes (PLED). We also demonstrate that larger MoOx NCs (30–50 nm) successfully composite MoOx with Ag nanowires (NW) to form a highly conducting, transparent top anode with exceptional contact properties. This yields state-of-the-art semitransparent polymer: fullerene solar cells with PCE of 6.5% and overall transmission >30%. The remarkable performance of reflective and semitransparent OPVs is due to the uncommonly high fill factors achieved using a carefully designed strategy for implementation of MoOx nanocrystals as HTL materials. © 2016 Elsevier Ltd

Solution-mediated cladding doping of commercial polymer optical fibers

Science.gov (United States)

Stajanca, Pavol; Topolniak, Ievgeniia; Pötschke, Samuel; Krebber, Katerina

2018-03-01

Solution doping of commercial polymethyl methacrylate (PMMA) polymer optical fibers (POFs) is presented as a novel approach for preparation of custom cladding-doped POFs (CD-POFs). The presented method is based on a solution-mediated diffusion of dopant molecules into the fiber cladding upon soaking of POFs in a methanol-dopant solution. The method was tested on three different commercial POFs using Rhodamine B as a fluorescent dopant. The dynamics of the diffusion process was studied in order to optimize the doping procedure in terms of selection of the most suitable POF, doping time and conditions. Using the optimized procedure, longer segment of fluorescent CD-POF was prepared and its performance was characterized. Fiber's potential for sensing and illumination applications was demonstrated and discussed. The proposed method represents a simple and cheap way for fabrication of custom, short to medium length CD-POFs with various dopants.

Removal of Parabens from Aqueous Solution Using β-Cyclodextrin Cross-Linked Polymer

Directory of Open Access Journals (Sweden)

Mhd Radzi Bin Abas

2010-09-01

Full Text Available The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI and toluene-2,6-diisocyanate (TDI, with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results.

X-ray small angle scattering of polymer solutions

International Nuclear Information System (INIS)

Koyama, Ryuzo

1975-01-01

In recent papers, the calculated results were reported on the angular dependence of the intensity of scattered light or X-ray by chain polymers, on the basis of a stiff chain model. As the results, the curves of S 2 P (theta) corresponding to Kratky plot, for different molecular expansion, showed a plateau, and the height of the plateau was proportional to the inverse of molecular expansion coefficient α 2 . But as seen later, there is some possibility that the assumption made in the calculation overestimated the expansion of small segments which theoretically determines scattering curves at large scattering angles, such as the plateau. Accordingly, modified calculation was carried out by adopting the stiff chain polymer model as the previous case. When the contour length of a chain segment is very long, it can be treated approximately as a Gaussian coil, thus the equation for a chain segment expansion coefficient α (t) was obtained. Then the mean square distance of chain segments of polymer molecules was able to be determined, and the equation for a particle scattering factor P(theta) was obtained. The numerical calculation of P(theta) showed that this modified assumption considerably decreased the effect of molecular expansion on P(theta), and the curves of S 2 P(theta) increased monotonously without showing the plateau. The result of this calculation was compared with the experimental curves of polystyrene-toluene solution, and the agreement better than before was obtained. (Kako, I.)

Fabrication of mesoporous silica/polymer composites through solvent evaporation process and investigation of their excellent low thermal expansion property.

Science.gov (United States)

Suzuki, Norihiro; Kiba, Shosuke; Yamauchi, Yusuke

2011-03-21

We fabricate mesoporous silica/epoxy polymer composites through a solvent evaporation process. The easy penetration of the epoxy polymers into mesopores is achieved by using a diluted polymer solution including a volatile organic solvent. After the complete solvent evaporation, around 90% of the mesopores are estimated to be filled with the epoxy polymer chains. Here we carefully investigate the thermal expansion behavior of the obtained mesoporous silica/polymer composites. Thermal mechanical analysis (TMA) charts revealed that coefficient of linear thermal expansion (CTE) gradually decreases, as the amount of the doped mesoporous silica increases. Compared with spherical silica particle without mesopores, mesoporous silica particles show a greater effect on lowering the CTE values. Interestingly, it is found that the CTE values are proportionally decreased with the decrease of the total amount of the polymers outside the mesopores. These data demonstrate that polymers embedded inside the mesopores become thermally stable, and do not greatly contribute to the thermal expansion behavior of the composites.

Comparison of acidic polymers for the removal of cobalt from water solutions by polymer assisted ultrafiltration

Energy Technology Data Exchange (ETDEWEB)

Dambies, Laurent, E-mail: chemjobs@netcourrir.com [Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw (Poland); Jaworska, Agnieszka, E-mail: a.jaworska@ichtj.waw.pl [Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw (Poland); Zakrzewska-Trznadel, Grazyna; Sartowska, Bozena [Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw (Poland)

2010-06-15

In this study, three sulfonated water-soluble polymers based on poly(vinyl alcohol) of different molecular weights (10,000, 50,000 and 100,000 Da) were prepared and tested against commercially available poly(acrylic acid) for the removal of cobalt using polymer assisted ultrafiltration. High rejection rates were obtained between pH 3 and 6 with sulfonated poly(vinyl alcohol) (PVA 10,000 and 50,000 Da) whereas poly(acrylic acid) (PAA) of similar molecular weights performed rather poorly in this pH range. Sulfonation improved significantly sorption capability of PVA. Sulfonated PVA 10,000 was the best complexing agent with rejection rate above 95% between pH 3 and 6. For unmodified PVA the rejection rate was only 30-45% at pH 6 and there was no rejection at pH 3 at all. PAA rejection rate was above 90% at pH 6 and only about 10% at pH 3. Large scale experiment in cross-flow, continuous apparatus conducted by using PVA-SO{sub 3}H 10,000 Da to remove {sup 60}Co radioisotope from water solutions showed excellent results demonstrating the potential of this polymer to purify acidic radioactive wastes containing cobalt radioisotopes.

Modeling of the branching influence on liquid–liquid equilibrium of binary and ternary polymer solutions by lattice–cluster theory

International Nuclear Information System (INIS)

Browarzik, Dieter; Langenbach, Kai; Enders, Sabine; Browarzik, Christina

2013-01-01

Highlights: ► Liquid–liquid equilibrium (LLE) is calculated with the lattice–cluster theory (LCT). ► Equations of the LCT are reduced to only three geometrical parameters. ► Branching influence on the LLE is modeled for binary and ternary polymer solutions. ► Branched and linear solvents and polymers are compared in their influence on LLE. ► Solutions of branched polymers in branched solvents show the best miscibility. -- Abstract: The liquid–liquid equilibrium (LLE) of ternary model systems of the type solvent A + polymer B + solvent C is treated in the framework of lattice–cluster theory (LCT). There are a linear and a branched type of A-molecules as well as a linear and two types of strongly branched polymer molecules. The C-molecules are assumed to occupy only one lattice site. For nine binary and six ternary polymer solutions the branching influence on LLE is discussed. Currently, the LCT is the most useful model to take the architecture of the molecules into account. However, particularly for ternary systems the model is not comfortable because of the very numerous terms of the Gibbs energy. Using some relationships between the geometrical parameters of the model a considerable simplification is possible. In this paper the new and simpler equations of the LCT are presented. For comparison with experimental data critical temperatures of solutions of linear and branched polyethylene samples in diphenyl ether are calculated

A new model and extension of Wong-Sandler mixing rule for prediction of (vapour + liquid) equilibrium of polymer solutions using EOS/GE

International Nuclear Information System (INIS)

Haghtalab, Ali; Espanani, Reza

2004-01-01

The cubic equation of state (CEOS) is a powerful method for calculation of (vapour + liquid) equilibrium (VLE) in polymer solutions. Using CEOS for both the vapour and liquid phases allows one to calculate the non-ideality of polymer solutions based on a single EOS approach. However, the traditional mixing rules are not appropriate to extend the CEOS to non-ideal mixtures such as polymer solutions. Several authors have applied the EOS/G E approach to predict (vapour + liquid) equilibria in polymer solutions, however, incorporating an appropriate excess Gibbs free energy for the new mixing rule is a major step. In this research, the NRTL-NRF model was extended in terms of volume fraction of polymer and solvent (instead of mole fraction), then equilibrium calculations were carried out using PRSV EOS and Wong-Sandler mixing rules. Using the adjustable parameters as a function of solution temperature, the NRTL-NRF model can be used as a predictive model. In comparison with NRTL model, the results of the new NRTL-NRF model show better accuracy

Effect of Dilute Apple Juice and Preferred Fluids vs Electrolyte Maintenance Solution on Treatment Failure Among Children With Mild Gastroenteritis: A Randomized Clinical Trial.

Science.gov (United States)

Freedman, Stephen B; Willan, Andrew R; Boutis, Kathy; Schuh, Suzanne

2016-05-10

Gastroenteritis is a common pediatric illness. Electrolyte maintenance solution is recommended to treat and prevent dehydration. Its advantage in minimally dehydrated children is unproven. To determine if oral hydration with dilute apple juice/preferred fluids is noninferior to electrolyte maintenance solution in children with mild gastroenteritis. Randomized, single-blind noninferiority trial conducted between the months of October and April during the years 2010 to 2015 in a tertiary care pediatric emergency department in Toronto, Ontario, Canada. Study participants were children aged 6 to 60 months with gastroenteritis and minimal dehydration. Participants were randomly assigned to receive color-matched half-strength apple juice/preferred fluids (n=323) or apple-flavored electrolyte maintenance solution (n=324). Oral rehydration therapy followed institutional protocols. After discharge, the half-strength apple juice/preferred fluids group was administered fluids as desired; the electrolyte maintenance solution group replaced losses with electrolyte maintenance solution. The primary outcome was a composite of treatment failure defined by any of the following occurring within 7 days of enrollment: intravenous rehydration, hospitalization, subsequent unscheduled physician encounter, protracted symptoms, crossover, and 3% or more weight loss or significant dehydration at in-person follow-up. Secondary outcomes included intravenous rehydration, hospitalization, and frequency of diarrhea and vomiting. The noninferiority margin was defined as a difference between groups of 7.5% for the primary outcome and was assessed with a 1-sided α=.025. If noninferiority was established, a 1-sided test for superiority was conducted. Among 647 randomized children (mean age, 28.3 months; 331 boys [51.1%]; 441 (68.2%) without evidence of dehydration), 644 (99.5%) completed follow-up. Children who were administered dilute apple juice experienced treatment failure less often than those

Interaction Mechanisms between Air Bubble and Molybdenite Surface: Impact of Solution Salinity and Polymer Adsorption.

Science.gov (United States)

Xie, Lei; Wang, Jingyi; Yuan, Duowei; Shi, Chen; Cui, Xin; Zhang, Hao; Liu, Qi; Liu, Qingxia; Zeng, Hongbo

2017-03-07

The surface characteristics of molybdenite (MoS 2 ) such as wettability and surface interactions have attracted much research interest in a wide range of engineering applications, such as froth flotation. In this work, a bubble probe atomic force microscope (AFM) technique was employed to directly measure the interaction forces between an air bubble and molybdenite mineral surface before/after polymer (i.e., guar gum) adsorption treatment. The AFM imaging showed that the polymer coverage on the surface of molybdenite could achieve ∼5.6, ∼44.5, and ∼100% after conditioning in 1, 5, and 10 ppm polymer solution, respectively, which coincided with the polymer coverage results based on contact angle measurements. The electrolyte concentration and surface treatment by polymer adsorption were found to significantly affect bubble-mineral interaction and attachment. The experimental force results on bubble-molybdenite (without polymer treatment) agreed well with the calculations using a theoretical model based on the Reynolds lubrication theory and augmented Young-Laplace equation including the effect of disjoining pressure. The overall surface repulsion was enhanced when the NaCl concentration decreased from 100 to 1 mM, which inhibited the bubble-molybdenite attachment. After conditioning the molybdenite surface in 1 ppm polymer solution, it was more difficult for air bubbles to attach to the molybdenite surface due to the weakened hydrophobic interaction with a shorter decay length. Increasing the polymer concentration to 5 ppm effectively inhibited bubble attachment on mineral surface, which was mainly due to the much reduced hydrophobic interaction as well as the additional steric repulsion between the extended polymer chains and bubble surface. The results provide quantitative information on the interaction mechanism between air bubbles and molybdenite mineral surfaces on the nanoscale, with useful implications for the development of effective polymer

Thermodynamics of dilute aqueous solutions of imidazolium based ionic liquids

International Nuclear Information System (INIS)

Singh, Tejwant; Kumar, Arvind

2011-01-01

Research highlights: → The thermodynamic behaviour of aqueous imidazolium ILs has been investigated. → Volumetric and ultrasonic results indicated the hydrophobic hydration of ILs. → Viscometric studies revealed studied ionic liquids as water-structure makers. → Hydration number increased with increase in alkyl chain length of the cation. - Abstract: Experimental measurements of density ρ, speed of sound u, and viscosity η of aqueous solutions of various 1-alkyl-3-methylimidazolium based ionic liquid (IL) solutions have been performed in dilute concentration regime at 298.15 K to get insight into hydration behaviour of ILs. The investigated ILs are based on 1-alkyl-3-methylimidazolium cation, [C n mim] having [BF 4 ] - , [Cl] - , [C 1 OSO 3 ] - , and [C 8 OSO 3 ] - as anions where n = 4 or 8. Several thermodynamic parameters like apparent molar volume φ V , isentropic compressibility β s , and viscosity B-coefficients have been derived from experimental data. Limiting value of apparent molar volume has been discussed in terms of intrinsic molar volume (V int ) molar electrostriction volume (V elec ), molar disordered (V dis ), and cage volume (V cage ). Viscosity B-coefficients have been used to quantify the kosmotropic or chaotropic nature of ILs. Hydration number of ILs obtained using elctrostriction volume, isentropic compressibility, viscosity, and differential scanning calorimetry have been found to be comparative within the experimental error. The hydrophobic hydration has found to play an important role in hydration of ILs as compared to hydration due to hydrogen bonding and electrostriction. Limiting molar properties, hydration numbers, and B-coefficients have been discussed in terms of alkyl chain length of cation or nature of anion.

A Solution-Doped Polymer Semiconductor:Insulator Blend for Thermoelectrics

KAUST Repository

Kiefer, David; Yu, Liyang; Fransson, Erik; Gó mez, André s; Primetzhofer, Daniel; Amassian, Aram; Campoy-Quiles, Mariano; Mü ller, Christian

2016-01-01

Poly(ethylene oxide) is demonstrated to be a suitable matrix polymer for the solution-doped conjugated polymer poly(3-hexylthiophene). The polarity of the insulator combined with carefully chosen processing conditions permits the fabrication of tens of micrometer-thick films that feature a fine distribution of the F4TCNQ dopant:semiconductor complex. Changes in electrical conductivity from 0.1 to 0.3 S cm−1 and Seebeck coefficient from 100 to 60 μV K−1 upon addition of the insulator correlate with an increase in doping efficiency from 20% to 40% for heavily doped ternary blends. An invariant bulk thermal conductivity of about 0.3 W m−1 K−1 gives rise to a thermoelectric Figure of merit ZT ∼ 10−4 that remains unaltered for an insulator content of more than 60 wt%. Free-standing, mechanically robust tapes illustrate the versatility of the developed dopant:semiconductor:insulator ternary blends.

A Solution-Doped Polymer Semiconductor:Insulator Blend for Thermoelectrics

KAUST Repository

Kiefer, David

2016-09-01

Poly(ethylene oxide) is demonstrated to be a suitable matrix polymer for the solution-doped conjugated polymer poly(3-hexylthiophene). The polarity of the insulator combined with carefully chosen processing conditions permits the fabrication of tens of micrometer-thick films that feature a fine distribution of the F4TCNQ dopant:semiconductor complex. Changes in electrical conductivity from 0.1 to 0.3 S cm−1 and Seebeck coefficient from 100 to 60 μV K−1 upon addition of the insulator correlate with an increase in doping efficiency from 20% to 40% for heavily doped ternary blends. An invariant bulk thermal conductivity of about 0.3 W m−1 K−1 gives rise to a thermoelectric Figure of merit ZT ∼ 10−4 that remains unaltered for an insulator content of more than 60 wt%. Free-standing, mechanically robust tapes illustrate the versatility of the developed dopant:semiconductor:insulator ternary blends.

Understanding Interfacial Alignment in Solution Coated Conjugated Polymer Thin Films

International Nuclear Information System (INIS)

Qu, Ge; Zhao, Xikang; Newbloom, Gregory M.; Zhang, Fengjiao; Mohammadi, Erfan

2017-01-01

Domain alignment in conjugated polymer thin films can significantly enhance charge carrier mobility. However, the alignment mechanism during meniscus-guided solution coating remains unclear. Furthermore, interfacial alignment has been rarely studied despite its direct relevance and critical importance to charge transport. In this study, we uncover a significantly higher degree of alignment at the top interface of solution coated thin films, using a donor–acceptor conjugated polymer, poly(diketopyrrolopyrrole-co-thiopheneco- thieno[3,2-b]thiophene-co-thiophene) (DPP2T-TT), as the model system. At the molecular level, we observe in-plane π–π stacking anisotropy of up to 4.8 near the top interface with the polymer backbone aligned parallel to the coating direction. The bulk of the film is only weakly aligned with the backbone oriented transverse to coating. At the mesoscale, we observe a well-defined fibril-like morphology at the top interface with the fibril long axis pointing toward the coating direction. Significantly smaller fibrils with poor orientational order are found on the bottom interface, weakly aligned orthogonal to the fibrils on the top interface. The high degree of alignment at the top interface leads to a charge transport anisotropy of up to 5.4 compared to an anisotropy close to 1 on the bottom interface. We attribute the formation of distinct interfacial morphology to the skin-layer formation associated with high Peclet number, which promotes crystallization on the top interface while suppressing it in the bulk. As a result, we further infer that the interfacial fibril alignment is driven by the extensional flow on the top interface arisen from increasing solvent evaporation rate closer to the meniscus front.

Self-Assembly of Telechelic Tyrosine End-Capped PEO Star Polymers in Aqueous Solution.

Science.gov (United States)

Edwards-Gayle, Charlotte J C; Greco, Francesca; Hamley, Ian W; Rambo, Robert P; Reza, Mehedi; Ruokolainen, Janne; Skoulas, Dimitrios; Iatrou, Hermis

2018-01-08

We investigate the self-assembly of two telechelic star polymer-peptide conjugates based on poly(ethylene oxide) (PEO) four-arm star polymers capped with oligotyrosine. The conjugates were prepared via N-carboxy anhydride-mediated ring-opening polymerization from PEO star polymer macroinitiators. Self-assembly occurs above a critical aggregation concentration determined via fluorescence probe assays. Peptide conformation was examined using circular dichroism spectroscopy. The structure of self-assembled aggregates was probed using small-angle X-ray scattering and cryogenic transmission electron microscopy. In contrast to previous studies on linear telechelic PEO-oligotyrosine conjugates that show self-assembly into β-sheet fibrils, the star architecture suppresses fibril formation and micelles are generally observed instead, a small population of fibrils only being observed upon pH adjustment. Hydrogelation is also suppressed by the polymer star architecture. These peptide-functionalized star polymer solutions are cytocompatible at sufficiently low concentration. These systems present tyrosine at high density and may be useful in the development of future enzyme or pH-responsive biomaterials.

Recovery of glycols, sugars, and Related Multiple -OH Compounds from Dilute-Aqueous Solution by Regenerable Adsorption onto Activated Carbons

Energy Technology Data Exchange (ETDEWEB)

Chinn, Daniel [Univ. of California, Berkeley, CA (United States)

1999-06-01

The present research explores the use of adsorption onto activated carbons as a means of recover glycerol, glycols, and sugars from dilute-aqueous solution. Our work is focused on understanding the mechanisms of adsorption onto carbons, assessing the degree of adsorption reversibility with precision, and implementing a bench-scale recovery process that results in a higher product concentration and reduction of the energy load for final purification.

Gold nanorod linking to control plasmonic properties in solution and polymer nanocomposites.

Science.gov (United States)

Ferrier, Robert C; Lee, Hyun-Su; Hore, Michael J A; Caporizzo, Matthew; Eckmann, David M; Composto, Russell J

2014-02-25

A novel, solution-based method is presented to prepare bifunctional gold nanorods (B-NRs), assemble B-NRs end-to-end in various solvents, and disperse linked B-NRs in a polymer matrix. The B-NRs have poly(ethylene glycol) grafted along its long axis and cysteine adsorbed to its ends. By controlling cysteine coverage, bifunctional ligands or polymer can be end-grafted to the AuNRs. Here, two dithiol ligands (C6DT and C9DT) are used to link the B-NRs in organic solvents. With increasing incubation time, the nanorod chain length increases linearly as the longitudinal surface plasmon resonance shifts toward lower adsorption wavelengths (i.e., red shift). Analogous to step-growth polymerization, the polydispersity in chain length also increases. Upon adding poly(ethylene glycol) or poly(methyl methacrylate) to chloroform solution with linked B-NR, the nanorod chains are shown to retain end-to-end linking upon spin-casting into PEO or PMMA films. Using quartz crystal microbalance with dissipation (QCM-D), the mechanism of nanorod linking is investigated on planar gold surfaces. At submonolayer coverage of cysteine, C6DT molecules can insert between cysteines and reach an areal density of 3.4 molecules per nm(2). To mimic the linking of Au NRs, this planar surface is exposed to cysteine-coated Au nanoparticles, which graft at 7 NPs per μm(2). This solution-based method to prepare, assemble, and disperse Au nanorods is applicable to other nanorod systems (e.g., CdSe) and presents a new strategy to assemble anisotropic particles in organic solvents and polymer coatings.

Turbulent structures of non-Newtonian solutions containing rigid polymers

Science.gov (United States)

Mohammadtabar, M.; Sanders, R. S.; Ghaemi, S.

2017-10-01

The turbulent structure of a channel flow of Xanthan Gum (XG) polymer solution is experimentally investigated and compared with water flow at a Reynolds number of Re = 7200 (based on channel height and properties of water) and Reτ = 220 (based on channel height and friction velocity, uτ0). The polymer concentration is varied from 75, 100, and 125 ppm to reach the point of maximum drag reduction (MDR). Measurements are carried out using high-resolution, two-component Particle Image Velocimetry (PIV) to capture the inner and outer layer turbulence. The measurements showed that the logarithmic layer shifts away from the wall with increasing polymer concentration. The slopes of the mean velocity profile for flows containing 100 and 125 ppm XG are greater than that measured for XG at 75 ppm, which is parallel with the slope obtained for deionized water. The increase in slope results in thickening buffer layer. At MDR, the streamwise Reynolds stresses are as large as those of the Newtonian flow while the wall-normal Reynolds stresses and Reynolds shear stresses are significantly attenuated. The sweep-dominated region in the immediate vicinity of the wall extends further from the wall with increasing polymer concentration. The near-wall skewness intensifies towards positive streamwise fluctuations and covers a larger wall-normal length at larger drag reduction values. The quadrant analysis at y + 0 = 25 shows that the addition of polymers inclines the principal axis of v versus u plot to almost zero (horizontal) as the joint probability density function of fluctuations becomes symmetric with respect to the u axis at MDR. The reduction of turbulence production is mainly associated with the attenuation of the ejection motions. The spatial-correlation of the fluctuating velocity field shows that increasing the polymer concentration increases the spatial coherence of u fluctuations in the streamwise direction while they appear to have the opposite effect in the wall

Temperature-induced phase separation and hydration in aqueous polymer solutions studied by NMR and IR spectroscopy: comparison of poly(N-vinylcaprolactam) and acrylamide-based polymers

Czech Academy of Sciences Publication Activity Database

Spěváček, Jiří; Dybal, Jiří

2014-01-01

Roč. 336, č. 1 (2014), s. 39-46 ISSN 1022-1360. [International IUPAC Conference on Polymer-Solvent Complexes and Intercalates /9./ - POLYSOLVAT-9. Kiev, 11.09.2012-14.09.2012] R&D Projects: GA ČR GA202/09/1281 Institutional support: RVO:61389013 Keywords : aqueous polymer solutions * FT-IR * NMR Subject RIV: CD - Macromolecular Chemistry

On the dynamics of polymer mixtures in solution using the RPA

International Nuclear Information System (INIS)

Benmouna, M.

1989-09-01

The dynamics of polymer mixtures and copolymers in solution is investigated using the Random Phase Approximation (RPA). It is shown that the known results for the intermediate scattering functions are recovered in the Rouse limit only. If hydrodynamic interaction is not negligible, a discrepancy appears. This discrepancy can be observed by combining static and dynamic scattering experiments. (author). 10 refs

Reaction enthalpy from the binding of multivalent cations to anionic polyelectrolytes in dilute solutions

Science.gov (United States)

Hansch, Markus; Kaub, Hans Peter; Deck, Sascha; Carl, Nico; Huber, Klaus

2018-03-01

Dilute solutions of sodium poly(styrene sulfonate) (NaPSS) in the presence of Al3+, Ca2+, and Ba2+ were analysed by means of isothermal titration calorimetry (ITC) in order to investigate the heat effect of bond formation between those cations and the anionic SO3- residues of NaPSS. The selection of the cations was guided by the solution behavior of the corresponding PSS salts from a preceding study [M. Hansch et al., J. Chem. Phys. 148(1), 014901 (2018)], where bonds between Ba2+ and anionic PSS showed an increasing solubility with decreasing temperature and Al3+ exhibited the inverse trend. Unlike to Al3+ and Ba2+, Ca2+ is expected to behave as a purely electrostatically interacting bivalent cation and was thus included in the present study. Results from ITC satisfactorily succeeded to explain the temperature-dependent solution behavior of the salts with Al3+ and Ba2+ and confirmed the non-specific behavior of Ca2+. Additional ITC experiments with salts of Ca2+ and Ba2+ and sodium poly(acrylate) complemented the results on PSS by data from a chemically different polyanion. Availability of these joint sets of polyanion-cation combinations not only offers the chance to identify common features and subtle differences in the solution behavior of polyelectrolytes in the presence of multi-valent cations but also points to a new class of responsive materials.

Determination of micro-quantities of several elements in soil solution by isotope dilution and activation analyses

International Nuclear Information System (INIS)

Cho, C.M.; Axmann, H.

1965-01-01

Determination of small quantities of plant nutrients in the soil solution of flooded rice soils is a difficult problem. The concentrations of Mn, Fe and P, for example, in some soil solutions are so small that no chemical method gives any accurate result. Neutron activation analysis was reported to give a much lower limit of detectability for several elements, while for elements with low-induced activity after neutron irradiation, substoichiometric isotopic dilution analysis was applied. One of the advantages of neutron activation analysis lies in the fact that simultaneous activation of every inducible element in a sample takes place. This gives an opportunity to determine many elements by one sample preparation and irradiation. This, however, is not a simple task since identification of the activated products and their quantitative estimation becomes very difficult. Certain operations of separation must be carried out before activity measurements. Ion-exchange resin columns and chemical separation following the addition of carriers were successfully used for the determination of many elements after neutron irradiation. These procedures, however, cannot be directly applied to the determination of the elements of agronomic interest. A procedure was developed to determine several elements of agronomic interest. Times of irradiation and cooling, quick separation by ion-exchange columns, together with chemical precipitation for β-emitters of relatively long half-lives, were all combined to get the maximum benefit from neutron activation analysis. For Fe, for which no satisfactory neutron activation analysis has yet been developed, a modified substoichiometric double isotope dilution procedure is applied

Diffusion of drag-reducing polymer solutions within a rough-walled turbulent boundary layer

Science.gov (United States)

Elbing, Brian R.; Dowling, David R.; Perlin, Marc; Ceccio, Steven L.

2010-04-01

The influence of surface roughness on diffusion of wall-injected, drag-reducing polymer solutions within a turbulent boundary layer was studied with a 0.94 m long flat-plate test model at speeds of up to 10.6 m s-1 and Reynolds numbers of up to 9×106. The surface was hydraulically smooth, transitionally rough, or fully rough. Mean concentration profiles were acquired with planar laser induced fluorescence, which was the primary flow diagnostic. Polymer concentration profiles with high injection concentrations (≥1000 wppm) had the peak concentration shifted away from the wall, which was partially attributed to a lifting phenomenon. The diffusion process was divided into three zones—initial, intermediate, and final. Studies of polymer injection into a polymer ocean at concentrations sufficient for maximum drag reduction indicated that the maximum initial zone length is of the order of 100 boundary layer thicknesses. The intermediate zone results indicate that friction velocity and roughness height are important scaling parameters in addition to flow and injection conditions. Lastly, the current results were combined with those in Petrie et al. ["Polymer drag reduction with surface roughness in flat-plate turbulent boundary layer flow," Exp. Fluids 35, 8 (2003)] to demonstrate that the influence of polymer degradation increases with increased surface roughness.

Thermodynamics of dilute aqueous solutions of imidazolium based ionic liquids

Energy Technology Data Exchange (ETDEWEB)

Singh, Tejwant [Salt and Marine Chemicals Division, Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research (CSIR), G.B. Marg, Bhavnagar 364002 (India); Kumar, Arvind, E-mail: arvind@csmcri.or [Salt and Marine Chemicals Division, Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research (CSIR), G.B. Marg, Bhavnagar 364002 (India)

2011-06-15

Research highlights: The thermodynamic behaviour of aqueous imidazolium ILs has been investigated. Volumetric and ultrasonic results indicated the hydrophobic hydration of ILs. Viscometric studies revealed studied ionic liquids as water-structure makers. Hydration number increased with increase in alkyl chain length of the cation. - Abstract: Experimental measurements of density {rho}, speed of sound u, and viscosity {eta} of aqueous solutions of various 1-alkyl-3-methylimidazolium based ionic liquid (IL) solutions have been performed in dilute concentration regime at 298.15 K to get insight into hydration behaviour of ILs. The investigated ILs are based on 1-alkyl-3-methylimidazolium cation, [C{sub n}mim] having [BF{sub 4}]{sup -}, [Cl]{sup -}, [C{sub 1}OSO{sub 3}]{sup -}, and [C{sub 8}OSO{sub 3}]{sup -} as anions where n = 4 or 8. Several thermodynamic parameters like apparent molar volume {phi}{sub V}, isentropic compressibility {beta}{sub s}, and viscosity B-coefficients have been derived from experimental data. Limiting value of apparent molar volume has been discussed in terms of intrinsic molar volume (V{sub int}) molar electrostriction volume (V{sub elec}), molar disordered (V{sub dis}), and cage volume (V{sub cage}). Viscosity B-coefficients have been used to quantify the kosmotropic or chaotropic nature of ILs. Hydration number of ILs obtained using elctrostriction volume, isentropic compressibility, viscosity, and differential scanning calorimetry have been found to be comparative within the experimental error. The hydrophobic hydration has found to play an important role in hydration of ILs as compared to hydration due to hydrogen bonding and electrostriction. Limiting molar properties, hydration numbers, and B-coefficients have been discussed in terms of alkyl chain length of cation or nature of anion.

Flow induced/ refined solution crystallization of a semiconducting polymer

Science.gov (United States)

Nguyen, Ngoc A.

Organic photovoltaics, a new generation of solar cells, has gained scientific and economic interests due to the ability of solution-processing and potentially low-cost power production. Though, the low power conversion efficiency of organic/ plastic solar cells is one of the most pertinent challenges that has appealed to research communities from many different fields including materials science and engineering, electrical engineering, chemical engineering, physics and chemistry. This thesis focuses on investigating and controlling the morphology of a semi-conducting, semi-crystalline polymer formed under shear-flow. Molecular structures and processing techniques are critical factors that significantly affect the morphology formation in the plastic solar cells, thus influencing device performance. In this study, flow-induced solution crystallization of poly (3-hexylthiophene) (P3HT) in a poor solvent, 2-ethylnapthalene (2-EN) was utilized to make a paint-like, structural liquid. The polymer crystals observed in this structured paint are micrometers long, nanometers in cross section and have a structure similar to that formed under quiescent conditions. There is pi-pi stacking order along the fibril axis, while polymer chain folding occurs along the fibril width and the order of the side-chain stacking is along fibril height. It was revealed that shear-flow not only induces P3HT crystallization from solution, but also refines and perfects the P3HT crystals. Thus, a general strategy to refine the semiconducting polymer crystals from solution under shear-flow has been developed and employed by simply tuning the processing (shearing) conditions with respect to the dissolution temperature of P3HT in 2-EN. The experimental results demonstrated that shear removes defects and allows more perfect crystals to be formed. There is no glass transition temperature observed in the crystals formed using the flow-induced crystallization indicating a significantly different

Study of the dosimetric properties using organometallic polymers in solution

International Nuclear Information System (INIS)

Fernandes, David Moreira

2012-01-01

This work aimed to study the dosimetric characteristics of the polymer of the polymer ''poly-[ 1, l-bis (ethynyl) -4,4-biphenyl (bis-tributylphosphine) Pt (11)]'' (Pt-DEBP) compared to radiation gamma. The Pt-DEBP polymer, containing ten monomer units, was then dissolved in organic solvents as chloroform and toluene. The samples were irradiated at four concentrations (0.0500, 0.0375, 0.0250, 0.0113 mg / mL) in duplicate, with radiation doses ranging from 1 to 90 Gy. The results were evaluated based on spectroscopic techniques such as optical absorption spectroscopy (UV -Vis), fluorescence (emission), time resolved fluorescence (FRT) and Fourier transform infrared (FTIR). For DEBP-Pt solutions in chloroform, there is a shift in the position of the main optical absorption band (πt - π*) to lower wavelength (blue-shift), allied to a decreasing absorption intensity with increasing radiation dose. In fluorescence spectroscopy, there was a shift to longer wavelengths (redshift) allied to an increasing emission intensity with increasing radiation dose. FRT experiments on irradiated samples dissolved in chloroform indicated the presence of a new emitter center. FTIR spectra show the incorporation of chlorine in the polymer chain, justifying the blue-shift observed in the absorption spectra and the new emission center. In addition, the behavior of linear results in the absorption and fluorescence studies was investigated based on the relationship between the wavelength of maximum absorption/emission and the radiation dose. For both cases, a linear behavior was observed in relation to the sample concentration. Repeatability and stability tests were also performed. For the samples dissolved in toluene, there was no significant shift of the spectrum of absorption or fluorescence for all doses. The results show that the Pt-DEBP polymer dissolved in chloroform can be used as a dosimeter for x-ray doses between 1 - 30 Gy based on the changes in absorption and/or emission

Responsive Copolymers for Enhanced Petroleum Recovery

Energy Technology Data Exchange (ETDEWEB)

McCormick, C.; Hester, R.

2001-02-27

The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

Effect of alkyl chain length and temperature on the thermodynamic properties of ionic liquids 1-alkyl-3-methylimidazolium bromide in aqueous and non-aqueous solutions at different temperatures

International Nuclear Information System (INIS)

Sadeghi, Rahmat; Shekaari, Hemayat; Hosseini, Rahim

2009-01-01

The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C 3 ), hexyl (C 6 ), heptyl (C 7 ), and octyl (C 8 )) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol . kg -1 were taken. The values of the compressibilities, expansivity and apparent molar properties for [C n mim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich-Mayer and the Pitzer's equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute-solvent and solute-solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made

Effect of alkyl chain length and temperature on the thermodynamic properties of ionic liquids 1-alkyl-3-methylimidazolium bromide in aqueous and non-aqueous solutions at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Sadeghi, Rahmat [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)], E-mail: rahsadeghi@yahoo.com; Shekaari, Hemayat [Department of Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil (Iran, Islamic Republic of); Hosseini, Rahim [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)

2009-02-15

The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C{sub 3}), hexyl (C{sub 6}), heptyl (C{sub 7}), and octyl (C{sub 8})) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol . kg{sup -1} were taken. The values of the compressibilities, expansivity and apparent molar properties for [C{sub n}mim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich-Mayer and the Pitzer's equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute-solvent and solute-solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made.

Dilution and volatilization of groundwater contaminant discharges in streams

DEFF Research Database (Denmark)

Aisopou, Angeliki; Bjerg, Poul Løgstrup; Sonne, Anne Thobo

2015-01-01

measurement. The solution was successfully applied to published field data obtained in a large and a small Danish stream and provided valuable information on the risk posed by the groundwater contaminant plumes. The results provided by the dilution and volatilization model are very different to those obtained......An analytical solution to describe dilution and volatilization of a continuous groundwater contaminant plume into streams is developed for risk assessment. The location of groundwater plume discharge into the stream (discharge through the side versus bottom of the stream) and different...

Chemical metallization of KMPR photoresist polymer in aqueous solutions

Science.gov (United States)

Zeb, Gul; Duong, Xuan Truong; Vu, Ngoc Pi; Phan, Quang The; Nguyen, Duc Tuong; Ly, Viet Anh; Salimy, Siamak; Le, Xuan Tuan

2017-06-01

While conventional methods for preparing thin films of metals and metallic alloys on insulating substrates in the field of microelectromechanical systems (MEMS) include vapor deposition techniques, we demonstrate here that electroless deposition can be considered as an alternate efficient approach to metallize the surface of insulating substrates, such as KMPR epoxy photoresist polymer. In comparison with the physical and chemical vapor deposition methods, which are well-established for metallization of photoresist polymers, our electroless nickel plating requires only immersing the substrates into aqueous solutions in open air at low temperatures. Thin films of nickel alloy have been deposited electrolessly on KMPR surface, through a cost-effective and environmental chromium-free process, mediated through direct grafting of amine palladium complexes in aqueous medium. This covalent organic coating provides excellent adhesion between KMPR and the nickel film and allows better control of the palladium catalyst content. Covalent grafting and characterization of the deposited nickel film have been carried out by means of Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy techniques.

Structural parameters of polyethylenes obtained using a palladium catalyst: dilute solution and solid state studies

International Nuclear Information System (INIS)

Meneghetti, Simoni Plentz; Lutz, Pierre J.; Duval, M.; Kress, Jacky; Lapp, A.

2001-01-01

Polyethylenes were obtained using palladium catalyst [(Ar N=C(Me)-C(Me)=N Ar) Pd(CH 2 ) 3 (COOMe)] + BAr' 4 - (VERSIPOL TM ); Ar2,6-i-Pr 2 -C 6 H 3 and Ar'3,5-(CF 3 ) 2 -C 6 H 3 . The combination of dilute solution and solid state characterization of these polyethylenes revealed strong differences between structural parameters of samples prepared under almost identical conditions except ethylene pressure (6, 3 and 1 bar). These differences can be explained by the fact that samples prepared at 6 bar are almost linear, with only a few short branches, whereas those synthesized at 1 bar are highly branched or even hyper branched. (author)

Separation and accumulation of acitinides with the aid of a phosphoric acid polymer

International Nuclear Information System (INIS)

Novikov, A.; Geckeler, K.E.

1993-01-01

A new method for the separation and enrichment of actinides based on the use of polymer reagents is presented, in this study, poly(ethyleneimine methylphosphonic acid) was used for the interaction with actinide ions in the homogeneous phase. In conjunction with membrane filtration this reagent allows both the separation and the enrichment of actinides from dilute solutions. The retention profiles for the series of actinides U(VI), Np(V), Pu(IV), Am(III), Cm(III), Cf(III) were investigated at different pH. Retention differences between 0% and 100% were found depending on the actinide element and pH. Thus, these elements can be separated and enriched form aqueous solutions of binary or multi-component mixtures. (orig.)

Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

Science.gov (United States)

Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

2016-01-01

Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V−1s−1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

Role of Elasto-Inertial Turbulence in Polymer Drag Reduction

Science.gov (United States)

Dubief, Yves; Sid, Samir; Terrapon, Vincent

2017-11-01

Elasto-Inertial Turbulence (EIT) is a peculiar state of turbulence found in dilute polymer solutions flowing in parallel wall flows over a wide range of Reynolds numbers. At subcritical Reynolds numbers, appropriate boundary conditions trigger EIT, a self-sustaining cycle of energy transfers between thin sheets of stretched polymers and velocity perturbations, which translates into an increase of friction drag. For critical and supercritical Reynolds numbers, polymer additives may lead to significant drag reduction, bounded by the asymptotic state known as Maximum Drag Reduction (MDR). The present research investigates the role of EIT in the dynamics of critical and supercritical Reynolds number wall flows. Using high-fidelity direct numerical simulations of channel flows and the FENE-P model, we establish that (i) EIT is two-dimensional, (ii) the scales essential to the existence of EIT are sub-Kolmogorov, and (iii) EIT drives MDR at low and possibly moderate Reynolds number turbulent flows. These findings were validated in two different codes and using unprecedented resolutions for polymer flows. YD is grateful for the support of Binational Science Foundation. SS and VT acknowledges Fonds de la Recherche Scientifique (FNRS), MarieCurie Career Integration Grant and computing allocation from University of Liege and PRACE.

Mirror symmetry breaking of silicon polymers--from weak bosons to artificial helix.

Science.gov (United States)

Fujiki, Michiya

2009-01-01

From elemental particles to human beings, matter and living worlds in our universe are dissymmetric with respect to mirror symmetry. Since the early 19th century, the origin of biomolecular handedness has been puzzling scientists. Nature's elegant bottom-up preference, however, sheds light on new concepts of generating, amplifying, and switching artificial polymers, supramolecules, liquid crystals, and organic crystals that can exhibit ambidextrous circular dichroism in the UV/Visible region with efficiency in production under milder ambient conditions. In the 1920s, Kipping, who first synthesized polysilanes with phenyl groups, had much interest in the handedness of inorganic and organic substances from 1898 to 1909 in his early research life. Polysilanes--which are soluble Si-Si bonded chain-like near-UV chromophores that carry a rich variety of organic groups--may become a bridge between animate and inanimate polymer systems. The present account focuses on several mirror symmetry breaking phenomena exemplified in polysilanes carrying chiral and/or achiral side groups, which are in isotropic dilute solution, as polymer particles dispersed in solution, and in a double layer film immobilized at the solid surface, and subtle differences in the helix, by dictating ultimately ultraweak chiral forces at subatomic, atomic, and molecular levels. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

An iterative method for hydrodynamic interactions in Brownian dynamics simulations of polymer dynamics

Science.gov (United States)

Miao, Linling; Young, Charles D.; Sing, Charles E.

2017-07-01

Brownian Dynamics (BD) simulations are a standard tool for understanding the dynamics of polymers in and out of equilibrium. Quantitative comparison can be made to rheological measurements of dilute polymer solutions, as well as direct visual observations of fluorescently labeled DNA. The primary computational challenge with BD is the expensive calculation of hydrodynamic interactions (HI), which are necessary to capture physically realistic dynamics. The full HI calculation, performed via a Cholesky decomposition every time step, scales with the length of the polymer as O(N3). This limits the calculation to a few hundred simulated particles. A number of approximations in the literature can lower this scaling to O(N2 - N2.25), and explicit solvent methods scale as O(N); however both incur a significant constant per-time step computational cost. Despite this progress, there remains a need for new or alternative methods of calculating hydrodynamic interactions; large polymer chains or semidilute polymer solutions remain computationally expensive. In this paper, we introduce an alternative method for calculating approximate hydrodynamic interactions. Our method relies on an iterative scheme to establish self-consistency between a hydrodynamic matrix that is averaged over simulation and the hydrodynamic matrix used to run the simulation. Comparison to standard BD simulation and polymer theory results demonstrates that this method quantitatively captures both equilibrium and steady-state dynamics after only a few iterations. The use of an averaged hydrodynamic matrix allows the computationally expensive Brownian noise calculation to be performed infrequently, so that it is no longer the bottleneck of the simulation calculations. We also investigate limitations of this conformational averaging approach in ring polymers.

A new tool for an old job: Using fixed cell scanning calorimetry to investigate dilute aqueous solutions

International Nuclear Information System (INIS)

Woolley, E.M.

2007-01-01

The development of fixed twin cell temperature scanning calorimeters has enabled the more efficient determination of heat capacities of dilute aqueous solutions with a precision comparable to that of the Picker flow heat capacity calorimeters developed nearly 40 years ago. Experiments require less than 0.5 cm 3 of solution, and results can be obtained routinely over the temperature range (278 to 395) K at pressures up to a few bars. Multiple scanning of samples by both increasing and decreasing temperature allows assessment of instrument drift, solute stability, and reproducibility of results. Chemical calibration is essential to take full advantage of the precision and sensitivity of the calorimeters. The calorimetric output is a direct measure of the difference in heat capacity per unit volume of a solution and of a reference liquid, usually water. Thus, densities of the solution and reference liquid are needed to transform the results into heat capacities per unit mass of solution. Examples of solutes that have been investigated include a variety of inorganic and organic compounds that dissolve to give simple ionic or neutral species, or that produce complexes or species that exist in equilibrium distributions that can change as the temperature is scanned. Appropriate selection of the results from experiments on combinations of solutes allows calculation of standard state (zero concentration) thermodynamic quantities for chemical processes and reactions over the ranges of temperature scanned at the solution compositions investigated. Results for a few specific systems are presented and discussed for some representative classes of solutes that have been investigated in our laboratory since 1998

Preparation of Sandy Soil Stabilizer for Roads Based on Radiation Modified Polymer Composite

International Nuclear Information System (INIS)

Elnahas, H.H.

2016-01-01

Radiation modified polymer composite (RMPC) was studied to build an extremely durable sandy road, construct a trail or bath, or control dust and erosion. A dilute solution of composite binds sandy soil fines through a coagulation bonding process. The result is a dense soil structure that has superior resistance to cracks and water penetration and can also solve erosion control problems. In erosion control applications, diluted composite is merely sprayed into sandy soil without compaction, effectively sealing the surface to prevent air-born dust or deterioration from erosion. The prepared composite has an elastic and melt-able film formation that imparts thermal compacting to the stabilized sandy soil after full dryness for sandy road leveling, repairing and restoration processes. The prepared composite is environmentally economical when compared with traditional sandy soil stabilizing (SSS) or sealing methods.

Removal of phenol from aqueous solution using polymer inclusion membrane based on mixture of CTA and CA

Science.gov (United States)

Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar

2018-03-01

Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. In the present work, the removal of phenol from aqueous solution across polymer inclusion membrane (PIM), based on mixture of cellulose triacetate and cellulose acetate as support (75/25%), calix[4]resorcinarene derivative as a carrier and 2-nitrophenyl octyl ether (2-NPOE) as plasticizer was investigated. The experimental part of this investigation involved the influence of carrier nature, plasticizer concentration, pH phases, and phenol initial concentration on the removal efficiency of phenol from synthetic wastewater. A PIM containing 0.1 g (of mixture polymer), (0.15 g/g mixture of polymer) of carrier and (0.03 ml/g mixture of polymer) of 2-NPOE provided the highest percentage of phenol removal efficiency over a 6-day transport; the removal was found to be about 95%, indeed the removal was found to be highly dependent of pH phases. The feed solution in these transport experiments was at pH 2, while the stripping solution contained 0.20 M NaOH. This study claims that the PIM with a mixture of cellulose derivatives can be used effectively to remove phenols from wastewaters.

Effect of Aging Temperature on Corrosion Behavior of Sintered 17-4 PH Stainless Steel in Dilute Sulfuric Acid Solution

Science.gov (United States)

Szewczyk-Nykiel, Aneta; Kazior, Jan

2017-07-01

The general corrosion behavior of sintered 17-4 PH stainless steel processed under different processing conditions in dilute sulfuric acid solution at 25 °C was studied by open-circuit potential measurement and potentiodynamic polarization technique. The corrosion resistance was evaluated based on electrochemical parameters, such as polarization resistance, corrosion potential, corrosion current density as well as corrosion rate. The results showed that the precipitation-hardening treatment could significantly improve the corrosion resistance of the sintered 17-4 PH stainless steel in studied environment. As far as the influence of aging temperature on corrosion behavior of the sintered 17-4 PH stainless steel is concerned, polarization resistance and corrosion rate are reduced with increasing aging temperature from 480 up to 500 °C regardless of the temperature of solution treatment. It can be concluded that the highest corrosion resistance in 0.5 M H2SO4 solution exhibits 17-4 PH after solution treatment at 1040 °C followed by aging at 480 °C.

Factors responsible for the aggregation behavior of hydrophobic polyelectrolyte PEA in aqueous solution studied by molecular dynamics simulations.

Science.gov (United States)

Sappidi, Praveenkumar; Natarajan, Upendra

2017-08-01

Self-association (i.e. interchain aggregation) behavior of atactic poly(ethacrylic acid) PEA in dilute aqueous solution as function of degree-of-neutralization by Na + counter-ions (i.e. charge fraction f) was investigated by molecular dynamics simulations. Aggregation is found to occur in the range 0≤f≤0.7 in agreement with experimental results compared at specified polymer concentration C p =0.36mol/l in dilute solution. The macromolecular solution was characterized and analysed for radius-of-gyration, torsion angle distribution, inter and intra-molecular hydrogen bonds, radial distribution functions of intermolecular and inter-atomic pairs, inter-chain contacts and solvation enthalpy. The PEA chains form aggregate through attractive inter-chain interaction via hydrogen bonding, in the range fenthalpy. The PEA solvation enthalpy becomes increasingly favorable with increase in f. The transition enthalpy change, in going from uncharged (acid) state to fully charged state (f=1) is unfavorable towards aggregate formation. Copyright © 2017 Elsevier Inc. All rights reserved.

Enthalpies of dilution of aqueous Li{sub 2}B{sub 4}O{sub 7} solutions at 298.15K and application of ion-interaction model

Energy Technology Data Exchange (ETDEWEB)

Yin Guoyin [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Yao Yan [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China) and Graduate School of Chinese Academy of Sciences, Beijing 100039 (China)]. E-mail: yaoy@isl.ac.cn; Jiao Baojuan [Department of Chemistry, Northwest University, Xi' an 710069 (China); Chen Sanping [Department of Chemistry, Northwest University, Xi' an 710069 (China); Gao Shengli [Department of Chemistry, Northwest University, Xi' an 710069 (China)

2005-09-15

The enthalpies of dilution have been measured for aqueous Li{sub 2}B{sub 4}O{sub 7} solutions from 0.0212 to 2.1530molkg{sup -1} at 298.15K. The relative apparent molar enthalpies, L{sub {phi}}, and relative partial molar enthalpies of the solvent and solute, L-bar{sub 1} and L-bar{sub 2} were calculated. The thermodynamic properties of the complex aqueous solutions were represented with a modified Pitzer ion-interaction model.

Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent.

Science.gov (United States)

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

2015-06-07

We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters {AiBCj} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient B2 as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.

Thermally Activated Delayed Fluorescence in Polymers: A New Route toward Highly Efficient Solution Processable OLEDs.

Science.gov (United States)

Nikolaenko, Andrey E; Cass, Michael; Bourcet, Florence; Mohamad, David; Roberts, Matthew

2015-11-25

Efficient intermonomer thermally activated delayed fluorescence is demonstrated for the first time, opening a new route to achieving high-efficiency solution processable polymer light-emitting device materials. External quantum efficiency (EQE) of up to 10% is achieved in a simple fully solution-processed device structure, and routes for further EQE improvement identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The exact solution of a three-dimensional lattice polymer confined in a slab with sticky walls

Energy Technology Data Exchange (ETDEWEB)

Brak, R; Iliev, G K; Owczarek, A L [Department of Mathematics and Statistics, University of Melbourne, Parkville, Vic 3010 (Australia); Whittington, S G [Department of Chemistry, University of Toronto, Toronto M5S 3H6 (Canada)

2010-04-02

We present the exact solution of a three-dimensional lattice model of a polymer confined between two sticky walls, that is within a slab. We demonstrate that the model behaves in a similar way to its two-dimensional analogues and agrees with Monte Carlo evidence based upon simulations of self-avoiding walks in slabs. The model on which we focus is a variant of the partially directed walk model on the cubic lattice. We consider both the phase diagram of relatively long polymers in a macroscopic slab and the effective force of the polymer on the walls of the slab.

Interpolymer reactions of nonionic polymers with polyacrylic acid in aqueous solutions

Directory of Open Access Journals (Sweden)

E. Shaikhutdinov

2012-03-01

Full Text Available Results of fundamental investigations in the intermacromolecular reactions and interpolymer complexes to be performed by authors with co-workes within last 20 years have been intergrated and summarized in the present review. The raw of fundamental regularities in the effect of factors of different nature (pH, ionic strength, temperature, hydrophilic-hydrophobic balance of macrochain, etc. on the complexation of nonionic polymers with polycarboxylic acids in aqueous solutions has been revealed. Critical pH upon complexation (pHcrit. has been used for evaluation of the complexing ability of the polymers. It was shown tha tdepending on pHcrit. all systems can be divided into 2 groups, namely, weak complexing and strongly complexing. The existence of two critical pH upon complexation responsible for formation typical interpolymer complexes and hydrophilic associations has been demonstrated by the method of luminescence spectroscopy.

Application of a novel 3-fluid nozzle spray drying process for the microencapsulation of therapeutic agents using incompatible drug-polymer solutions.

Science.gov (United States)

Sunderland, Tara; Kelly, John G; Ramtoola, Zebunnissa

2015-04-01

The aim of this study was to evaluate a novel 3-fluid concentric nozzle (3-N) spray drying process for the microencapsulation of omeprazole sodium (OME) using Eudragit L100 (EL100). Feed solutions containing OME and/or EL100 in ethanol were assessed visually for OME stability. Addition of OME solution to EL100 solution resulted in precipitation of OME followed by degradation of OME reflected by a colour change from colourless to purple and brown. This was related to the low pH of 2.8 of the EL100 solution at which OME is unstable. Precipitation and progressive discoloration of the 2-fluid nozzle (2-N) feed solution was observed over the spray drying time course. In contrast, 3-N solutions of EL100 or OME in ethanol were stable over the spray drying period. Microparticles prepared using either nozzle showed similar characteristics and outer morphology however the internal morphology was different. DSC showed a homogenous matrix of drug and polymer for 2-N microparticles while 3-N microparticles had defined drug and polymer regions distributed as core and coat. The results of this study demonstrate that the novel 3-N spray drying process can allow the microencapsulation of a drug using an incompatible polymer and maintain the drug and polymer in separate regions of the microparticles.

Chemical solution deposition of YBCO thin film by different polymer additives

International Nuclear Information System (INIS)

Wang, W.T.; Li, G.; Pu, M.H.; Sun, R.P.; Zhou, H.M.; Zhang, Y.; Zhang, H.; Yang, Y.; Cheng, C.H.; Zhao, Y.

2008-01-01

A polymer-assisted chemical solution deposition approach has been proposed for the preparation of YBCO thin film. Different additives like PVB (polyvinyl butyral), PEG (polyethylene glycol) and PVP (polyvinylpyrrolidone) have been used to adjust the final viscosity of the precursor solution and thus the film formation. In this fluorine-free approach, YBCO has been deposited on single crystal substrates with metal acetates being starting materials. Biaxially textured YBCO thin films have been obtained. However, different additives lead to different microstructure. Dense, smooth and crack-free YBCO film prepared with PVB as additive yields sharp superconducting transition around T c = 90 K as well as high J c (0 T, 77 K) over 3 MA/cm 2

Chemical solution deposition of YBCO thin film by different polymer additives

Energy Technology Data Exchange (ETDEWEB)

Wang, W.T.; Li, G.; Pu, M.H.; Sun, R.P.; Zhou, H.M.; Zhang, Y. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); Zhang, H. [Department of Physics, Peking University, Beijing 100871 (China); Yang, Y. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); Cheng, C.H. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); School of Materials Science and Engineering, University of New South Wale, Sydney, 2052 NSW (Australia); Zhao, Y. [Key Laboratory of Magnetic Levitation Technologies and Maglev Trains, Ministry of Education of China, Superconductivity R and D Center (SRDC), Mail Stop 165, Southwest Jiaotong University, Chengdu 610031 (China); School of Materials Science and Engineering, University of New South Wale, Sydney, 2052 NSW (Australia)], E-mail: yzhao@swjtu.edu.cn

2008-09-15

A polymer-assisted chemical solution deposition approach has been proposed for the preparation of YBCO thin film. Different additives like PVB (polyvinyl butyral), PEG (polyethylene glycol) and PVP (polyvinylpyrrolidone) have been used to adjust the final viscosity of the precursor solution and thus the film formation. In this fluorine-free approach, YBCO has been deposited on single crystal substrates with metal acetates being starting materials. Biaxially textured YBCO thin films have been obtained. However, different additives lead to different microstructure. Dense, smooth and crack-free YBCO film prepared with PVB as additive yields sharp superconducting transition around T{sub c} = 90 K as well as high J{sub c} (0 T, 77 K) over 3 MA/cm{sup 2}.

Further development of IDGS: Isotope dilution gamma-ray spectrometry

International Nuclear Information System (INIS)

Li, T.K.; Parker, J.L.; Kuno, Y.; Sato, S.; Kamata, M.; Akiyama, T.

1991-01-01

The isotope dilution gamma-ray spectrometry (IDGS) technique for determining the plutonium concentration and isotopic composition of highly radioactive spent-fuel dissolver solutions has been further developed. Both the sample preparation and the analysis have been improved. The plutonium isotopic analysis is based on high-resolution, low-energy gamma-ray spectrometry. The plutonium concentration in the dissolver solutions then is calculated from the measured isotopic differences among the spike, the dissolver solution, and the spiked dissolver solution. Plutonium concentrations and isotopic compositions of dissolver solutions analyzed from this study agree well with those obtained by traditional isotope dilution mass spectrometry (IDMS) and are consistent with the first IDGS experimental result. With the current detector efficiency, sample size, and a 100-min count time, the estimated precision is ∼0.5% for 239 Pu and 240 Pu isotopic analyses and ∼1% for the plutonium concentration analysis. 5 refs., 2 figs., 7 tabs

Use of the fluorescence quantum yield for the determination of the number-average molecular weight of polymers of epicatechin with 4β→8 interflavin bonds

Science.gov (United States)

D. Cho; W.L. Mattice; L.J. Porter; Richard W. Hemingway

1989-01-01

Excitation at 280 nm produces a structureless emission band with a maximum at 321-324 nm for dilute solutions of catechin, epicatechin, and their oligomers in l,4-dioxane or water. The fluorescence quantum yield, Q, has been measured in these two solvents for five dimers, a trimer, a tetramer, a pentamer, a hexamer, and a polymer in which the monomer...

Atmospheric Pressure Plasma Jet Treatment of Poly-ε-caprolactone Polymer Solutions To Improve Electrospinning.

Science.gov (United States)

Grande, Silvia; Van Guyse, Joachim; Nikiforov, Anton Y; Onyshchenko, Iuliia; Asadian, Mahtab; Morent, Rino; Hoogenboom, Richard; De Geyter, Nathalie

2017-09-27

An atmospheric pressure plasma jet (APPJ) specifically designed for liquid treatment has been used in this work to improve the electrospinnability of a 5 w/v % solution of poly-ε-caprolactone (PCL) in a mixture of chloroform and N,N-dimethylformamide. Untreated PCL solutions were found to result in nonuniform fibers containing a large number of beads, whereas plasma-treated solutions (exposure time of 2-5 min) enabled the generation of beadless, uniform nanofibers with an average diameter of 450 nm. This enhanced electrospinnability was found to be mainly due to the highly increased conductivity of the plasma-modified PCL solutions. Consequently, more stretching of the polymer jet occurred during electrospinning, leading to the generation of bead-free fibers. Plasma treatment also results in an increased viscosity and decreased pH values. To explain these observed changes, optical emission spectroscopy (OES) has been used to examine the excited species present in the APPJ in contact with the PCL solution. This study revealed that the peaks attributed to H, CH, CH 2 , and C 2 species could be responsible for the degradation of solvent molecules and/or PCL structures during the plasma treatment. Size exclusion chromatography and X-ray photoelectron spectroscopy results showed that the molecular weight and the chemical composition of PCL were not significantly affected by the APPJ treatment. Plasma exposure mainly results in the degradation of the solvent molecules instead of modifying the PCL macromolecules, preserving the original polymer as much as possible. A hypothesis for the observed macroscopic changes in viscosity and pH values could be the generation of new chemical species such as HCl and/or HNO 3 . These species are characterized by their high conductivity, low pH values, and strong polarity and could enhance the solvent quality for PCL, leading to the expansion of the polymer coil, which could in turn explain the observed enhanced viscosity after plasma

All-solution processed polymer light-emitting diodes with air stable metal-oxide electrodes

NARCIS (Netherlands)

Bruyn, P. de; Moet, D.J.D.; Blom, P.W.M.

2012-01-01

We present an all-solution processed polymer light-emitting diode (PLED) using spincoated zinc oxide (ZnO) and vanadium pentoxide (V2O5) as electron and hole injecting contact, respectively. We compare the performance of these devices to the standard PLED design using PEDOT:PSS as anode and Ba/Al as

Self-Assembled CNT-Polymer Hybrids in Single-Walled Carbon Nanotubes Dispersed Aqueous Triblock Copolymer Solutions

Science.gov (United States)

Vijayaraghavan, D.; Manjunatha, A. S.; Poojitha, C. G.

2018-04-01

We have carried out scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), electrical conductivity, and 1H NMR studies as a function of temperature on single-walled carbon nanotubes (SWCNTs) dispersed aqueous triblock copolymer (P123) solutions. The single-walled carbon nanotubes in this system aggregate to form bundles, and the bundles aggregate to form net-like structures. Depending on the temperature and phases of the polymer, this system exhibits three different self-assembled CNT-polymer hybrids. We find CNT-unimer hybrid at low temperatures, CNT-micelle hybrid at intermediate temperatures wherein the polymer micelles are adsorbed in the pores of the CNT nets, and another type of CNT-micelle hybrid at high temperatures wherein the polymer micelles are adsorbed on the surface of the CNT bundles. Our DSC thermogram showed two peaks related to these structural changes in the CNT-polymer hybrids. Temperature dependence of the 1H NMR chemical shifts of the molecular groups of the polymer and the AC electrical conductivity of the composite also showed discontinuous changes at the temperatures at which the CNT-polymer hybrid's structural changes are seen. Interestingly, for a higher CNT concentration (0.5 wt.%) in the system, the aggregated polymer micelles adsorbed on the CNTs exhibit cone-like and cube-like morphologies at the intermediate and at high temperatures respectively.

Microfluidic rheometry of a polymer solution by micron resolution particle image velocimetry: a model validation study

International Nuclear Information System (INIS)

Hemaka Bandalusena, H C; Zimmerman, William B; Rees, Julia M

2009-01-01

The main purpose of this study is to model non-Newtonian fluid flows in microgeometries. Velocity fields of dilute xanthan gum solutions in a microfluidic T-junction have been measured for pressure-driven flow using micron resolution particle image velocimetry (µ-PIV). Xanthan gum at a fixed concentration is a power-law fluid. Varying the concentration changes the rheology, effectively altering the power-law parameters reflecting the changes in the fluid's shear response since viscoelasticity and extensional viscosity are negligible for dilute solutions of this substance. As the flow is forced to turn the corner of the T-junction, a range of shear rates, and hence viscosities, is produced. If this feature could be incorporated into a viscometer, then potentially the constitutive parameters of a complex fluid could be ascertained from a single experiment. A mathematical model based on a finite element technique has been developed to simulate the fluid flow in the experimental system. Model predictions of the velocity field are found to agree well (less than 5% error) with observations, thus validating the model

A novel polymer of Al2(SO43-poly(acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonate ionic hybrid prepared by dispersion polymerization

Directory of Open Access Journals (Sweden)

2010-03-01

Full Text Available A novel polymer Al2(SO43-poly(acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonate (Al2(SO43-P(AM/AMPS had been synthesized by dispersion polymerization in an aqueous solution of ammonium sulfate and aluminum sulfate, using poly(2-acrylamido-2-methyl-1-propanesulfonate P(AMPS as stabilizer, acrylamide (AM and 2-acrylamido-2-methyl-1-propanesulfonate (AMPS as monomers, poly(2-acrylamido-2-methyl-1-propanesulfonate (PAMPS as stabilizer and [2-(2-imidazdino-2-ylpropane]dihydrochloride (VA-044 as initiator. The average particle size of polymer dispersion ranged from 0.2 to 0.3 µm, the molecular weight was from 4.3•106 to 5.7•106 g•mol-1. The polymer was characterized by infrared (IR spectroscopy, thermogravimetry (TGA and transmission electron microscopy (TEM. The swelling property of the dispersion polymer was studied by particle size distribution. When the polymer dispersion was diluted with deionized water, particle sizes decreased several times. When the polymer dispersion was diluted with salt water, the particle size increased with increasing concentration of salt. The effects of Al2(SO43 and stabilizer on the particle size and the relative molecular weight of the polymer were investigated, respectively. The optimum conditions for the stable Al2(SO43-P(AM/AMPS dispersion were that the concentration of Al2(SO43 was 1.12 wt%, the concentration of PAMPS stabilizer was 3 wt% and the concentration of initiator was 0.2 mol•l-1 and the monomers concentration was 14 wt%.

Development of polymer-extractant composite beads for separation of radionuclides

International Nuclear Information System (INIS)

Kumar, Manmohan; Singh, Krishankant; Bajaj, P.N.

2009-01-01

A novel micro porous polymer-extractant composite bead system, containing liquid extractant encapsulated in the core of a polymeric shell, with required porosity and hydrophilicity, to allow exchange of radionuclides without, any significant leaching out of the encapsulated extractant, has been developed for solid-liquid extraction of radionuclides from acidic waste solutions. The reuse of the beads is possible as there is practically no change in its radionuclide extraction efficiency, after repeated extraction second time. The high porosity and hydrophilicity of the synthesized TBP-encapsulated polymeric beads is evident from the presence of ∼ 78% water in the swollen condition. Evaluation of the synthesized beads for extraction of uranium and plutonium from aqueous acidic waste solutions, indicated possibility of their use under the conditions of PUREX process. The aliquate 336-encapsulated polymeric beads showed selective extraction of plutonium from aqueous nitrate solutions in the presence of uranium, and back extraction of the loaded plutonium, using dilute nitric acid or ascorbic acid. (author)

Activity coefficients at infinite dilution and enthalpies of solution of methanol, 1-butanol, and 1-hexanol in 1-hexyl-3-methyl-imidazolium bis(trifluoromethyl-sulfonyl) imide

International Nuclear Information System (INIS)

Heintz, Andreas; Verevkin, Sergey P.; Lehmann, Jochen K.; Vasiltsova, Tatiana V.; Ondo, Daniel

2007-01-01

Activity coefficients at infinite dilution γ i ∼ of methanol, 1-butanol, and 1-hexanol in the ionic liquid 1-hexyl-3-methyl-imidazolium bis(trifluoromethyl-sulfonyl) imide ([HMIM][NTf 2 ]) have been determined by gas chromatography using the ionic liquids as stationary phase. The measurements were carried out at different temperatures between 298K and 396K. From the temperature dependence of the limiting activity coefficients partial molar excess enthalpies at infinite dilution H i E,∼ of the alcohol in the ionic liquid have been derived. Additionally, enthalpies of solution of the same alcohols in the [HMIM][NTf 2 ] have been measured at T=298.15K in the range of low concentrations using titration calorimetry. Results at infinite dilution, H i E,∼ , are compared with those indirectly obtained from activity coefficients in infinite dilution γ i ∼ . Within the experimental error of both methods thermodynamic consistency has been confirmed

Discrepancy between different estimates of the hydrodynamic diameter of polymer-coated iron oxide nanoparticles in solution

International Nuclear Information System (INIS)

Regmi, R.; Gumber, V.; Subba Rao, V.; Kohli, I.; Black, C.; Sudakar, C.; Vaishnava, P.; Naik, V.; Naik, R.; Mukhopadhyay, A.; Lawes, G.

2011-01-01

We have synthesized iron oxide nanoparticles coated with a monolayer of dextran, with molecular weights of the polymer between 5 and 670 kDa. Transmission electron microscopy images confirm that the hard core has a crystalline diameter of approximately 12 nm. The hydrodynamic diameters of these coated nanoparticles in solution measured using dynamical light scattering and estimated from magnetic susceptibility studies vary from near 90 nm for the lightest polymer to 140 nm for the heaviest polymer. Conversely, fluorescence correlation spectroscopy measurements yield a diameter of approximately 55 nm for the 15–20 kDa dextran coated nanoparticles, which is consistent with the expected value estimated from the sum of the hard-core diameter and monolayer dextran coating. We discuss the implications of this discrepancy for applications involving polymer-coated magnetic nanoparticles.

GRAIN-BOUNDARY PRECIPITATION UNDER IRRADIATION IN DILUTE BINARY ALLOYS

Institute of Scientific and Technical Information of China (English)

S.H. Song; Z.X. Yuan; J. Liu; R.G.Faulkner

2003-01-01

Irradiation-induced grain boundary segregation of solute atoms frequently bring about grain boundary precipitation of a second phase because of its making the solubility limit of the solute surpassed at grain boundaries. Until now the kinetic models for irradiation-induced grain boundary precipitation have been sparse. For this reason, we have theoretically treated grain boundary precipitation under irradiation in dilute binary alloys. Predictions ofγ'-Ni3Si precipitation at grain boundaries ave made for a dilute Ni-Si alloy subjected to irradiation. It is demonstrated that grain boundary silicon segregation under irradiation may lead to grain boundaryγ'-Ni3 Si precipitation over a certain temperature range.

Highly sensitive and selective hyphenated technique (molecularly imprinted polymer solid-phase microextraction-molecularly imprinted polymer sensor) for ultra trace analysis of aspartic acid enantiomers.

Science.gov (United States)

Prasad, Bhim Bali; Srivastava, Amrita; Tiwari, Mahavir Prasad

2013-03-29

The present work is related to combination of molecularly imprinted solid-phase microextraction and complementary molecularly imprinted polymer-sensor. The molecularly imprinted polymer grafted on titanium dioxide modified silica fiber was used for microextraction, while the same polymer immobilized on multiwalled carbon nanotubes/titanium dioxide modified pencil graphite electrode served as a detection tool. In both cases, the surface initiated polymerization was found to be advantageous to obtain a nanometer thin imprinted film. The modified silica fiber exhibited high adsorption capacity and enantioselective diffusion of aspartic acid isomers into respective molecular cavities. This combination enabled double preconcentrations of d- and l-aspartic acid that helped sensing both isomers in real samples, without any cross-selectivity and matrix complications. Taking into account 6×10(4)-fold dilution of serum and 2×10(3)-fold dilution of cerebrospinal fluid required by the proposed method, the limit of detection for l-aspartic acid is 0.031ngmL(-1). Also, taking into account 50-fold dilution required by the proposed method, the limit of detection for d-aspartic acid is 0.031ngmL(-1) in cerebrospinal fluid. Copyright © 2013 Elsevier B.V. All rights reserved.

Stacking layered structure of polymer light emitting diodes prepared by evaporative spray deposition using ultradilute solution for improving carrier balance

International Nuclear Information System (INIS)

Aoki, Youichi; Shakutsui, Masato; Fujita, Katsuhiko

2009-01-01

Polymer light-emitting diodes (PLEDs) with staking layered structures are prepared by the evaporative spray deposition using ultradilute solution (ESDUS) method, which has enabled forming a polymer layer onto another polymer layer even if both polymers are soluble in a solvent used for the preparation. By this method, polymers having various HOMO and LUMO levels can be stacked as a hole transport layer, an emitting layer and an electron transport layer as commonly employed in small molecule-based organic light emitting diodes. Here we demonstrated that a PLED having a tri-layer structure using three kinds of polymers showed significant improvement in quantum efficiency compared with those having a single or bi-layer structure of corresponding polymers.

Activity coefficients at infinite dilution and physicochemical properties for organic solutes and water in the ionic liquid 1-(3-hydroxypropyl)pyridinium bis(trifluoromethylsulfonyl)-amide

International Nuclear Information System (INIS)

Marciniak, Andrzej

2011-01-01

Highlights: → The γ 13 ∞ and KL for 46 solutes in the ionic liquid [N-C3OHPY][NTf2] were determined by GLC at different temperatures. → The partial molar excess Gibbs energies ΔG 1 E,∞ , enthalpies ΔH 1 E,∞ and entropies ΔS 1 E,∞ at infinite dilution were calculated. → The selectivities for aliphatics/aromatics hydrocarbons separation problem were calculated and compared to other ILs, NMP and sulfolane. → The selectivities for selected compounds which form azeotropic mixtures were calculated. - Abstract: The activity coefficients at infinite dilution, γ 13 ∞ and gas-liquid partition coefficients, K L for 46 solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, acetic acid, and water in the ionic liquid 1-(3-hydroxypropyl)pyridinium bis(trifluoromethylsulfonyl)-amide were determined by gas-liquid chromatography at the temperatures from (308.15 to 378.15) K. The partial molar excess Gibbs free energies ΔG 1 E,∞ , enthalpies ΔH 1 E,∞ and entropies ΔS 1 E,∞ at infinite dilution were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The selectivities for aliphatic/aromatic hydrocarbons separation problem were calculated from the γ 13 ∞ and compared to the literature values for other ionic liquids based on bis(trifluoromethylsulfonyl)-amide anion, NMP and sulfolane. It was found that the investigated ionic liquid shows much higher selectivity at infinite dilution than the general used organic solvents such as NMP, sulfolane and other ionic liquids. Additionally the selectivities for selected compounds which form azeotropic mixtures were calculated.

Vapor-Liquid Equilibrium in Diluted Polymer plus Solvent Systems

Czech Academy of Sciences Publication Activity Database

Bogdanić, Grozdana; Wichterle, Ivan

2011-01-01

Roč. 56, č. 4 (2011), s. 1080-1083 ISSN 0021-9568 R&D Projects: GA ČR GA104/07/0444 Grant - others:MZOŠ(HR) 061-0000000-3029 Institutional research plan: CEZ:AV0Z40720504 Keywords : polymer * prediction * total pressure Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.693, year: 2011

Activity coefficients at infinite dilution and physicochemical properties for organic solutes and water in the ionic liquid 1-(2-methoxyethyl)-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide

International Nuclear Information System (INIS)

Marciniak, Andrzej; Wlazło, Michał

2012-01-01

Highlights: The and KL for 61 solutes in the ionic liquid [COC2mPIP][NTf2] were determined by IGC at different temperatures. ► The partial molar excess Gibbs energies, enthalpies and entropies at infinite dilution were calculated. ► The selectivities for selected compounds which form azeotropic mixtures were calculated and compared to other ILs. ► LFER system constants as a function of temperature for [COC2mPIP][NTf2] were calculated. - Abstract: The activity coefficients at infinite dilution, γ ∞ and gas–liquid partition coefficients, K L for 61 solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, esters, 1-nitropropane, butanal, acetonitrile, and water in the ionic liquid 1-(2-methoxyethyl)-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide were determined by inverse gas chromatography at the temperatures from (318.15 to 368.15) K. The partial molar excess Gibbs free energies ΔG 1 E,∞ , enthalpies ΔH 1 E,∞ and entropies ΔS 1 E,∞ at infinite dilution were calculated from the experimental γ ∞ values obtained over the temperature range. The selectivities for selected compounds, which form azeotropic mixtures, were calculated from the γ ∞ and compared to the literature values for other ionic liquids based on bis(trifluoromethylsulfonyl)-amide anion.

Activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide

International Nuclear Information System (INIS)

Domanska, Urszula; Marciniak, Andrzej

2009-01-01

The activity coefficients at infinite dilution, γ 13 ∞ for 36 solutes: alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, tetrahydrofuran, ethers, acetone, and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide [bmPY][NTf 2 ] were determined by gas-liquid chromatography at temperatures from 298.15 K to 368.15 K. The partial molar excess enthalpies at infinite dilution values ΔH 1 E,∞ were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The selectivity for different separation problems were calculated from the γ 13 ∞ and compared to the literature values for other ionic liquids, N-methyl-2-pyrrolidinone (NMP) and sulfolane.

Interaction Studies of Dilute Aqueous Oxalic Acid

Directory of Open Access Journals (Sweden)

Kiran Kandpal

2007-01-01

Full Text Available Molecular conductance λm, relative viscosity and density of oxalicacid at different concentration in dilute aqueous solution were measured at 293 K.The conductance data were used to calculate the value association constant.Viscosity and density data were used to calculate the A and B coefficient ofJone-Dole equation and apparent molar volume respectively. The viscosityresults were utilized for the applicability of Modified Jone-Dole equation andStaurdinger equations. Mono oxalate anion acts, as structure maker and thesolute-solvent interaction were present in the dilute aqueous oxalic acid.

Shear Strength of Stabilized Kaolin Soil Using Liquid Polymer

Science.gov (United States)

Azhar, A. T. S.; Fazlina, M. I. S.; Nizam, Z. M.; Fairus, Y. M.; Hakimi, M. N. A.; Riduan, Y.; Faizal, P.

2017-08-01

The purpose of this research is to investigate the suitability of polymer in soil stabilization by examining its strength to withstand compressive strength. Throughout this research study, manufactured polymer was used as a chemical liquid soil stabilizer. The liquid polymer was diluted using a proposed dilution factor of 1 : 3 (1 part polymer: 3 parts distilled water) to preserve the workability of the polymer in kaolin mixture. A mold with a diameter of 50 mm and a height of 100 mm was prepared. Kaolin soil was mixed with different percentages of polymer from 10%, 15%, 20%, 25%, 30% and 35% of the mass of the kaolin clay sample. Kaolin mixtures were tested after a curing period of 3 days, 7 days, 14 days and 28 days respectively. The physical properties were determined by conducting a moisture content test and Atterberg limit test which comprise of liquid limit, plastic limit and shrinkage limit. Meanwhile, the mechanical properties of the soil shear strength were identified through an unconfined compressive strength (UCS) test. Stabilized kaolin soil showed the highest compressive strength value when it was mixed with 35% of polymer compared to other percentages that marked an increment in strength which are 45.72% (3 days), 67.57% (7 days), 81.73% (14 days) and 77.84% (28 days). Hence, the most effective percentage of liquid polymer which should be used to increase the strength of kaolin soil is 35%.

Electron pairing in dilute liquid metal-metal halide solutions

Energy Technology Data Exchange (ETDEWEB)

Selloni, A.; Car, R.; Parrinello, M.; Carnevali, P.

1987-09-10

Spin density functional theory is used to describe the interaction between solvated electrons in KCl in the high dilution limit. In agreement with recent calculations based on the path integral method our results for antiparallel spin predict a strong tendency to form localized bielectronic complexes. At variance with numerical path integral, our method can efficiently treat the case of parallel spins. For this case we find that electrons repel each other and localize into separate F-center-like states.

Effect of pH Value on the Electrochemical and Stress Corrosion Cracking Behavior of X70 Pipeline Steel in the Dilute Bicarbonate Solutions

Science.gov (United States)

Cui, Z. Y.; Liu, Z. Y.; Wang, L. W.; Ma, H. C.; Du, C. W.; Li, X. G.; Wang, X.

2015-11-01

In this work, effects of pH value on the electrochemical and stress corrosion cracking (SCC) behavior of X70 pipeline steel in the dilute bicarbonate solutions were investigated using electrochemical measurements, slow strain rate tensile tests and surface analysis techniques. Decrease of the solution pH from 6.8 to 6.0 promotes the anodic dissolution and cathodic reduction simultaneously. Further decrease of the pH value mainly accelerates the cathodic reduction of X70 pipeline steel. As a result, when the solution pH decreases form 6.8 to 5.5, SCC susceptibility decreases because of the enhancement of the anodic dissolution. When the solution pH decreases from 5.5 to 4.0, SCC susceptibility increases gradually because of the acceleration of cathodic reactions.

Activity coefficients at infinite dilution of organic solutes in the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate using gas-liquid chromatography at T = (313.15, 323.15, and 333.15) K

International Nuclear Information System (INIS)

Olivier, Eugene; Letcher, Trevor M.; Naidoo, Paramespri; Ramjugernath, Deresh

2010-01-01

Activity coefficients at infinite dilution were determined for 24 solutes (n-alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, alkylbenzenes, and alcohols) in the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate by gas-liquid chromatography at three different temperatures T = (313.15, 323.15, 333.15) K. The partial molar excess enthalpy values at infinite dilution were calculated from the experimental results over the same temperature range. Selectivities and capacities at infinite dilution for the hexane/benzene and methanol/benzene separation problems were calculated from experimental infinite dilution activity coefficient values. The activity coefficients, enthalpies, selectivities, and capacities are discussed and compared to literature values for other ionic liquids, as well as industrial molecular solvents.

A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

OpenAIRE

Moia, Davide; Giovannitti, Alexander; Szumska, Anna A.; Schnurr, Martin; Rezasoltani, Elham; Maria, Iuliana P.; Barnes, Piers R. F.; McCulloch, Iain; Nelson, Jenny

2017-01-01

We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient t...

''Over the horizon'' SANS: Measurements on near-surface Poiseuille shear-induced ordering of dilute solutions of threadlike micelles

International Nuclear Information System (INIS)

Hamilton, W.A.; Butler, P.D.; Hayter, J.B.; Magid, L.J.; Kreke, P.J.

1995-01-01

Although the behavior of a fluid under shear near a surface can be expected to be critically important to its drag and lubrication properties, most shear measurements to date have been of the bulk. This paper outlines the use of a specially developed Poiseuille shear cell at grazing incidence to measure the small-angle neutron scattering (SANS) signal from the first few tens of microns in the interfacial region. The authors illustrate the technique with measurements made on the near-surface ordering in flow past a quartz surface of dilute surfactant solutions comprising highly extended self-assembling ''threadlike'' micelles

Research on the structure in solution of optically active synthetic polymers (propylene polysulphide, propylene polyoxide, tertio-butyl polysulphide)

International Nuclear Information System (INIS)

Sarrazin, Brigitte

1971-03-01

It was proposed to study the structure of sulphur-containing synthetic polymers, stereo-regular, optically active in solution and able to adopt a spiral conformation, with special reference to propylene polysulphide. Two methods were used, the first mathematical (conformational energy calculations) and the second physico-chemical, essentially spectroscopic. By conformational analysis it is possible to choose the most probable structures liable to be adopted by a given polymer in solution while the spectro-polarimetric study should, in principle, invalidate or confirm certain of these hypotheses. The conformational energy calculations showed that in fact there is no energy conformation low enough to be stable in solution. Strictly speaking however we can refer to a region of stability in which steric hindrance is low and many energy minima exist. These minima are indistinguishable both by their energy values and by their spatial localizations and are all enclosed in the region bounded by the barriers due to steric hindrance. This uncertainty does not arise from approximations made in the calculations, but from the multitude of stereochemical structure possible. Investigations into the variation of the optical rotary dispersion and the circular dichroism as a function of temperature indicated the existence of three or more equilibrium states in the dioxane. The spectra appear to be the summation of the optical activities of the numerous simultaneously possible conformations. It appears that polymers, such as propylene polysulphide or propylene polyoxide do not have stable structures in solution. These are molecules of great flexibility possessing a large number of degrees of freedom. These properties distinguish them from the natural polymers, carrying precise information, such as DNA which must consequently have stable conformations. (author) [fr

Gel phase formation in dilute triblock copolyelectrolyte complexes

Science.gov (United States)

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

2017-02-01

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

Dilution thermodynamics of the biologically relevant cation mixtures

International Nuclear Information System (INIS)

Kaczyński, Marek; Borowik, Tomasz; Przybyło, Magda; Langner, Marek

2014-01-01

Graphical abstract: - Highlights: • Dilution energetics of Ca 2+ can be altered by the aqueous phase ionic composition. • Dissipated heat upon Ca 2+ dilution is drastically reduced in the K + presence. • Reduction of the enthalpy change upon Ca 2+ dilution is K + concentration dependent. • The cooperativity of Ca 2+ hydration might be of great biological relevance providing a thermodynamic argument for the specific ionic composition of the intracellular environment. - Abstract: The ionic composition of intracellular space is rigorously controlled by a variety of processes consuming large quantities of energy. Since the energetic efficiency is an important evolutional criterion, therefore the ion fluxes within the cell should be optimized with respect to the accompanying energy consumption. In the paper we present the experimental evidence that the dilution enthalpies of the biologically relevant ions; i.e. calcium and magnesium depend on the presence of monovalent cations; i.e. sodium and potassium. The heat flow generated during the dilution of ionic mixtures was measured with the isothermal titration calorimetry. When calcium was diluted together with potassium the dilution enthalpy was drastically reduced as the function of the potassium concentration present in the solution. No such effect was observed when the potassium ions were substituted with sodium ones. When the dilution of magnesium was investigated the dependence of the dilution enthalpy on the accompanying monovalent cation was much weaker. In order to interpret experimental evidences the ionic cluster formation is postulated. The specific organization of such cluster should depend on ions charges, sizes and organization of the hydration layers

A Dilute-Limit Heat of Solution of 3d Transition Metals in Iron Studied with 57Fe Moessbauer Spectroscopy

International Nuclear Information System (INIS)

Chojcan, Jan

2004-01-01

The room-temperature 57 Fe Moessbauer spectra for binary iron-based solid solutions Fe 1-x D x with D=V, Cr, Mn and Co, were analysed in terms of binding energy E b between two D atoms in the Fe-D system. The extrapolated values of E b for x=0 were used for computation of the dilute-limit heat of solution of D metals in iron. The results were compared with those derived from calorimetric data concerning the heat of formation of the systems mentioned as well as with those resulting from the Miedema's model of alloys. The comparison shows that our Moessbauer spectroscopy findings are in a qualitative agreement with the available calorimetric data and they are at variance with corresponding Miedema's values for Fe-Mn and Fe-Co systems.

Nano-scale patterns of polymers and their structural phase transitions

Energy Technology Data Exchange (ETDEWEB)

Matsushita, Yushu [Tokyo Univ. (Japan). Inst. for Solid State Physics

1998-03-01

Nano-scale patterns formed by polymers and their related soft materials were investigated by measuring neutron scattering from them. Two apparatuses installed at cold neutron guides in JRR-3M, a small angle neutron scattering (SANS) apparatus and a neutron reflectometer, which give out elastic scattering intensities, were used. Chain dimensions of polystyrenes diluted with low molecular weight homologous polystyrenes, orientation behaviour of microphase-separated block copolymer in concentrated solutions under shear, shrinkage and recovery of polyvinylalcohol gel with temperature and structural phase transition of microemulsion under high-pressure and so on were measured by SANS, while microphase-separated polystyrene(S)/poly(2-vinylpyridine)(P) interfaces of a PSP triblock copolymer was observed by specular neutron reflectivity measurements. (author)

Dynamical scaling in polymer solutions investigated by the neutron spin echo technique

International Nuclear Information System (INIS)

Richter, D.; Ewen, B.

1979-01-01

Chain dynamics in polymer solutions was investigated by means of the recently developed neutron spin echo spectroscopy. - By this technique, it was possible for the first time to verify unambiguously the scaling predictions of the Zimm model in the case of single chain behaviour and to observe the cross over to many chain behaviour. The segmental diffusion of single chains exhibits deviations from a simple exponential law, indicating the importance of memory effects. (orig.) [de

Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

International Nuclear Information System (INIS)

Minelli, Matteo; Doghieri, Ferruccio

2014-01-01

Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps

Activity coefficients at infinite dilution and physicochemical properties for organic solutes and water in the ionic liquid 1-(3-hydroxypropyl)pyridinium bis(trifluoromethylsulfonyl)-amide

Energy Technology Data Exchange (ETDEWEB)

Marciniak, Andrzej, E-mail: a.marciniak@ch.pw.edu.pl [Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland)

2011-10-15

Highlights: > The {gamma}{sub 13}{sup {infinity}} and KL for 46 solutes in the ionic liquid [N-C3OHPY][NTf2] were determined by GLC at different temperatures. > The partial molar excess Gibbs energies {Delta}G{sub 1}{sup E,{infinity}}, enthalpies {Delta}H{sub 1}{sup E,{infinity}} and entropies {Delta}S{sub 1}{sup E,{infinity}} at infinite dilution were calculated. > The selectivities for aliphatics/aromatics hydrocarbons separation problem were calculated and compared to other ILs, NMP and sulfolane. > The selectivities for selected compounds which form azeotropic mixtures were calculated. - Abstract: The activity coefficients at infinite dilution, {gamma}{sub 13}{sup {infinity}} and gas-liquid partition coefficients, K{sub L} for 46 solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, acetic acid, and water in the ionic liquid 1-(3-hydroxypropyl)pyridinium bis(trifluoromethylsulfonyl)-amide were determined by gas-liquid chromatography at the temperatures from (308.15 to 378.15) K. The partial molar excess Gibbs free energies {Delta}G{sub 1}{sup E,{infinity}}, enthalpies {Delta}H{sub 1}{sup E,{infinity}} and entropies {Delta}S{sub 1}{sup E,{infinity}} at infinite dilution were calculated from the experimental {gamma}{sub 13}{sup {infinity}} values obtained over the temperature range. The selectivities for aliphatic/aromatic hydrocarbons separation problem were calculated from the {gamma}{sub 13}{sup {infinity}} and compared to the literature values for other ionic liquids based on bis(trifluoromethylsulfonyl)-amide anion, NMP and sulfolane. It was found that the investigated ionic liquid shows much higher selectivity at infinite dilution than the general used organic solvents such as NMP, sulfolane and other ionic liquids. Additionally the selectivities for selected compounds which form azeotropic mixtures were calculated.

Gas-liquid chromatography measurements of activity coefficients at infinite dilution of various organic solutes and water in tri-iso-butylmethylphosphonium tosylate ionic liquid

International Nuclear Information System (INIS)

Domanska, Urszula; Paduszynski, Kamil

2010-01-01

Activity coefficients at infinite dilution (γ 13 ∞ ) of 33 different solutes (including alkanes, cycloalkanes, alkenes, alkynes, benzene, alkylbenzenes, water, alcohols, MTBE, thiophene and THF) in the ionic liquid tri-iso-butylmethylphosphonium tosylate have been determined by using the GLC method and have been reported over the temperature range (298.15 to 368.15) K. The partial molar excess enthalpies of mixing at infinite dilution have been determined based on temperature dependence of γ 13 ∞ . Selectivity and capacity at infinite dilution has been also calculated for exemplary separation processes in systems n-hexane/benzene and n-hexane/thiophene, to evaluate if the studied ionic liquid is capable to be a good entrainer for these processes, e.g. in the liquid-liquid extraction. The obtained results are promising however the ionic liquid studied shows a lower selectivity than some of imidazolium-based ionic liquids. To our best knowledge, the results indicate that tri-iso-butylmethylphosphonium tosylate is the best for the separation problem of aliphatic hydrocarbons from aromatic hydrocarbons among all of the studied quaternary phosphonium-based ionic liquids.

Activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide

Energy Technology Data Exchange (ETDEWEB)

Domanska, Urszula [Physical Chemistry Department, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland)], E-mail: ula@ch.pw.edu.pl; Marciniak, Andrzej [Physical Chemistry Department, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland)

2009-12-15

The activity coefficients at infinite dilution, {gamma}{sub 13}{sup {infinity}} for 36 solutes: alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, tetrahydrofuran, ethers, acetone, and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide [bmPY][NTf{sub 2}] were determined by gas-liquid chromatography at temperatures from 298.15 K to 368.15 K. The partial molar excess enthalpies at infinite dilution values {delta}H{sub 1}{sup E,{infinity}} were calculated from the experimental {gamma}{sub 13}{sup {infinity}} values obtained over the temperature range. The selectivity for different separation problems were calculated from the {gamma}{sub 13}{sup {infinity}} and compared to the literature values for other ionic liquids, N-methyl-2-pyrrolidinone (NMP) and sulfolane.

Dilution and Mixing in transient velocity fields: a first-order analysis

Science.gov (United States)

Di Dato, Mariaines; de Barros, Felipe, P. J.; Fiori, Aldo; Bellin, Alberto

2017-04-01

An appealing remediation technique is in situ oxidation, which effectiveness is hampered by difficulties in obtaining good mixing of the injected oxidant with the contaminant, particularly when the contaminant plume is contained and therefore its deformation is physically constrained. Under such conditions (i.e. containment), mixing may be augmented by inducing temporal fluctuations of the velocity field. The temporal variability of the flow field may increase the deformation of the plume such that diffusive mass flux becomes more effective. A transient periodic velocity field can be obtained by an engineered sequence of injections and extractions from wells, which may serve also as a hydraulic barrier to confine the plume. Assessing the effectiveness of periodic flows to maximize solute mixing is a difficult task given the need to use a 3D setup and the large number of possible flow configurations that should be analyzed in order to identify the optimal one. This is the typical situation in which analytical solutions, though approximated, may assist modelers in screening possible alternative flow configurations such that solute dilution is maximized. To quantify dilution (i.e. a precondition that enables reactive mixing) we utilize the concept of the dilution index [1]. In this presentation, the periodic flow takes place in an aquifer with spatially variable hydraulic conductivity field which is modeled as a Stationary Spatial Random Function. We developed a novel first-order analytical solution of the dilution index under the hypothesis that the flow can be approximated as a sequence of steady state configurations with the mean velocity changing with time in intensity and direction. This is equivalent to assume that the characteristic time of the transient behavior is small compared to the period characterizing the change in time of the mean velocity. A few closed paths have been analyzed quantifying their effectiveness in enhancing dilution and thereby mixing

Conformation of Single Pentablock Ionomer Chains in Dilute Solutions

Energy Technology Data Exchange (ETDEWEB)

Aryal, Dipak [Clemson Univ., SC (United States); Perahia, Dvora [Clemson Univ., SC (United States); Grest, Gary S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2015-04-01

The conformation of single chain pentablock ionomers (A-B-C-B-A) containing randomly sulfonated polystyrene in the center block, tethered to poly-ethylene-r-propylene end-capped by poly-t-butyl styrene is studied in dilute solutions by molecular dynamics simulations. Multi-block copolymers offer a means to tailor several properties into one molecule, taking advantage of their rich phase diagram together with unique properties of specific blocks. For this pentablock the ionic block facilitates transport while the A and B components are incorporated for mechanical stability. The present study investigates the confirmation of a single chain of pentablock ionomer of molecular weight M_w ~ 50,000 g/mol and sulfonated polystyrene of the same molecular weight as that of the center block for six sulfonation fractions f from f=0.0-0.55. For the sulfonated systems Na⁺ counterions are included. Results for the equilibrium conformation of the chains and the three blocks in water and 1:1 mixture of cyclohexane and n-heptane are compared to simulations in implicit poor solvents with dielectric constants ε =1.0 and 77.73. In water, the pentablock is collapsed with sulfonated groups on the outer surface. As the sulfonation fraction f increases, the ionic, center block is increasingly segregated from the hydrophobic regions. In the 1:1 mixture of cyclohexane and heptane both the flexible and end blocks are swollen while the center ionic block is collasped for f>0, while for f=0 all blocks are swollen. In both implicit poor solvents the pentablock is collapsed into a nearly spherical shape for all f. The sodium counterions are dispersed widely throughout the simulation cell for both water and ε =77.73 whereas for ε =1.0 the counterions are largely condensed on the collapsed pentablock.

Enthalpies of the dissolution and dilution of aqueous solutions of rubidium and cesium diclofenac at 293.15-318.15 K

Science.gov (United States)

Manin, N. G.; Perlovich, G. L.; Fini, A.

2014-03-01

Enthalpies of the dissolution and dilution of aqueous solutions of rubidium and cesium diclofenac (RbDC and CsDC) are measured at 293.15, 298.15, 308.15, and 318.15 K at concentrations of water of less than 0.1 mol/kg. The heat capacity of RbDC and CsDC crystal salts is determined. Changes in the thermodynamic properties of both a solution and its components vs. concentration and temperature is considered. An increase in the endothermicity of the dissolution of RbDC and CsDC with a rise in temperature is noted. It is shown that the dissolution of both RbDC and CsDC electrolytes in water is determined by the contribution from entropy. It is shown that in aqueous solutions of RbDC and CsDC, the degree of binding of water molecules is higher than in pure water at temperatures below 303.15 K.

The solubility of UO22+ in dilute sodium chloride solutions and in high-ionic strength sodium sulfate and chlorine brines

International Nuclear Information System (INIS)

Marquez, L.N.; Kadkhodayan, B.; Wruck, D.A.

1995-01-01

Uranium is a major component of high-level nuclear waste. In an oxidizing environment, UO 2 2+ would be expected to be the dominant dissolved species in solution. In addition to dilute solutions, because high-level nuclear waste may be stored in repositories containing salt, it is important to characterize the aqueous chemistry of UO 2 2+ and the solubility-controlling U(VI) solids in high-ionic strength brines as a function of pH. We have studied the solubility of UO 2 2+ by precipitation of solid phase in 0.001 molal NaCl, 5.2 molal NaCl, and saturated Na 2 SO 4 at pH values ranging from 5 to 12. The solution concentrations were measured by alpha particle liquid scintillation counting. The precipitated solids were characterized by powder x-ray diffraction, electron microscopy, infrared spectroscopy, and x-ray photoelectron spectroscopy

Polymer concentration and properties of elastic turbulence in a von Karman swirling flow

Science.gov (United States)

Jun, Yonggun; Steinberg, Victor

2017-10-01

We report detailed experimental studies of statistical, scaling, and spectral properties of elastic turbulence (ET) in a von Karman swirling flow between rotating and stationary disks of polymer solutions in a wide, from dilute to semidilute entangled, range of polymer concentrations ϕ . The main message of the investigation is that the variation of ϕ just weakly modifies statistical, scaling, and spectral properties of ET in a swirling flow. The qualitative difference between dilute and semidilute unentangled versus semidilute entangled polymer solutions is found in the dependence of the critical Weissenberg number Wic of the elastic instability threshold on ϕ . The control parameter of the problem, the Weissenberg number Wi, is defined as the ratio of the nonlinear elastic stress to dissipation via linear stress relaxation and quantifies the degree of polymer stretching. The power-law scaling of the friction coefficient on Wi/Wic characterizes the ET regime with the exponent independent of ϕ . The torque Γ and pressure p power spectra show power-law decays with well-defined exponents, which has values independent of Wi and ϕ separately at 100 ≤ϕ ≤900 ppm and 1600 ≤ϕ ≤2300 ppm ranges. Another unexpected observation is the presence of two types of the boundary layers, horizontal and vertical, distinguished by their role in the energy pumping and dissipation, which has width dependence on Wi and ϕ differs drastically. In the case of the vertical boundary layer near the driving disk, wvv is independent of Wi/Wic and linearly decreases with ϕ /ϕ * , while in the case of the horizontal boundary layer wvh its width is independent of ϕ /ϕ * , linearly decreases with Wi/Wic , and is about five times smaller than wvv. Moreover, these Wi and ϕ dependencies of the vertical and horizontal boundary layer widths are found in accordance with the inverse turbulent intensity calculated inside the boundary layers Vθh/Vθh rms and Vθv/Vθv rms , respectively

Buffer erosion in dilute groundwater

International Nuclear Information System (INIS)

Schatz, T.; Kanerva, N.; Martikainen, J.; Sane, P.; Olin, M.; Seppaelae, A.; Koskinen, K.

2013-08-01

One scenario of interest for repository safety assessment involves the loss of bentonite buffer material in contact with dilute groundwater flowing through a transmissive fracture interface. In order to examine the extrusion/erosion behavior of bentonite buffer material under such circumstances, a series of experiments were performed in a flow-through, 1 mm aperture, artificial fracture system. These experiments covered a range of solution chemistry (salt concentration and composition), material composition (sodium montmorillonite and admixtures with calcium montmorillonite), and flow velocity conditions. No erosion was observed for sodium montmorillonite against solution compositions from 0.5 g/L to 10 g/L NaCl. No erosion was observed for 50/50 calcium/sodium montmorillonite against 0.5 g/L NaCl. Erosion was observed for both sodium montmorillonite and 50/50 calcium/sodium montmorillonite against solution compositions ≤ 0.25 g/L NaCl. The calculated erosion rates for the tests with the highest levels of measured erosion, i.e., the tests run under the most dilute conditions (ionic strength (IS) < ∼1 mM), were well-correlated to flow velocity, whereas the calculated erosion rates for the tests with lower levels of measured erosion, i.e., the tests run under somewhat less dilute conditions (∼1 mM < IS < ∼4 mM), were not similarly correlated indicating that material and solution composition can significantly affect erosion rates. In every experiment, both erosive and non-erosive, emplaced buffer material extruded into the fracture and was observed to be impermeable to water flowing in the fracture effectively forming an extended diffusive barrier around the intersecting fracture/buffer interface. Additionally, a model which was developed previously to predict the rate of erosion of bentonite buffer material in low ionic strength water in rock fracture environments was applied to three different cases: sodium montmorillonite expansion in a vertical tube, a

Side Chain Engineering in Solution-Processable Conjugated Polymers

KAUST Repository

Mei, Jianguo

2014-01-14

Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer\\'s physical properties, including absorption, emission, energy level, molecular packing, and charge transport. To date, numerous flexible substituents suitable for constructing side chains have been reported. In this Perspective article, we advocate that the side chain engineering approach can advance better designs for next-generation conjugated polymers. © 2013 American Chemical Society.

Thermodynamics and activity coefficients at infinite dilution for organic solutes and water in the ionic liquid 1-butyl-1-methylmorpholinium tricyanomethanide

International Nuclear Information System (INIS)

Domańska, Urszula; Lukoshko, Elena Vadimovna

2014-01-01

Highlights: • Measurements of activity coefficients at infinite dilution using GLC. • Sixty one organic solvents in the ionic liquid 1-butyl-1-methylmorpholinium tricyanomethanide. • High selectivity for heptane/thiophene, or pyridine, or 1-nitropropane. • The excess thermodynamic functions and the gas–liquid partition coefficients were presented. • Possible entrainer for the extraction of sulphur and nitrogen-compounds from alkanes. -- Abstract: The activity coefficients at infinite dilution, γ 13 ∞ , for 61 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, water, thiophene, ethers, ketones, esters, aldehyde, acetonitrile, pyridine and 1-nitropropane in the ionic liquid (IL) 1-butyl-1-methylmorpholinium tricyanomethanide, [BMMOR][TCM] were determined by gas–liquid chromatography at six temperatures within the range of (318.15 to 368.15) K. The thermodynamic functions at infinite dilution as partial molar excess Gibbs free energy ΔG 1 E,∞ , enthalpy ΔH 1 E,∞ , and entropy term T ref ΔS 1 E,∞ were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The density of [BMMOR][TCM] was measured over the temperature range (288.15 to 368.15) K. The gas–liquid partition coefficient K L was calculated for all solutes. The values of selectivity and capacity for a few separation problems such as hexane/benzene, cyclohexane/benzene, heptane/thiophene at T = 328.15 K were calculated from γ 13 ∞ and compared to literature values for similar ionic liquids, viz. N-methyl-2-pyrrolidinone (NMP), and sulfolane. In comparison with the previously measured values for [BMPYR][TCM], the morpholinium IL presents high selectivity for the separation of aromatic hydrocarbons from aliphatic hydrocarbons, and especially thiophene, or piridine from heptane with a slightly lower capacity. New data show that [BMMOR][TCM] IL may be proposed as an alternative solvent for the separation of

Measurements of activity coefficients at infinite dilution for organic solutes and water in the ionic liquid 1-butyl-1-methylpyrrolidinium tricyanomethanide

International Nuclear Information System (INIS)

Domańska, Urszula; Lukoshko, Elena Vadimovna

2013-01-01

Highlights: • Measurements of activity coefficients at infinite dilution using GLC. • 62 organic solvents and water in the ionic liquid 1-butyl-1-methylpyrrolidinium tricyanomethanide. • High capacity for thiophene, 1.37 at T = 328.15 K. • Possible entrainer for extraction of sulfur, or nitrogen compounds from fuels. • The excess thermodynamic functions and the gas–liquid partition coefficients were calculated. -- Abstract: The activity coefficients at infinite dilution, γ 13 ∞ , for 62 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, water, thiophene, ethers, ketones, acetonitrile, pyridine and 1-nitropropane in the ionic liquid 1-butyl-1-methylpyrrolidinium tricyanomethanide, [BMPYR][TCM] were determined by gas–liquid chromatography at six temperatures over the range of (318.15 to 368.15) K. The partial molar excess Gibbs free energy, ΔG 1 E ∞, enthalpy ΔH 1 E ∞, and entropy term T ref ΔS 1 E ,∞ at infinite dilution were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The densities of [BMPYR][TCM] were measured within temperature range from 318.15 K to 368.15 K. The gas–liquid partition coefficients, K L were calculated for all solutes. The values of selectivity for few separation problems as hexane/benzene, cyclohexane/benzene, heptane/thiophene were calculated from γ 13 ∞ and compared to literature values for N-methyl-2-pyrrolidinone (NMP), sulfolane, and other ionic liquids based on [BMPYR] + cation. In comparison with the former measured ILs, [BMPYR][TCM] present quite high selectivity for the separation of aromatic hydrocarbons and aliphatics hydrocarbons, an average capacity for benzene. The data presented here shows that [BMPYR][TCM] ionic liquid can be used as an alternative solvent for the separation of thiophene from the aliphatic hydrocarbons

Synthesis of fast response crosslinked PVA-g-NIPAAm nanohydrogels by very low radiation dose in dilute aqueous solution

International Nuclear Information System (INIS)

Fathi, Marziyeh; Reza Farajollahi, Ali; Akbar Entezami, Ali

2013-01-01

Nanohydrogels of poly(vinyl alcohol)-g-N-isopropylacrylamide (PVA-g-NIPAAm) are synthesized by PVA and NIPAAm dilute aqueous solution using much less radiation dose of 1–20 Gy via intramolecular crosslinking at ambient temperature. The radiation synthesis of nanohydrogels is performed in the presence of tetrakis (hydroxymethyl) phosphonium chloride (THPC) due to its rapid oxygen scavenging abilities and hydrogen peroxide (H 2 O 2 ) as a source of hydroxyl radicals. The effect of radiation dose, feed composition ratio of PVA and H 2 O 2 is investigated on swelling properties such as temperature and pH dependence of equilibrium swelling ratio as well as deswelling kinetics. Experimental data exhibit high equilibrium swelling ratio and fast response time for the synthesized nanohydrogels. The average molecular weight between crosslinks (M c ) and crosslinking density (ρ x ) of the obtained nanohydrogels are calculated from swelling data as a function of radiation dose, H 2 O 2 and PVA amount. Fourier transform infrared spectroscopy (FT-IR), elemental analysis of nitrogen content and thermogravimetric analysis (TGA) are used to confirm the grafting reaction. Lower critical solution temperature (LCST) is measured around 33 °C by differential scanning calorimetry (DSC) for PVA-g-NIPAAm nanohydrogels. Dynamic light scattering (DLS) data demonstrate that the increase of radiation dose leads to the decreasing in dimension of nanohydrogels. Also, rheological studies are confirmed an improvement in the mechanical properties of the nanohydrogels with increasing the radiation dose. A cytotoxicity study exhibits a good biocompatibility for the obtained nanohydrogels. The prepared nanohydrogels show fast swelling/deswelling behavior, high swelling ratio, dual sensitivity and good cytocompatibility, which may find potential applications as biomaterial. - Highlights: ► A new radiation polymerization method is offered in dilute aqueous solution.► This method provides PVA

Solution electrospinning of particle-polymer composite fibres

DEFF Research Database (Denmark)

Christiansen, Lasse; Fojan, Peter

2016-01-01

-scale, is produced. The maximum polymer-silica weight-ratio yielding stable fibres has also been determined. The morphology of the fibres at different weight ratios has been investigated by optical microscopy and scanning electron microscope (SEM). Low aerogel concentrations yield few particles located in polymer...

Water-soluble metal-binding polymers with ultrafiltration: A technology for the removal, concentration, and recovery of metal ions from aqueous streams

International Nuclear Information System (INIS)

Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

1997-01-01

The use of water-soluble metal-binding polymers coupled with ultrafiltration (UF) is a technology under development to selectively concentrate and recover valuable or regulated metal-ions from dilute process or waste waters. The polymers have a sufficiently large molecular size that they can be separated and concentrated using commercially available UF technology. The polymers can then be reused by changing the solution conditions to release the metal-ions, which are recovered in a concentrated form for recycle or disposal. Pilot-scale demonstrations have been completed for a variety of waste streams containing low concentrations of metal ions including electroplating wastes (zinc and nickel) and nuclear waste streams (plutonium and americium). Many other potential commercial applications exist including remediation of contaminated solids. An overview of both the pilot-scale demonstrated applications and small scale testing of this technology are presented

Water-soluble metal-binding polymers with ultrafiltration: A technology for the removal, concentration, and recovery of metal ions from aqueous streams

Energy Technology Data Exchange (ETDEWEB)

Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

1997-12-31

The use of water-soluble metal-binding polymers coupled with ultrafiltration (UF) is a technology under development to selectively concentrate and recover valuable or regulated metal-ions from dilute process or waste waters. The polymers have a sufficiently large molecular size that they can be separated and concentrated using commercially available UF technology. The polymers can then be reused by changing the solution conditions to release the metal-ions, which are recovered in a concentrated form for recycle or disposal. Pilot-scale demonstrations have been completed for a variety of waste streams containing low concentrations of metal ions including electroplating wastes (zinc and nickel) and nuclear waste streams (plutonium and americium). Many other potential commercial applications exist including remediation of contaminated solids. An overview of both the pilot-scale demonstrated applications and small scale testing of this technology are presented.

(Liquid plus liquid) equilibria of binary polymer solutions using a free-volume UNIQUAC-NRF model

DEFF Research Database (Denmark)

Radfarnia, H.R.; Ghotbi, C.; Taghikhani, V.

2006-01-01

+ liquid) equilibria (LLE) for a number of binary polymer solutions at various temperatures. The values for the binary characteristic energy parameters for the proposed model and the FV-UNIQUAC model along with their average relative deviations from the experimental data were reported. It should be stated...

Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR Methodology

Directory of Open Access Journals (Sweden)

Run-Cang Sun

2013-01-01

Full Text Available The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA, nitrobenzene oxidation (NBO, and derivatization followed by reductive cleavage (DFRC. Recent advances in nuclear magnetic resonance (NMR technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ, as well as their applications are reviewed.

Controlled swelling and degradation studies of alginate microbeads in dilute natrium-citrate solutions

Directory of Open Access Journals (Sweden)

Mitrović Dragana D.

2010-01-01

Full Text Available Alginate hydrogels are widely used in biomedicine due to alginate availability, hydrophilic nature, biocompatibility and biodegradability. Alginate microbeads are particularly attractive for applications in pharmacy and regenerative medicine due to high surface to volume ratio, low mass transfer limitations and simple implantation by injection. Aim of this work was to investigate possibilities for controlled degradation of alginate microbeads in cell culture medium (Dulbecco’s modified Eagle’s medium with Na-citrate added in small concentrations (0.05 - 0.5 mM. Alginate microbeads (1.5% w/w, 800 m in diameter were produced by electrostatic droplet extrusion and evaluated over a period of 10 days regarding appearance, kinetics and degree of swelling as well as biomechanical properties determined in a novel bioreactor with mechanical stimulation under in vivo-like conditions in articular cartilage (10% strain, 337.5 m/s compression rate. In the citrate concentration range investigated, microbeads initially swelled reaching an equilibrium value (~150-170% with respect to the initial mass, upon which they appeared stable for a certain period of time (1 to over 7 days followed by bead bursting and degradation. This degradation process indicated that Na+ ions from the solution initially replaced Ca2+ ions bound mainly to COO- groups in polymannuronate sequences inducing electrostatic repulsion of polymer chains and, consequently, swelling of the beads. Citrate ions assisted in this process by forming insoluble calcium citrate. Thus, the specific rate of the bead swelling increased with the increase in citrate concentration approaching a maximal value of ~0.34 d-1. In the last phase, the beads burst into pieces, which slowly continued to degrade by replacement of Ca2+ ions bonded to polyguluronate blocks in the egg-box structure. Compression moduli for packed beds of control, freshly produced microbeads, and microbeads swelled at the equilibrium

Free-radical-induced chain scission and cross-linking of polymers in aqueous solution. An overview

International Nuclear Information System (INIS)

Von Sonntag, C.

2002-01-01

Complete text of publication follows. In the radiolysis of N 2 O-saturated aqueous solutions OH are generated. In their reactions with polymers, they give rise to polymer-derived radicals. The kinetics of the formation and decay of these radicals are reviewed. The rate of reaction of a polymer with a reactive free radical is noticeably lower than that of an equivalent concentration of monomer due to the non-random distribution of the reaction sites. Once a larger number of radicals are formed on one polymer molecule, e.g. upon pulse radiolysis, close-by radicals recombine more rapidly while the more distant ones survive for much longer times than an equivalent concentration of freely diffusing radicals. Intermolecular cross-linking (between two polymer chains, increase in molecular weight) and intramolecular cross-linking (formation of small loops, no increase in polymer weight) are competing processes, and their relative yields thus depend on the dose rate and polymer concentration. Hydrogen-transfer reactions within the polymer, e.g. transformation of a secondary radical into a tertiary one, are common and facilitated by the high local density of reactive sites. Due to repulsive forces, the lifetime of radicals of charged polymers is substantially increased. This enables even relatively slow b-fragmentation reactions to become of importance. In the case of poly(methacrylic acid), where β-fragmentation is comparatively fast, this even leads to an unzipping, and as a consequence of the efficient release of methacrylic acid the situation of equilibrium polymerization is approached. Heterolytic β-fragmentation is possible when adequate leaving groups are available, e.g. in polynucleotides and DNA. In the presence of O 2 , chain scission occurs via oxyl radicals as intermediates. Some implications for technical applications are discussed

Mass transport in polyelectrolyte solutions

Science.gov (United States)

Schipper, F. J. M.; Leyte, J. C.

1999-02-01

The self-diffusion coefficients of the three components of a salt-free heavy-water solution of polymethacrylic acid, completely neutralized with tetra-methylammonium hydroxide, were measured over a broad concentration range. Three concentration regions were observed for the self-diffusion of both the polyions and the counterions. At polyion concentrations below 0.01 mol monomer kg-1, the dilute concentration regime for the polymer, the polyion self-diffusion coefficient approaches the self-diffusion coefficient of a freely diffusing rod upon dilution. At polyelectrolyte concentrations above 0.1 mol monomer kg-1, the self-diffusion coefficients of the solvent, the counterions and the polymer decreased with concentration, suggesting that this decrease is due to a topological constraint on the motions of the components. In the intermediate-concentration region, the self-diffusion coefficients of the polyions and the counterions are independent of the concentration. The polyion dynamic behaviour is, in the intermediate- and high-concentration regions, reasonably well described by that of a hard sphere, with a radius of 3.7 nm. A correct prediction for the solvent dynamics is given by the obstruction effect of this hard sphere on the solvent. The relative counterion self-diffusion coefficient is predicted almost quantitatively over the entire concentration range with the Poisson-Boltzmann-Smoluchowski model for the spherical cell, provided that the sphere radius and the number of charges are chosen appropriately (approximately the number of charges in a persistence length). Using this model, the dependence of the counterion self-diffusion coefficient on the ionic strength, polyion concentration and counterion radius is calculated quantitatively over a large concentration range.

Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics

KAUST Repository

Zhang, Zhen

2017-05-19

Aggregation-induced emission (AIE) active core cross-linked multiarm star polymers, carrying polystyrene (PS), polyethylene (PE), or polyethylene-b-polycaprolactone (PE-b-PCL) arms, have been synthesized through an “arm-first” strategy, by atom transfer radical copolymerization (ATRP) of a double styrene-functionalized tetraphenylethene (TPE-2St) used as a cross-linker with linear arm precursors possessing terminal ATRP initiating moieties. Polyethylene macroinitiator (PE–Br) was prepared via the polyhomologation of dimethylsulfoxonium methylide with triethylborane followed by oxidation/hydrolysis and esterification of the produced PE–OH with 2-bromoisobutyryl bromide; polyethylene-block-poly(ε-caprolactone) diblock macroinitiator was derived by combining polyhomologation with ring-opening polymerization (ROP). All synthesized star polymers showed AIE-behavior either in solution or in bulk. At high concentration in good solvents (e.g., THF, or toluene) they exhibited low photoluminescence (PL) intensity due to the inner filter effect. In sharp contrast to the small molecule TPE-2St, the star polymers were highly emissive in dilute THF solutions. This can be attributed to the cross-linked structure of poly(TPE-2St) core which restricts the intramolecular rotation and thus induces emission. In addition, the PL intensity of PE star polymers in THF(solvent)/n-hexane(nonsolvent) mixtures, due to their nearly spherical shape, increased when the temperature decreased from 55 to 5 °C with a linear response in the range 40–5 °C.

Sugar yields from dilute oxalic acid pretreatment of maple wood compared to those with other dilute acids and hot water.

Science.gov (United States)

Zhang, Taiying; Kumar, Rajeev; Wyman, Charles E

2013-01-30

Dilute oxalic acid pretreatment was applied to maple wood to improve compatibility with downstream operations, and its performance in pretreatment and subsequent enzymatic hydrolysis was compared to results for hydrothermal and dilute hydrochloric and sulfuric acid pretreatments. The highest total xylose yield of ∼84% of the theoretical maximum was for both 0.5% oxalic and sulfuric acid pretreatment at 160 °C, compared to ∼81% yield for hydrothermal pretreatment at 200 °C and for 0.5% hydrochloric acid pretreatment at 140 °C. The xylooligomer fraction from dilute oxalic acid pretreatment was only 6.3% of the total xylose in solution, similar to results with dilute hydrochloric and sulfuric acids but much lower than the ∼70% value for hydrothermal pretreatment. Combining any of the four pretreatments with enzymatic hydrolysis with 60 FPU cellulase/g of glucan plus xylan in the pretreated maple wood resulted in virtually the same total glucose plus xylose yields of ∼85% of the maximum possible. Copyright © 2012 Elsevier Ltd. All rights reserved.

Activity coefficients at infinite dilution and physicochemical properties for organic solutes and water in the ionic liquid 4-(2-methoxyethyl)-4-methylmorpholinium trifluorotris(perfluoroethyl)phosphate

International Nuclear Information System (INIS)

Wlazło, Michał; Marciniak, Andrzej

2012-01-01

Highlights: ► The γ 13 ∞ and K L for 62 solutes in the IL [COC 2 mMOR][FAP] were determined by IGC. ► Partial molar excess thermodynamic functions at infinite dilution were calculated. ► The selectivities and capacities for selected separation problems were calculated. ► LFER system constants as a function of T for [COC 2 mMOR][FAP] were calculated. - Abstract: This paper presents new data on activity coefficients at infinite dilution, γ ∞ for 62 different solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, and water in the ionic liquid 4-(2-methoxyethyl)-4-methylmorpholinium trifluorotris(perfluoroethyl)phosphate, [COC 2 mMOR][FAP]. The data were determined by inverse gas chromatography at six temperatures from T = 318.15 K to T = 368.15 K. These values were compared with ionic liquid based on the same cation and bis(trifluoromethylsulfonyl)-amide anion, [COC 2 mMOR][NTf 2 ]. Additionally the partial molar excess Gibbs free energies ΔG 1 E,∞ , enthalpies ΔH 1 E,∞ , and entropies ΔS 1 E,∞ at infinite dilution were calculated from the experimental γ ∞ values obtained over the temperatures range. The selectivities and capacities at infinite dilution for hexane/benzene, cyclohexane/benzene, and heptane/thiophene extraction problems were calculated from the γ ∞ to verify the possibility of investigated ionic liquid as an entrainer in liquid–liquid extraction and desulphurization of fuels. Obtained values were compared with literature data of other ionic liquids based on trifluorotris(perfluoroethyl)phosphate and bis(trifluoromethylsulfonyl)-amide anions and industrial solvents: NMP and sulfolane. Also the Abraham solvation parameter model was used for evaluation of the solvation characteristic of the ionic liquid. Linear free energy relationship (LFER) system constants as a function of temperature were calculated.

Muonated cyclohexadienyl radicals observed by level crossing resonance in dilute solutions of benzene in hexane subjected to muon-irradiation

International Nuclear Information System (INIS)

Walker, D.C.; Barnabas, M.V.; Venkateswaran, K.

1988-11-01

Benzene is used here as a scavenger of muonium to produce the muonated cyclohexadienyl radical in dilute solutions in n-hexane. The radical was identified by level crossing resonance spectroscopy (LCR) by observing the proton resonance of the -CHMu group occurring at 2.059T. Its yield is found to equal the sum of the muonium atom yield and the 'missing' muon yield in hexane (total 35% of the incident muons). Consequently, the complete dispersement of muons in different chemical associations is now accounted for in a saturated hydrocarbon liquid, and is seen to be similar to that in water

Recovery of Cu(II from diluted aqueous solutions by non-dispersive solvent extraction

Directory of Open Access Journals (Sweden)

Alguacil, E. J.

2002-08-01

Full Text Available The removal of copper from diluted aqueous solutions with ACORGA M5640 extractant using non-dispersive solvent extraction technology was studied. It was possible to remove Cu(II below the international standars from solutions having initially as low concentration as 0,01 g/l under various experimental conditions, i.e aqueous pH 4.0, 10 % v/v ACORGA M5640 in Exxol D100, an organic flow of 100 ml/min, and an aqueous flow 50ml/min. Since the removal occurs by chelating ion exchange between copper from solution and protons from the extractant, the former was stripped by using a 180 g/l sulphuric acid solution which flowed (50 ml/min through the tube side organic was passed (400 ml/min through the shell side of the fibers of the module

Se estudia la eliminación del cobre presente en disoluciones acuosas diluidas empleando el agente de extracción ACORGA M5640 y la tecnología de extracción con disolventes no dispersiva. Bajo las condiciones experimentales estudiadas, pH de la fase acuosa 4,0 ±0,1, 10 % v/v ACORGA M5640 en Exxsol D100, flujo de la fase orgánica 100 ml/min, flujo de la fase acuosa 50 ml/min, es posible eliminar el Cu(II, por debajo de los límites marcados internacionalmente, en disoluciones con un contenido tan bajo como 0,01 g/1 del metal. Debido a que la extracción transcurre mediante un intercambio catiónico (y formación de un compuesto tipo quelato entre el cobre presente en el medio acuoso y los protones del agente de extracción, el metal se puede reextraer mediante la utilización de una disolución de 180 g/1 de ácido sulfúrico que fluye (50 ml/min a través de la parte interior de las fibras del módulo, mientras que la fase orgánica fluye (400 ml/min por la parte exterior de las mismas fibras.

Composite systems of dilute and dense couplings

International Nuclear Information System (INIS)

Raymond, J R; Saad, D

2008-01-01

Composite systems, where couplings are of two types, a combination of strong dilute and weak dense couplings of Ising spins, are examined through the replica method. The dilute and dense parts are considered to have independent canonical disordered or uniform bond distributions; mixing the models by variation of a parameter γ alongside inverse temperature β we analyse the respective thermodynamic solutions. We describe the variation in high temperature transitions as mixing occurs; in the vicinity of these transitions we exactly analyse the competing effects of the dense and sparse models. By using the replica symmetric ansatz and population dynamics we described the low temperature behaviour of mixed systems

Activity coefficients at infinite dilution measurements for organic solutes in the ionic liquid 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide using g.l.c. at T=(298.15, 313.15, and 333.15) K

International Nuclear Information System (INIS)

Letcher, Trevor M.; Marciniak, Andrzej; Marciniak, MaIgorzata; Domanska, Urszula

2005-01-01

The activity coefficients at infinite dilution, γ 13 ∞ (where 1 refers to the solute and 3 to the solvent), for both polar and non-polar solutes (alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, benzene, carbon tetrachloride, and methanol) in the ionic liquid 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide [HMIM][Tf 2 N] at three temperatures T=(298.15, 313.15, and 333.15) K have been determined by gas-liquid chromatography. The interaction at the gas-liquid interface between the solutes and the solvent was examined by varying solvent liquid loading on the column. Corrected retention values, taking carrier gas and solute imperfections into account, were determined and used to calculate the activity coefficients at infinite dilution. The results have been used to predict the solvent potential for the hexane/benzene separation from calculated selectivity values. The results were compared to γ 13 ∞ for similar systems found in the literature in an attempt to understand the effect of the nature of the cation and anion has on solute-solvent interactions. The partial molar excess enthalpies at infinite dilution values ΔH 1 E∞ were calculated from the experimental γ 13 ∞ values obtained over the temperature range

Monte Carlo simulations of lattice models for single polymer systems

Science.gov (United States)

Hsu, Hsiao-Ping

2014-10-01

Single linear polymer chains in dilute solutions under good solvent conditions are studied by Monte Carlo simulations with the pruned-enriched Rosenbluth method up to the chain length N ˜ O(10^4). Based on the standard simple cubic lattice model (SCLM) with fixed bond length and the bond fluctuation model (BFM) with bond lengths in a range between 2 and sqrt{10}, we investigate the conformations of polymer chains described by self-avoiding walks on the simple cubic lattice, and by random walks and non-reversible random walks in the absence of excluded volume interactions. In addition to flexible chains, we also extend our study to semiflexible chains for different stiffness controlled by a bending potential. The persistence lengths of chains extracted from the orientational correlations are estimated for all cases. We show that chains based on the BFM are more flexible than those based on the SCLM for a fixed bending energy. The microscopic differences between these two lattice models are discussed and the theoretical predictions of scaling laws given in the literature are checked and verified. Our simulations clarify that a different mapping ratio between the coarse-grained models and the atomistically realistic description of polymers is required in a coarse-graining approach due to the different crossovers to the asymptotic behavior.

Monte Carlo simulations of lattice models for single polymer systems

International Nuclear Information System (INIS)

Hsu, Hsiao-Ping

2014-01-01

Single linear polymer chains in dilute solutions under good solvent conditions are studied by Monte Carlo simulations with the pruned-enriched Rosenbluth method up to the chain length N∼O(10 4 ). Based on the standard simple cubic lattice model (SCLM) with fixed bond length and the bond fluctuation model (BFM) with bond lengths in a range between 2 and √(10), we investigate the conformations of polymer chains described by self-avoiding walks on the simple cubic lattice, and by random walks and non-reversible random walks in the absence of excluded volume interactions. In addition to flexible chains, we also extend our study to semiflexible chains for different stiffness controlled by a bending potential. The persistence lengths of chains extracted from the orientational correlations are estimated for all cases. We show that chains based on the BFM are more flexible than those based on the SCLM for a fixed bending energy. The microscopic differences between these two lattice models are discussed and the theoretical predictions of scaling laws given in the literature are checked and verified. Our simulations clarify that a different mapping ratio between the coarse-grained models and the atomistically realistic description of polymers is required in a coarse-graining approach due to the different crossovers to the asymptotic behavior

Using in-situ polymerization of conductive polymers to enhance the electrical properties of solution-processed carbon nanotube films and fibers.

Science.gov (United States)

Allen, Ranulfo; Pan, Lijia; Fuller, Gerald G; Bao, Zhenan

2014-07-09

Single-walled carbon nanotubes/polymer composites typically have limited conductivity due to a low concentration of nanotubes and the insulating nature of the polymers used. Here we combined a method to align carbon nanotubes with in-situ polymerization of conductive polymer to form composite films and fibers. Use of the conducting polymer raised the conductivity of the films by 2 orders of magnitude. On the other hand, CNT fiber formation was made possible with in-situ polymerization to provide more mechanical support to the CNTs from the formed conducting polymer. The carbon nanotube/conductive polymer composite films and fibers had conductivities of 3300 and 170 S/cm, respectively. The relatively high conductivities were attributed to the polymerization process, which doped both the SWNTs and the polymer. In-situ polymerization can be a promising solution-processable method to enhance the conductivity of carbon nanotube films and fibers.

Know your facts on polymer floods

Energy Technology Data Exchange (ETDEWEB)

Mungan, N

1967-06-01

The influence of mobility ratio on the recovery of oil by waterflooding is reviewed in general. It is shown that, for mobility ratios more unfavorable than ten, additional oil recovery obtainable by polymer flooding may be too small to prove a profitable application. Polymers achieve the lower water mobilities by two mechanisms: (1) by reducing the permeability of the porous media through polymer trapping in the pores; and (2) by yielding a high solution viscosity, due to speudo-plastic nature of the polymer solutions. Adsorption, connate water saturation and reservoir heterogeneity are very important in the field use of polymers. Laboratory data is presented showing that for a given polymer solution oil recoveries are greatest where adsorption is reduced and when the porous medium is heterogeneous.

Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates

KAUST Repository

Zhao, Kui

2016-07-13

We demonstrate that local and long range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the dielectric surface with solution-state disentanglement and pre-aggregation of P3HT in a theta solvent, leading to a very significant enhancement of the field effect carrier mobility. The pre-aggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of pre-aggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of pre-aggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to un-aggregated polymer chains. Additional investigations reveal the combined pre-aggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known pre-aggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

Activity coefficients at infinite dilution and physicochemical properties for organic solutes and water in the ionic liquid 1-(2-hydroxyethyl)-3-methylimidazolium trifluorotris(perfluoroethyl)phosphate

International Nuclear Information System (INIS)

Marciniak, Andrzej; Wlazło, Michał

2013-01-01

Highlights: • γ ∞ and K L for 65 solutes in the IL [C 2 OHmim][FAP] were determined by IGC. • Partial molar thermodynamics functions ΔG 1 E,∞ , ΔH 1 E,∞ and ΔS 1 E,∞ were calculated. • Selectivities and capacities for alkanes/thiophene separation problems were calculated. • LFER system constants as a function of T for [C 2 OHmim][FAP] were calculated. • Results were compared to other ILs based on the same cation and anion. -- Abstract: This work presents new data of activity coefficients at infinite dilution, γ ∞ of different organic solutes and water in the 1-(2-hydroxyethyl)-3-methylimidazolium trifluorotris(perfluoroethyl)phosphate, [C 2 OHmim][FAP] ionic liquid. Values of γ ∞ were determined for 65 organic solutes, including alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, esters, 1-nitropropane, aldehydes, acetonitrile and water by inverse gas chromatography within the temperature range from (318.15 to 368.15) K. The basic thermodynamic functions, such as partial molar excess Gibbs energies, ΔG 1 E,∞ , enthalpies, ΔH 1 E,∞ and entropies, ΔS 1 E,∞ at infinite dilution were calculated from the experimental γ ∞ values obtained over the temperature range. Additionally the gas–liquid partition coefficients, K L were determined. Experimental values of gas–liquid partition coefficients were used to determine the coefficients in the Abraham solvation parameter model (LFER). Results are compared to previously investigated ionic liquids with the same [C 2 OHmim] + cation and [FAP] − anion. The selectivity and capacity at infinite dilution for alkanes/thiophene extraction problems were calculated from experimental γ ∞ values to verify the possibility of investigated ionic liquid as an entrainer in liquid–liquid extraction

Ambipolar Small-Molecule:Polymer Blend Semiconductors for Solution-Processable Organic Field-Effect Transistors.

Science.gov (United States)

Kang, Minji; Hwang, Hansu; Park, Won-Tae; Khim, Dongyoon; Yeo, Jun-Seok; Kim, Yunseul; Kim, Yeon-Ju; Noh, Yong-Young; Kim, Dong-Yu

2017-01-25

We report on the fabrication of an organic thin-film semiconductor formed using a blend solution of soluble ambipolar small molecules and an insulating polymer binder that exhibits vertical phase separation and uniform film formation. The semiconductor thin films are produced in a single step from a mixture containing a small molecular semiconductor, namely, quinoidal biselenophene (QBS), and a binder polymer, namely, poly(2-vinylnaphthalene) (PVN). Organic field-effect transistors (OFETs) based on QBS/PVN blend semiconductor are then assembled using top-gate/bottom-contact device configuration, which achieve almost four times higher mobility than the neat QBS semiconductor. Depth profile via secondary ion mass spectrometry and atomic force microscopy images indicate that the QBS domains in the films made from the blend are evenly distributed with a smooth morphology at the bottom of the PVN layer. Bias stress test and variable-temperature measurements on QBS-based OFETs reveal that the QBS/PVN blend semiconductor remarkably reduces the number of trap sites at the gate dielectric/semiconductor interface and the activation energy in the transistor channel. This work provides a one-step solution processing technique, which makes use of soluble ambipolar small molecules to form a thin-film semiconductor for application in high-performance OFETs.

Sequestration of chromium by exopolysaccharides of Nostoc and Gloeocapsa from dilute aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Sharma, Mona [Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar-125 001 (India); Kaushik, Anubha [Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar-125 001 (India)], E-mail: aks_10@yahoo.com; Somvir,; Bala, Kiran; Kamra, Anjana [Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar-125 001 (India)

2008-09-15

This article reports the chromium removal potential of exopolysaccharides (EPS) of two indigenously isolated cyanobacterial strains, Gloeocapsa calcarea and Nostoc punctiforme. The biosorption was studied by varying pH from 2 to 6 and initial chromium concentration from 5 to 20 mg/L to find out the optimized conditions for maximum chromium removal by EPS. Two equilibrium models, Langmuir and Freundlich, were used to explain these results. The Freundlich model was found to be better applicable to the experimental data as compared to Langmuir as inferred from high value of coefficient of determination whereas the optimal conditions were found to be same for the two (pH 2 and initial chromium concentration 20 mg/L). EPS production by the two strains was also studied which was found to be higher for Gloeocapsa. On the basis of experimental results and model parameters, it can be inferred that the EPS extracted from Nostoc has comparatively high biosorption capacity and can be utilized for the removal of chromium from dilute aqueous solution. Adsorption of chromium on EPS was further confirmed by surface morphology observed in scanning electron micrographs.

Sequestration of chromium by exopolysaccharides of Nostoc and Gloeocapsa from dilute aqueous solutions

International Nuclear Information System (INIS)

Sharma, Mona; Kaushik, Anubha; Somvir,; Bala, Kiran; Kamra, Anjana

2008-01-01

This article reports the chromium removal potential of exopolysaccharides (EPS) of two indigenously isolated cyanobacterial strains, Gloeocapsa calcarea and Nostoc punctiforme. The biosorption was studied by varying pH from 2 to 6 and initial chromium concentration from 5 to 20 mg/L to find out the optimized conditions for maximum chromium removal by EPS. Two equilibrium models, Langmuir and Freundlich, were used to explain these results. The Freundlich model was found to be better applicable to the experimental data as compared to Langmuir as inferred from high value of coefficient of determination whereas the optimal conditions were found to be same for the two (pH 2 and initial chromium concentration 20 mg/L). EPS production by the two strains was also studied which was found to be higher for Gloeocapsa. On the basis of experimental results and model parameters, it can be inferred that the EPS extracted from Nostoc has comparatively high biosorption capacity and can be utilized for the removal of chromium from dilute aqueous solution. Adsorption of chromium on EPS was further confirmed by surface morphology observed in scanning electron micrographs

A Mathematical Model of Repeated Impregnation of Porous Bodies with Solutions of Polymers

Directory of Open Access Journals (Sweden)

I. V. Glebov

2015-01-01

Full Text Available The paper describes basic methods of impregnating porous bodies with solutions of polymers and their use to manufacture prepregs. It also describes the existing methods of manufacturing multilayer prepregs to produce aerospace coating of the spacecraft "Soyuz". It is shown that these prepregs have to meet high requirements for the content of the polymer, as compared with other composite materials, about 35 - 40% of the mass. Methods used for their manufacturing are long-term and non-controllable. The assumption is made that using the vacuum impregnation technology of a woven material will allow to accelerate the manufacturing process of these prepregs and improve their quality.In reviewing the technical literature have been found works on modeling the processes of impregnation, but they are aimed only at studying the speed of the woven material impregnation by various fluids and determining the time of impregnation. There were no models found to define prepreg parameters during the process of multiple impregnations. The aim of this work is to develop the simple mathematical model, which enables us to predict the polymer content of volatile products in the prepreg after each cycle of multiple impregnation of woven material with a solution of the polymer.To consider the vacuum impregnation method are used the prepregs based on silica and silica-nylon stitch-bonding fabric and bakelite varnish LBS-4 containing 50 - 60% of phenol resin and the solvent with minor impurities of pure phenol and water, as an example. To describe the process of vacuum impregnation of the porous work-piece is developed a mathematical description of the process of filling the porous space of the material with a varnish. It is assumed that the varnish components fill the porous space of the material in the same proportion as they are contained in the varnish.It is shown that a single impregnation cannot ensure the content of phenol resin in the prepreg over 32%, which does

Synthesis and characterization of a molecularly imprinted polymer for the isolation of the 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) in solution.

Science.gov (United States)

Ncube, Somandla; Kunene, Phumlile; Tavengwa, Nikita T; Tutu, Hlanganani; Richards, Heidi; Cukrowska, Ewa; Chimuka, Luke

2017-09-01

A smart sorbent consisting of benzo[k]fluoranthene-imprinted and indeno[1 2 3-cd]pyrene-imprinted polymers mixed at 1:1 (w/w) was successfully screened from several cavity-tuning experiments and used in the isolation of polycyclic aromatic hydrocarbons from spiked solution. The polymer mixture showed high cross selectivity and affinity towards all the 16 US-EPA priority polycyclic aromatic hydrocarbons. The average extraction efficiency from a cyclohexane solution was 65 ± 13.3% (n = 16, SD). Batch adsorption and kinetic studies confirmed that the binding of polycyclic aromatic hydrocarbons onto the polymer particles resulted in formation of a monolayer and that the binding process was the rate limiting step. The imprinted polymer performance studies confirmed that the synthesized polymer had an imprinting efficiency of 103.9 ± 3.91% (n = 3, SD). A comparison of the theoretical number of cavities and the experimental binding capacity showed that the overall extent of occupation of the imprinted cavities in the presence of excess polycyclic aromatic hydrocarbons was 128 ± 6.45% (n = 3, SD). The loss of selectivity was estimated at 2.9% with every elution cycle indicating that the polymer can be re-used several times with limited loss of selectivity and sensitivity. The polymer combination has shown to be an effective adsorbent that can be used to isolate all the 16 US-EPA priority polycyclic aromatic hydrocarbons in solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation and electrochemistry of a pyrene-linked iron terpyridine and its anodic redox polymer

International Nuclear Information System (INIS)

Lin, Hsiao-Chu; Straus, Daniel A.; Johnson, Victoria Anne; Lu, Jia E.; Lopez, Louise; Terrill, Roger H.

2012-01-01

An iron(II)bis-terpyridine complex bearing 4′ pendant pyrenyl groups on each ligand (Fe(tpySCH 2 -pyr) 2 2+ ) was synthesized, characterized electrochemically and was shown to form a novel redox polymer via anodic electropolymerization. Immersion of glassy carbon electrodes into dilute acetonitrile solutions of the complex and then into clean electrolyte established that the complex will physisorb onto glassy carbon at 0.1 monolayer coverage from 500 μM solution. Anodic cyclic voltammetry of the pyrenyl iron compound revealed well-resolved Fe(II/III) centered redox waves near 0.9 V and an irreversible, pyrene centered oxidation at ca. 1.1 V. The Fe(II/III) waves grew in magnitude over time and persisted in fresh complex-free electrolyte indicating a surface electropolymerization reaction most likely mediated via the pyrene pendant groups, and exhibiting facile charge transport through a ca. 100 nm polymer film. Spectroelectrochemical analysis of Fe(tpySCH 2 -pyr) 2 (OTf) 2 films grown on indium–tin oxide transparent electrodes confirmed the presence of a Fe(II/III) redox-active film that has a nearly Nernstian response, but with a small Fe(II) component that does not oxidize interfacially.

Evaluation of the numerical solution of polymer flooding; Avaliacao da solucao numerica da injecao de polimeros em reservatorios de petroleo

Energy Technology Data Exchange (ETDEWEB)

Teixeira, Vinicius Ligiero; Pires, Adolfo Puime; Bedrikovetsky, Pavel G. [Universidade Estadual do Norte Fluminense (UENF), Macae, RJ (Brazil). Lab. de Engenharia e Exploracao do Petroleo (LENEP)

2004-07-01

Enhanced Oil Recovery (EOR) methods include injection of different fluids into reservoirs to improve oil displacement. The EOR methods may be classified into the following kinds: injection of chemical solutions, injection of solvents and thermal methods. The chemical fluids most commonly injected are polymers, surfactants, micellar solutions, etc. Displacement of oil by any of these fluids involves complex physico-chemical processes of interphase mass transfer, phase transitions and transport properties changes. These processes can be divided into two main categories: thermodynamical and hydrodynamical ones. They occur simultaneously during the displacement, and are coupled in the modern mathematical models of EOR. The model for one-dimensional displacement of oil by polymer solutions is analyzed in this paper. The Courant number is fixed, and we compare the results of different runs of a numerical simulator with the analytical solution of this problem. Each run corresponds to a different spatial discretization. (author)

Study on the enthalpy of solution and enthalpy of dilution for the ionic liquid [C3mim][Val] (1-propyl-3-methylimidazolium valine)

International Nuclear Information System (INIS)

Guan Wei; Li Long; Ma Xiaoxue; Tong Jing; Fang Dawei; Yang Jiazhen

2012-01-01

Graphical abstract: The thermodynamic cycle for estimation of the hydration enthalpy of ionic liquid [C 3 mim][Val]. Highlights: ► A new amino acid ionic liquid [C 3 mim][Val] was prepared. ► The molar enthalpies of solution of the ionic liquid. ► The hydration enthalpy of the cation [C 3 mim] + was estimated. ► The molar enthalpies of dilution, of aqueous [C 3 mim][Val] were measured. - Abstract: A new amino acid ionic liquid (AAIL) [C 3 mim][Val] (1-propyl-3-methylimidazolium valine) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar solution enthalpies of the ionic liquid [C 3 mim][Val] with known amounts of water and with different concentrations in molality were measured at T = 298.15 K. In terms of standard addition method (SAM) and Archer’s method, the standard molar enthalpy of solution for [C 3 mim][Val] without water, Δ s H m ∘ = (−55.7 ± 0.4) kJ · mol −1 , was obtained. The hydration enthalpy of the cation [C 3 mim] + , ΔH + ([C 3 mim] + ) = −226 kJ · mol −1 , was estimated in terms of Glasser’s theory. Using the RD496-III heat conduction microcalorimeter, the molar enthalpies of dilution, Δ D H m (m i → m f ), of aqueous [C 3 mim][Val] with various values of molality were measured. The values of Δ D H m (m i → m f ) were fitted to Pitzer’s ion-interaction model and the values of apparent relative molar enthalpy, φ L, calculated using Pitzer’s ion-interaction model.

EXTRACTION AND SORPTION BENZOIC ACID FROM AQUEOUS SOLUTIONS OF POLYMERS BASED ON N-VINYLAMIDES

Directory of Open Access Journals (Sweden)

A. G. Savvina

2015-01-01

Full Text Available The widespread use of aromatic acids (benzoic acid, salicylic as preservatives necessitates their qualitative and quantitative determination in food. Effective and common way to separation and concentration of aromatic acids liquid extraction. Biphasic system of water-soluble polymers based on (poly-N-vinyl pyrrolidone, and poly-N-vinylcaprolactam satisfy the requirements of the extraction system. When sorption concentration improved definition of the metrological characteristics, comply with the requirements for sensitivity and selectivity definition appears possible, use of inexpensive and readily available analytical equipment. When studying the adsorption of benzoic acid used as a sorbent crosslinked polymer based on N-vinyl pyrrolidone, obtained by radical polymerisation of a functional monomer and crosslinker. In the extraction of benzoic acid to maximize the allocation of water and the organic phase of the polymer used salt solutions with concentrations close to saturation. Regardless of the nature of the anion salt is used as salting-out agent, aromatic acids sorption increases with the size of the cations. In the experiment the maximum recovery rate (80% benzoic acid obtained in the PVP (0.2 weight%. Ammonium sulphate. The dependence stepepni benzoic acid extraction from time sorption sorbent mass and the pH of the aqueous phase. To establish equilibrium in the system, for 20 minutes. The dependence of the degree of extraction of the acid pH indicates that the acid is extracted into the molecular form. The maximum adsorption is reached at pH 3,5, with its efficiency decreases symbatically reduce the amount of undissociated acid molecules in solution.

Advances in the stabilisation of swollen polymer by radiation

International Nuclear Information System (INIS)

Hidi, P.; Napper, D.H.; Sangster, D.F.

1998-01-01

Anionic surfactants form polymer micelle complexes (PMCs) along the chains of hydrophobic/hydrophilic polymers in an aqueous latex. The charges on these PMCs repel each other allowing access by the solution and causing the particles to swell to up to sixty times their volume in the poly(vinyl acetate) (PVAc) / sodium dodecyl sulphate (SDS) system. Swelling starts at 4.5 mM SDS which is well below the critical micelle concentration (8.3 mM). The particle size was measured by Dynamic Light Scattering (DLS) and verified by weighing the sediment after ultracentrifuging. We attributed the limitation of swelling to the presence of entanglements which were not loosened during swelling. The fully swollen material contained 1.8% PVAc, 1.6% SDS and 96.6% water. If the SDS concentration was lowered by dialysis or by dilution, the SDS of the PMCs dispersed and the particles reverted to slightly less than their original size, ie the swelling was reversible. The somewhat smaller size was accounted for by the leaching into the solution of low molecular weight polymer as individual chains incorporating PMCs along their length and thus similar to a polyelectrolyte. With sodium tetradecyl sulphate the threshold is 1 mM and the particles swell up to 200 fold. Prolonged attack by free radicals either by irradiation or by chemical sources would be expected to give a more or less continuous array of single charges along the chain and this might be more effective in loosening entanglements. Alternatively or additionally, the radicals might cause main chain scission. Both would lead to faster dissolution. The results obtained have some ramifications for polymerisation at surfactant concentrations above the critical micelle concentration

Solution-Mediated Annealing of Polymer Optical Fiber Bragg Gratings at Room Temperature

DEFF Research Database (Denmark)

Fasano, Andrea; Woyessa, Getinet; Janting, Jakob

2017-01-01

In this letter, we investigate the response of poly(methylmethacrylate) (PMMA) microstructured polymer optical fiber Bragg gratings (POFBGs) after immersion inmethanol/water solutions at room temperature. As the glass transition temperature of solution-equilibrated PMMA differs from the one...... of solvent-free PMMA, different concentrations of methanol and water lead to various degrees of frozen-in stress relaxation in the fiber. After solvent evaporation, we observe a permanent blue-shift in the grating resonance wavelength. The main contribution in the resonance wavelength shift arises from...... a permanent change in the size of the fiber. The results are compared with conventional annealing. The proposed methodology is cost-effective as it does not require a climate chamber. Furthermore, it enables an easy-to-control tuning of the resonance wavelength of POFBGs....

Preparation of solid water-equivalent radioactive standards

CSIR Research Space (South Africa)

Morris, WM

2004-02-01

Full Text Available polyelectrolite and belongs to the class of superabsorbent polymers. The crosslinking renders this polymer insoluble in water, while the ionic nature draws water into the polymer network to dilute the ionic strength. This allows the polymer to absorb up to 3000... times its weight in pure water (Garner et al., 1997). When an acid- or salt-containing solution is added to polyacrylate, the polymer network preferen- tially absorbs the charged particles and less water is required to dilute the ionic strength. Since...

Laboratory studies of 2H evaporator scale dissolution in dilute nitric acid

International Nuclear Information System (INIS)

Oji, L.

2014-01-01

The rate of 2H evaporator scale solids dissolution in dilute nitric acid has been experimentally evaluated under laboratory conditions in the SRNL shielded cells. The 2H scale sample used for the dissolution study came from the bottom of the evaporator cone section and the wall section of the evaporator cone. The accumulation rate of aluminum and silicon, assumed to be the two principal elemental constituents of the 2H evaporator scale aluminosilicate mineral, were monitored in solution. Aluminum and silicon concentration changes, with heating time at a constant oven temperature of 90 deg C, were used to ascertain the extent of dissolution of the 2H evaporator scale mineral. The 2H evaporator scale solids, assumed to be composed of mostly aluminosilicate mineral, readily dissolves in 1.5 and 1.25 M dilute nitric acid solutions yielding principal elemental components of aluminum and silicon in solution. The 2H scale dissolution rate constant, based on aluminum accumulation in 1.5 and 1.25 M dilute nitric acid solution are, respectively, 9.21E-04 ± 6.39E-04 min -1 and 1.07E-03 ± 7.51E-05 min -1 . Silicon accumulation rate in solution does track the aluminum accumulation profile during the first few minutes of scale dissolution. It however diverges towards the end of the scale dissolution. This divergence therefore means the aluminum-to-silicon ratio in the first phase of the scale dissolution (non-steady state conditions) is different from the ratio towards the end of the scale dissolution. Possible causes of this change in silicon accumulation in solution as the scale dissolution progresses may include silicon precipitation from solution or the 2H evaporator scale is a heterogeneous mixture of aluminosilicate minerals with several impurities. The average half-life for the decomposition of the 2H evaporator scale mineral in 1.5 M nitric acid is 12.5 hours, while the half-life for the decomposition of the 2H evaporator scale in 1.25 M nitric acid is 10.8 hours

On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions.

Science.gov (United States)

Mun, Ellina A; Hannell, Claire; Rogers, Sarah E; Hole, Patrick; Williams, Adrian C; Khutoryanskiy, Vitaliy V

2014-01-14

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

Certain laws governing the influence of high molecular polymer additives on specific electrical conductivity and viscosity of zincate alkaline solution

Energy Technology Data Exchange (ETDEWEB)

Dmitrenko, V.Ye.; Toropetsera, T.N.; Zubov, M.S.

1983-01-01

A study was made of the influence of polymer additives of different nature: polyelectrolyte, copolymer of ethylene with maleic anhydride, polymethacrylic acid and nonpolyectrolyte copolymer of vinyl alcohol with vinyleneglycol and polyvinyleneglycol on specific electrical conductance and viscosity of the zincate alkaline solution. It is indicated that with an increase in the content of additives, the specific conductance of the solution diminishes according to a linear law, while the viscosity rises. The additives of polyelectrolyte nature reduce more strongly the specific conductance and increase the viscosity than the nonpolyelectrolyte additives. From a comparison of the data on specific conductance and viscosity the following conclusion is drawn: the more the polymer ''structures'' the zincate alkaline solution, the more strongly it reduces its specific electrical conductance.

Activity coefficients at infinite dilution of organic solutes in the ionic liquid trihexyltetradecylphosphonium bis (trifluoromethylsulfonyl) imide using gas–liquid chromatography at T = (313.15, 333.15, 353.15 and 373.15) K

International Nuclear Information System (INIS)

Tumba, Kaniki; Letcher, Trevor M.; Naidoo, Paramespri; Ramjugernath, Deresh

2013-01-01

Highlights: • Activity coefficients at infinite dilution measured in the ionic liquid [3C 6 C 14 P][BTI]. • 22 solutes investigated at T = (313.15, 333.15, 353.15, 373.15) K using glc. • Selectivities and capacities for selected separations compared to other IL’s and solvents. -- Abstract: Activity coefficients at infinite dilution for organic solutes, which include n-alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, alkylbenzenes, alcohols and ketones, in the ionic liquid trihexyltetradecylphosphonium bis (trifluoromethylsulfonyl) imide were measured by gas–liquid chromatography using the latter as the stationary phase. This ionic liquid had previously been studied and reported in literature; however due to significant discrepancies in the reported infinite activity coefficient values, there was justification for further study and reporting. The temperature range investigated in this study is significantly wider and at higher temperatures than presented previously in the literature. From the experimental infinite dilution activity coefficient data at the four different temperatures T = (313.15, 333.15, 353.15 and 373.15) K, partial molar excess enthalpies at infinite dilution were calculated. Values of the selectivity for hexane/benzene and methanol/benzene separations were determined from experimental values of the activity coefficients at infinite dilution and these results were compared to literature values for other ionic liquids, as well as for industrial solvents. The capacities were also determined as it gives an indication of the solvent extraction behavior of the ionic liquid

Activity coefficients at infinite dilution of organic solutes in the ionic liquid trihexyl(tetradecyl)phosphonium tetrafluoroborate using gas-liquid chromatography at T = (313.15, 333.15, 353.15, and 373.15) K

International Nuclear Information System (INIS)

Tumba, Kaniki; Reddy, Prashant; Naidoo, Paramespri; Ramjugernath, Deresh

2011-01-01

Research highlights: → Activity coefficients at infinite dilution in the ionic liquid [3C 6 C 14 P][BF 4 ]. → Twenty-seven solutes investigated at T = (313.15, 333.15, 353.15, and 373.15) K. → [3C 6 C 14 P][BF 4 ] shows promise for the separation of aromatic and alcohol mixtures. - Abstract: Activity coefficients at infinite dilution have been measured by gas-liquid chromatography for 27 organic solutes (n-alkanes, 1-alkenes, 1-alkynes, cycloalkanes, aromatics, alcohols, and ketones) in the ionic liquid trihexyl(tetradecyl)phosphonium tetrafluoroborate [3C 6 C 14 P][BF 4 ]. The measurements were carried out at four different temperatures viz.T = (313.15, 333.15, 353.15, and 373.15) K. From the experimental data, partial molar excess enthalpy values at infinite dilution were calculated for the experimental temperature range. The selectivity values for the separation of n-hexane/benzene, cyclohexane/benzene, and methanol/benzene mixtures were determined from the experimental infinite dilution activity coefficient values. These values were compared to those available in the literature for other ionic liquids and commercial solvents, so as to assess the feasibility of employing [3C 6 C 14 P][BF 4 ] in solvent-enhanced industrial separations.

Side Chain Engineering in Solution-Processable Conjugated Polymers

KAUST Repository

Mei, Jianguo; Bao, Zhenan

2014-01-01

Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer's physical properties, including absorption

Branched multifunctional polyether polyketals: variation of ketal group structure enables unprecedented control over polymer degradation in solution and within cells.

Science.gov (United States)

Shenoi, Rajesh A; Narayanannair, Jayaprakash K; Hamilton, Jasmine L; Lai, Benjamin F L; Horte, Sonja; Kainthan, Rajesh K; Varghese, Jos P; Rajeev, Kallanthottathil G; Manoharan, Muthiah; Kizhakkedathu, Jayachandran N

2012-09-12

Multifunctional biocompatible and biodegradable nanomaterials incorporating specific degradable linkages that respond to various stimuli and with defined degradation profiles are critical to the advancement of targeted nanomedicine. Herein we report, for the first time, a new class of multifunctional dendritic polyether polyketals containing different ketal linkages in their backbone that exhibit unprecedented control over degradation in solution and within the cells. High-molecular-weight and highly compact poly(ketal hydroxyethers) (PKHEs) were synthesized from newly designed α-epoxy-ω-hydroxyl-functionalized AB(2)-type ketal monomers carrying structurally different ketal groups (both cyclic and acyclic) with good control over polymer properties by anionic ring-opening multibranching polymerization. Polymer functionalization with multiple azide and amine groups was achieved without degradation of the ketal group. The polymer degradation was controlled primarily by the differences in the structure and torsional strain of the substituted ketal groups in the main chain, while for polymers with linear (acyclic) ketal groups, the hydrophobicity of the polymer may play an additional role. This was supported by the log P values of the monomers and the hydrophobicity of the polymers determined by fluorescence spectroscopy using pyrene as the probe. A range of hydrolysis half-lives of the polymers at mild acidic pH values was achieved, from a few minutes to a few hundred days, directly correlating with the differences in ketal group structures. Confocal microscopy analyses demonstrated similar degradation profiles for PKHEs within live cells, as seen in solution and the delivery of fluorescent marker to the cytosol. The cell viability measured by MTS assay and blood compatibility determined by complement activation, platelet activation, and coagulation assays demonstrate that PKHEs and their degradation products are highly biocompatible. Taken together, these data

Analysis of the variation of the activity of a "9"9"mTc sample after dilution with saline solution

International Nuclear Information System (INIS)

Kuahara, L.T.; Correa, E.L.; Potiens, M.P.A.

2016-01-01

The activity meter is essential equipment in nuclear medicine services.To ensure its good operation and know the factors which may influence its readings is vital for the activity administered to the patient be correct. Many factors may influence the activity meter accuracy, such as the type of container, geometry, and radioactive material volume. The aim of this study was to analyze the measurements variations in 0.5 ml and 1.0 ml of "9"9"mTc pure and diluted in 2.5 ml of saline solution, in containers used in nuclear medicine. Variations of up to 4 % in measured values were found. (author)

Cylindrical polymer brushes with dendritic side chains by iterative anionic reactions

KAUST Repository

Zhang, Hefeng

2015-05-01

We report in this paper an easy method for the synthesis of cylindrical polymer brushes with dendritic side chains through anionic reaction. The synthesis is accomplished by iteratively grafting a living block copolymer, polyisoprene-. b-polystyrenyllithium (PI-. b-PSLi), to the main chain and subsequently to the branches in a divergent way. PI segment is short and serves as a precursor for multifunctional branching unit. The grafting reaction involves two successive steps: i) epoxidation of internal double bonds of PI segments, either in main chain or side chains; ii) ring-opening addition to the resulting epoxy group by the living PI-. b-PSLi. Repeating the two steps affords a series of cylindrical polymer brushes with up to 3rd generation and extremely high molecular weight. The branching multiplicity depends on the average number of oxirane groups per PI segment, usually ca. 8 in the present work. The high branching multiplicity leads to tremendous increase in molecular weights of the cylindrical products with generation growth. Several series of cylindrical polymer brushes with tunable aspect ratios are prepared using backbones and branches with controlled lengths. Shape anisotropy is investigated in dilute solution using light scattering technique. Worm-like single molecular morphology with large persistence length is observed on different substrates by atomic force microscopy.

Energy-efficient hydrogen separation by AB-type ladder-polymer molecular sieves

KAUST Repository

Ghanem, Bader

2014-07-19

The synthesis, microstructures, and exceptional gas transport properties of two new soluble ladder polymers, polymers of intrinsic microporosity (TPIM-1 and TPIM-2) containing triptycene moieties substituted with branched isopropyl and linear propyl chains at the 9,10-bridgeheads were reported. The precursor A-B monomers were modified with an o -difluoride functionality for enhanced activation for nucleophilic aromatic substitution. In a Schlenk tube, a mixture of the A-B monomer, 18-crown-6, anhydrous DMF and anhydrous potassium carbonate was stirred at 155 °C under nitrogen atmosphere for 20 min followed by the addition of toluene. The reaction was continued for another 45 min and more toluene was added. After another 45 min the reaction mixture was cooled to room temperature and poured into methanol. Slow evaporation of filtered, dilute 3-5 wt% chloroform solutions from a leveled glass plate yielded isotropic polymer films. Dry membranes were soaked in methanol for 24 h, air-dried, and then heated at 120°C for 24 h under high vacuum to remove any traces of residual solvent. TPIM-1 exhibits simultaneous boosts in permeability and selectivity, which highlights the significant potential of an isopropyl-substituted triptycene moiety as a contortion center for ladder PIMs.

Energy-efficient hydrogen separation by AB-type ladder-polymer molecular sieves

KAUST Repository

Ghanem, Bader; Swaidan, Raja; Ma, Xiaohua; Litwiller, Eric; Pinnau, Ingo

2014-01-01

The synthesis, microstructures, and exceptional gas transport properties of two new soluble ladder polymers, polymers of intrinsic microporosity (TPIM-1 and TPIM-2) containing triptycene moieties substituted with branched isopropyl and linear propyl chains at the 9,10-bridgeheads were reported. The precursor A-B monomers were modified with an o -difluoride functionality for enhanced activation for nucleophilic aromatic substitution. In a Schlenk tube, a mixture of the A-B monomer, 18-crown-6, anhydrous DMF and anhydrous potassium carbonate was stirred at 155 °C under nitrogen atmosphere for 20 min followed by the addition of toluene. The reaction was continued for another 45 min and more toluene was added. After another 45 min the reaction mixture was cooled to room temperature and poured into methanol. Slow evaporation of filtered, dilute 3-5 wt% chloroform solutions from a leveled glass plate yielded isotropic polymer films. Dry membranes were soaked in methanol for 24 h, air-dried, and then heated at 120°C for 24 h under high vacuum to remove any traces of residual solvent. TPIM-1 exhibits simultaneous boosts in permeability and selectivity, which highlights the significant potential of an isopropyl-substituted triptycene moiety as a contortion center for ladder PIMs.

Evaluation of disinfecting effect of 5% sodium hypochlorite solution diluted to 2:100 along with the use of disposable covers on HBV contaminated dental office surfaces and equipments

Directory of Open Access Journals (Sweden)

Arami S.

2008-04-01

Full Text Available Background and Aim: The efficiency of disinfecting materials and procedures in removal of contamination from dental surfaces and equipments is essential. In authors' previous study, daily use of 2:100 dilution of 5% sodium hypochlorite in water and disposable covers were recommended since HBV contamination was found on semi-critical parts of the operative dentistry department. The aim of this study was to evaluate the HBV contamination following application of the recommended procedures.Materials and Methods: The study was conducted in two parts. In the first cross-sectional part, samples were collected from 17 sites of dental surfaces. In the second interventional part samples were collected from 10 sites of 9 dental and 3 sites of 2 light cure units, before and after disinfection with 5% sodium hypochlorite solution diluted to 2:100. Sterile cotton swabs moistened with sterile BSAS (Bovine Serum Albumin in Sodium Chloride solution were used for sampling. Samples were tested by PCR technique in Pasteur Institute, Iran.Results: None of the samples collected in the first part of the study showed contamination. In the second part of the study, from 96 samples taken from various parts of dental and light cure units, before and after disinfection, there was only one HBV contaminated site before disinfection which showed no contamination after disinfection.Conclusion: Based on the results of this study, disinfecting procedure with 5% sodium hypochlorite solution diluted to 2:100 along with using disposable covers is effective in preventing HBV contamination.

Fluoride removal from diluted solutions by Donnan dialysis using full factorial design

Energy Technology Data Exchange (ETDEWEB)

Boubakri, Ali; Helali, Nawel; Tlili, Mohamed; Amor, Mohamed Ben [Center of Researches and Water Technologies, Soliman (Turkey)

2014-03-15

Excessive fluoride concentration in potable water can lead to fluorosis of teeth and bones. In the present study, Donnan dialysis (DD) is applied for the removal of fluoride ions from diluted sodium fluoride solutions. A four factor two level (2{sup 4}) full factorial design was used to investigate the influence of different physico-chemical parameters on fluoride removal efficiency (Y{sub F}) and fluoride flux (J{sub F}) through anion exchange membrane. The statistical design determines factors which have the important effects on Donnan dialysis performance and studies all interactions among the considered parameters. The four significant factors were initial fluoride concentration, feed flow rate, temperature and agitation speed. The experimental results and statistical analysis show that the temperature and agitation speed have positive effects on fluoride removal efficiency and the initial fluoride concentration has a negative effect. In the case of fluoride flux, feed flow rate and initial concentration are the main effect and all factors have a positive effect. The interaction between studied parameters was not negligible on two responses. A maximum fluoride removal of 75.52% was obtained under optimum conditions and the highest value of fluoride flux obtained was 2.4 mg/cm{sup 2}·h. Empirical regression models were also obtained and used to predict the flux and the fluoride removal profiles with satisfactory results.

Rapid adsorption of Pb, Cu and Cd from aqueous solutions by β-cyclodextrin polymers

Science.gov (United States)

He, Junyong; Li, Yulian; Wang, Chengming; Zhang, Kaisheng; Lin, Dongyue; Kong, Lingtao; Liu, Jinhuai

2017-12-01

Removing heavy metals from aqueous solutions has drawn more and more attentions these years because of their serious global health challenge to human society. To develop an adsorbent with low-cost and high-efficiency for removal of heavy metals (HMs), β-cyclodextrin (β-CD) polymers crosslinked with rigid aromatic groups were prepared and used for lead (Pb), copper (Cu) and cadmium (Cd) removal for the first time. The negatively charged β-CD polymers with large BET surface area were suitable to be used in HMs adsorption. The adsorption process completed in 5 min was well fit by Freundlich isotherm model and pseudo-second-order model. The intraparticle diffusion model was also appropriate to describe the adsorption of Pb, Cu and Cd on β-CD polymer. The maximum of adsorption capacities at 25 °C for Pb, Cu and Cd were 196.42, 164.43 and 136.43 mg/g when the initial concentration was 200 mg/L. The HMs adsorption process on the surface of β-CD polymer was an endothermic and spontaneous process. Both of the electrostatic interaction and distribution of Pb, Cu and Cd species influenced the adsorption process at different pH values. The order of removal efficiencies in multi-component adsorption for the three metal ions were Pb > Cu > Cd. The adsorption mechanisms were H+ ions on hydroxyl groups exchanged with heavy metal ions and electrostatic interactions. This study indicated that β-CD polymers could be developed into effective adsorbents for rapid removal of heavy metals.

Interaction of polymer with discotic clay particles

International Nuclear Information System (INIS)

Auvray, L.; Lal, J.

1999-01-01

Normally synthetic well defined monodisperse discotic laponite clays are known to form a gel phase at mass concentrations as low as a few percent in distilled water. Hydrosoluble polymer polyethylene oxide was added to this intriguing clay system, it was observed that it either prevents gelation or slows it down extremely depending on the polymer weight, concentration or the laponite concentration. Small Angle Neutron scattering (SANS) was used to study these systems because only by isotopic labeling can the structure of the adsorbed polymer layers be determined. The contrast variation technique is specifically used to determine separately the different partial structure factors of the clay and polymer. In this way the signal of the adsorbed chains is separated from the signal of the free chains in the dilute regime. Attempts have also been made to characterize the structure in the concentrated regime of laponite with polymer

Evaluation of synthetic water-soluble metal-binding polymers with ultrafiltration for selective concentration of americium and plutonium

International Nuclear Information System (INIS)

Smith, B.F.; Gibson, R.R.; Jarvinen, G.D.; Jones, M.M.; Lu, M.T.; Robison, T.W.; Schroeder, N.C.; Stalnaker, N.

1997-01-01

Routine counting methods and ICP-MS are unable to directly measure the new US Department of Energy (DOE) regulatory level for discharge waters containing alpha-emitting radionuclides of 30 pCi/L total alpha or the 0.05 pCi/L regulatory level for Pu or Am activity required for surface waters at the Rocky Flats site by the State of Colorado. This inability indicates the need to develop rapid, reliable, and robust analytical techniques for measuring actinide metal ions, particularly americium and plutonium. Selective separation or preconcentration techniques would aid in this effort. Water-soluble metal-binding polymers in combination with ultrafiltration are shown to be an effective method for selectively removing dilute actinide ions from acidic solutions of high ionic strength. The actinide-binding properties of commercially available water-soluble polymers and several polymers which have been reported in the literature were evaluated. The functional groups incorporated in the polymers were pyrrolidone, amine, oxime, and carboxylic, phosphonic, or sulfonic acid. The polymer containing phosphonic acid groups gave the best results with high distribution coefficients and concentration factors for 241 Am(III) and 238 Pu(III)/(IV) at pH 4 to 6 and ionic strengths of 0.1 to 4

Activity coefficients at infinite dilution of organic solutes in diethylene glycol and triethylene glycol from gas–liquid chromatography

International Nuclear Information System (INIS)

Williams-Wynn, Mark D.; Letcher, Trevor M.; Naidoo, Paramespri; Ramjugernath, Deresh

2013-01-01

Highlights: • γ 13 ∞ values reported for 25 organic solutes in the solvents DEG and TEG. • Measurements undertaken using the glc technique at T = (333.2, 348.2, and 363.2) K. • Measurements at elevated temperature possible by pre-saturation of carrier gas. • Comparison of DEG and TEG performance with a number of solvents. -- Abstract: The infinite dilution activity coefficients for 25 hydrocarbon solutes in diethylene glycol (DEG) and triethylene glycol (TEG) were measured using the gas–liquid chromatography technique with pre-saturation of the carrier gas. The hydrocarbon solutes included n-alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, alkylbenzenes and alkanols. At the temperatures at which measurements were conducted, the solvents were volatile, and pre-saturation was considered necessary. The measurements were made at T = (333.2, 348.2 and 363.2) K. Values of the selectivity and capacity relating to DEG and TEG, for two sets of mixtures, which are usually difficult to separate by distillation or solvent extraction, were calculated from the experimental results. The two sets of mixtures were: cyclohexane and benzene; and benzene and methanol. The results obtained in this work were then compared to values for other solvents, at similar temperatures, which were obtained or calculated from literature data

Sustainability of silver nanoparticles in solutions and polymer materials

International Nuclear Information System (INIS)

Khaydarov, R.R.; Malikov, Sh.; Khaydarov, R.A.; Mironov, V.V.

2006-01-01

The technology of obtaining stable silver nanoparticles in solutions and composite materials for attainment of antimicrobial and antifungal properties to different surfaces has been developed. The shape of particles is spherical, diameter is about 5 nm. Various concentrations of silver nanoparticles have been deposited onto surfaces of different materials (cotton and synthetic fabrics, fibroid sorbents and polymer materials). Different ways of treatment and densities of nanoparticles on the treated surface have been studied during 6 months with respect to the best sustainability. In order to prevent agglomeration of obtained metal nanoparticles on the surface of materials treated, stabilizing reagents (ethylene glycol, formic acid, sodium dodecyl sulphate, etc.) have been used and their relative efficacy has been examined. Residual concentrations of the nanoparticles on various fabrics after 1, 3, 5 and 10 cycles of washing have been also studied. The treated fabrics keep their antibacterial properties after at least 3 times of laundering. The best finishing process to attach silver nanoparticles combination to various materials has been compared with biocidal properties of such antibacterial agents as metal salt solutions and zinc pyrithione.The possibility of treatment of nuclear track membranes by silver nanoparticles in order to prevent microbial growth on the surface of membranes has been discussed. (author)

Spinning process variables and polymer solution effects in the die-swell phenomenon during hollow fiber membranes formation

Directory of Open Access Journals (Sweden)

Pereira C.C.

2000-01-01

Full Text Available During hollow fiber spinning many variables are involved whose effects are still not completely clear. However, its understanding is of great interest because the control of these variables may originate membranes with the desired morphologies and physical properties. In this work, the phase inversion process induced by the immersion precipitation technique was applied to prepare hollow fibers membranes. It was verified that some of the variables involved, can promote a visco-elastic polymer solution expansion, called die-swell phenomenon, which is undesired since it may lead to low reproducibility of the permeation properties. The effects of the distance between spinneret and precipitation bath, the bore liquid composition, and the polymer solution composition were analyzed and discussed in order to avoid this phenomenon. According to the results, it was verified that the parameters investigated might promote a delay precipitation, which restrained the visco-elastic expansion.

Liquid-liquid phase separation in dilute solutions of poly(styrene sulfonate) with multivalent cations: Phase diagrams, chain morphology, and impact of temperature

Science.gov (United States)

Hansch, Markus; Hämisch, Benjamin; Schweins, Ralf; Prévost, Sylvain; Huber, Klaus

2018-01-01

The dilute solution behavior of sodium poly(styrene sulfonate) is studied in the presence of trivalent Al3+ and bivalent Ba2+ cations at various levels of excess NaCl. The study evaluates the phase behavior and the morphology of the polyelectrolyte chains with increasing extent of decoration with the Al3+ and Ba2+ cations and analyses the effect of temperature on these decorated chains. The phase behavior is presented in the form of the cation concentration versus the respective poly(styrene sulfonate) concentration, recorded at the onset of precipitation. Whereas poly(styrene sulfonate) with Al3+ exhibits a linear phase boundary, denoted as the "threshold line," which increases with increasing poly(styrene sulfonate) concentration, Ba2+ cations show a threshold line which is independent of the poly(styrene sulfonate) concentration. An additional re-entrant phase, at considerably higher cation content than those of the threshold lines, is observed with Al3+ cations but not with Ba2+ cations. The threshold line and the re-entrant phase boundary form parts of the liquid-liquid phase boundary observed at the limit of low polymer concentration. The dimensions of the polyelectrolyte chains shrink considerably while approaching the respective threshold lines on increase of the Al3+ and Ba2+ cation content. However, subtle differences occur between the morphological transformation induced by Al3+ and Ba2+. Most strikingly, coils decorated with Al3+ respond very differently to temperature variations than coils decorated with Ba2+ do. As the temperature increases, the poly(styrene sulfonate) chains decrease their size in the presence of Al3+ cations but increase in size in the presence of Ba2+ cations.

The molecular properties of biochar carbon released in dilute acidic solution and its effects on maize seed germination.

Science.gov (United States)

Sun, Jingling; Drosos, Marios; Mazzei, Pierluigi; Savy, Davide; Todisco, Daniele; Vinci, Giovanni; Pan, Genxing; Piccolo, Alessandro

2017-01-15

It is not yet clear whether the carbon released from biochar in the soil solution stimulates biological activities. Soluble fractions (AQU) from wheat and maize biochars, whose molecular content was thoroughly characterized by FTIR, 13 C and 1 H NMR, and high-resolution ESI-IT-TOF-MS, were separated in dilute acidic solution to simulate soil rhizospheric conditions and their effects evaluated on maize seeds germination activity. Elongation of maize-seeds coleoptile was significantly promoted by maize biochar AQU, whereas it was inhibited by wheat biochar AQU. Both AQU fractions contained relatively small heterocyclic nitrogen compounds, whose structures were accounted by their spectroscopic properties. Point-of-Zero-Charge (PZC) values and van Krevelen plots of identified masses of soluble components suggested that the dissolved carbon from maize biochar behaved as humic-like supramolecular material capable to adhere to seedlings and deliver bioactive molecules. These findings contribute to understand the biostimulation potential of biochars from crop biomasses when applied in agricultural production. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of activity coefficients at infinite dilution of water and organic solutes (polar and non-polar) in the Ammoeng 100 ionic liquid at T = (308.15, 313.5, 323.15, and 333.15) K

International Nuclear Information System (INIS)

Reddy, Prashant; Chiyen, Kaleng J.; Deenadayalu, Nirmala; Ramjugernath, Deresh

2011-01-01

Highlights: → Activity coefficients at infinite dilution in the ionic liquid Ammoeng 100. → Twenty-seven solutes investigated at T = (308.15, 313.15, 323.15, and 333.15) K. → Ammoeng 100 not suited to aromatic/aliphatic and alkane/alcohol separations. - Abstract: Activity coefficients at infinite dilution (γ 13 ∞ ) have been determined for 27 solutes, viz. water and organic compounds (n-alkanes, cycloalkanes, 1-alkenes, 1-alkynes, aromatics, alcohols, and ketones) in the ionic liquid Ammoeng 100, by gas-liquid chromatography at four different temperatures, T = (308.15, 313.15, 323.15, and 333.15) K. Columns with different phase loadings (20 to 24)% of the ionic liquid in the stationary phase were employed to obtain γ 13 ∞ values at each temperature investigated. Partial molar excess enthalpies at infinite dilution (ΔH 1 E,∞ ) were calculated for the solutes from the temperature dependency relationship of the ln(γ 13 ∞ ) values for the temperature range in this study. The uncertainties in the determinations of the γ 13 ∞ and ΔH 1 E,∞ values are 6% and 10%, respectively. Selectivity values at infinite dilution (S ij ∞ ), have been computed from the γ 13 ∞ values to assess the potential candidacy of the Ammoeng 100 ionic liquid for the separation of alkane/alcohol mixtures. The results from this study have been compared to those available for several ionic liquids from previous investigations.

Lattice cluster theory of associating polymers. I. Solutions of linear telechelic polymer chains.

Science.gov (United States)

Dudowicz, Jacek; Freed, Karl F

2012-02-14

The lattice cluster theory (LCT) for the thermodynamics of a wide array of polymer systems has been developed by using an analogy to Mayer's virial expansions for non-ideal gases. However, the high-temperature expansion inherent to the LCT has heretofore precluded its application to systems exhibiting strong, specific "sticky" interactions. The present paper describes a reformulation of the LCT necessary to treat systems with both weak and strong, "sticky" interactions. This initial study concerns solutions of linear telechelic chains (with stickers at the chain ends) as the self-assembling system. The main idea behind this extension of the LCT lies in the extraction of terms associated with the strong interactions from the cluster expansion. The generalized LCT for sticky systems reduces to the quasi-chemical theory of hydrogen bonding of Panyioutou and Sanchez when correlation corrections are neglected in the LCT. A diagrammatic representation is employed to facilitate the evaluation of the corrections to the zeroth-order approximation from short range correlations. © 2012 American Institute of Physics

Study of the flow development of polymer solutions through capillaries

International Nuclear Information System (INIS)

Perez-Gonzalez, J.; De Vargas, L.; Tejero, M.

1991-01-01

Flow experiments through capillaries with semirigid and rigid polymers in aqueous solutions were carried out in order to study the dependence of the flow development on the molecular conformation and the length to diameter ratio (L/D), of the capillary at relatively low shear rates. It was found that the apparent viscosity has a strong dependence upon the ratio L/D for a given shear rate, although an asymptotic value is reached. This dependence was reflected in the non-linearity of Bagley's plots. The asymptotic value was attained at lower L/D values for semirigid molecules than for rigid ones, showing the influence of the molecular conformation on the flow field development due to the different modes of relaxation for each type of molecule. (Author)

Process for final storage of high level radioactive fission product solution

International Nuclear Information System (INIS)

Ellis, J.R.B.; Fries, B.A.

1984-01-01

In this process for the storage of an aqueous solution of radioactive nuclides, the solution is diluted with system water, which is obtained from a reservoir below the bottom of the sea in a porous geological stratum. After dilution, the diluted solution is injected into the same geological stratum under the bottom of the sea. (orig.) [de

All-Solution-Processed, Ambient Method for ITO-Free, Roll-Coated Tandem Polymer Solar Cells using Solution- Processed Metal Films

DEFF Research Database (Denmark)

Angmo, Dechan; Dam, Henrik Friis; Andersen, Thomas Rieks

2014-01-01

A solution-processed silver film is employed in the processing of top-illuminated indium-tin-oxide (ITO)-free polymer solar cells in single- and double-junction (tandem) structures. The nontransparent silver film fully covers the substrate and serves as the bottom electrode whereas a PEDOT...... in terms of surface morphological and topographical properties and to ITO in terms of flexibility. The slot–die coated Ag film demonstrates extremely low roughness (a root-meansquare roughness of 3 nm was measured over 240_320 mm2 area), is highly conductive (

A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

KAUST Repository

Moia, Davide

2017-11-28

We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient transport of electronic charge via the conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices.

Investigation of Possible Maillard Reaction Between Acyclovir and Dextrose upon Dilution Prior to Parenteral Administration.

Science.gov (United States)

Siahi Shadbad, Mohammad Reza; Ghaderi, Faranak; Hatami, Leila; Monajjemzadeh, Farnaz

2016-12-01

In this study the stability of parenteral acyclovir (ACV) when diluted in dextrose (DEX) as large volume intravenous fluid preparation (LVIF) was evaluated and the possible Maillard reaction adducts were monitored in the recommended infusion time. Different physicochemical methods were used to evaluate the Maillard reaction of dextrose with ACV to track the reaction in real infusion condition. Other large volume intravenous fluids were checked regarding the diluted drug stability profile. Differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and mass data proved the reaction of glucose with dextrose. A Maillard-specific high performance liquid chromatography (HPLC) method was used to track the reaction in real infusion condition in vitro. The nucleophilic reaction occurred in diluted parenteral preparations of acyclovir in 5% dextrose solutions. The best diluent solution was also selected as sodium chloride and introduced based on drug stability and also its adsorption onto different infusion sets (PVC or non PVC) to provide an acceptable administration protocol in clinical practices. Although, the Maillard reaction was proved and successfully tracked in diluted solutions, and the level of drug loss when diluted in dextrose was reported to be between 0.27 up to 1.03% of the initial content. There was no drug adsorption to common infusion sets. The best diluent for parenteral acyclovir is sodium chloride large volume intravenous fluid.

Soft interactions and volume exclusion by polymeric crowders can stabilize or destabilize transient structure in disordered proteins depending on polymer concentration.

Science.gov (United States)

Rusinga, Farai I; Weis, David D

2017-08-01

The effects of macromolecular crowding on the transient structure of intrinsically disordered proteins is not well-understood. Crowding by biological molecules inside cells could modulate transient structure and alter IDP function. Volume exclusion theory and observations of structured proteins suggest that IDP transient structure would be stabilized by macromolecular crowding. Amide hydrogen exchange (HX) of IDPs in highly concentrated polymer solutions would provide valuable insights into IDP transient structure under crowded conditions. Here, we have used mass spectrometry to measure HX by a transiently helical random coil domain of the activator of thyroid and retinoid receptor (ACTR) in solutions containing 300 g L -1 and 400 g L -1 of Ficoll, a synthetic polysaccharide, using a recently-developed strong cation exchange-based cleanup method [Rusinga, et al., Anal Chem 2017;89:1275-1282]. Transiently helical regions of ACTR exchanged faster in 300 g L -1 Ficoll than in dilute buffer. In contrast, one transient helix exchanged more slowly in 400 g L -1 Ficoll. Nonspecific interactions destabilize ACTR helicity in 300 g L -1 Ficoll because ACTR engages with the Ficoll polymer mesh. In contrast, 400 g L -1 Ficoll is a semi-dilute solution where ACTR cannot engage the Ficoll mesh. At this higher concentration, volume exclusion stabilizes ACTR helicity because ACTR is compacted in interstitial spaces between Ficoll molecules. Our results suggest that the interplay between nonspecific interactions and volume exclusion in different cellular compartments could modulate IDP function by altering the stability of IDP transient structures. Proteins 2017; 85:1468-1479. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Degradation of chitosan hydrogel dispersed in dilute carboxylic acids by solution plasma and evaluation of anticancer activity of degraded products

Science.gov (United States)

Chokradjaroen, Chayanaphat; Rujiravanit, Ratana; Theeramunkong, Sewan; Saito, Nagahiro

2018-01-01

Chitosan is a polysaccharide that has been extensively studied in the field of biomedicine, especially its water-soluble degraded products called chitooligosaccharides (COS). In this study, COS were produced by the degradation of chitosan hydrogel dispersed in a dilute solution (i.e., 1.55 mM) of various kinds of carboxylic acids using a non-thermal plasma technology called solution plasma (SP). The degradation rates of chitosan were influenced by the type of carboxylic acids, depending on the interaction between chitosan and each carboxylic acid. After SP treatment, the water-soluble degraded products containing COS could be easily separated from the water-insoluble residue of chitosan hydrogel by centrifugation. The production yields of the COS were mostly higher than 55%. Furthermore, the obtained COS products were evaluated for their inhibitory effect as well as their selectivity against human lung cancer cells (H460) and human lung normal cells (MRC-5).

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

Energy Technology Data Exchange (ETDEWEB)

Rumbles, Garry [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Reid, Obadiah G [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pace, Natalie A [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2018-02-19

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solid state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.

Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.

Science.gov (United States)

Little, Brian K; Lockhart, PaviElle; Slaten, B L; Mills, G

2013-05-23

Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.

Solution processing of polymer semiconductor: Insulator blends-Tailored optical properties through liquid-liquid phase separation control

KAUST Repository

Hellmann, Christoph; Treat, Neil D.; Scaccabarozzi, Alberto D.; Razzell Hollis, Joseph; Fleischli, Franziska D.; Bannock, James H.; de Mello, John; Michels, Jasper J.; Kim, Ji-Seon; Stingelin, Natalie

2014-01-01

© 2014 Wiley Periodicals, Inc. It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles.

Solution processing of polymer semiconductor: Insulator blends-Tailored optical properties through liquid-liquid phase separation control

KAUST Repository

Hellmann, Christoph

2014-12-17

© 2014 Wiley Periodicals, Inc. It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles.

Activity coefficients at infinite dilution for solutes in the trioctylmethylammonium bis(trifluoromethylsulfonyl)imide ionic liquid using gas-liquid chromatography

International Nuclear Information System (INIS)

Gwala, Nobuhle V.; Deenadayalu, Nirmala; Tumba, Kaniki; Ramjugernath, Deresh

2010-01-01

The activity coefficient at infinite dilution (γ 13 ∞ ) for 30 solutes: alkanes, alkenes, cycloalkanes, alkynes, ketones, alcohols, and aromatic compounds was determined from gas-liquid chromatography (glc) measurements at three temperatures (303.15, 313.15, and 323.15) K. The ionic liquid: trioctylmethylammonium bis(trifluoromethylsulfonyl)imide, was used as the stationary phase. For each temperature, γ 13 ∞ values were determined using two columns with different mass percent packing of the ionic liquid. The selectivity (S 12 ∞ ) value was calculated from the γ 13 ∞ to determine the suitability of the solvent as a potential entrainer for extractive distillation in the separation of an hexane/benzene mixture, indicative of a typical industrial separation problem for benchmarking purposes.

Polymer crowding and shape distributions in polymer-nanoparticle mixtures

Energy Technology Data Exchange (ETDEWEB)

Lim, Wei Kang; Denton, Alan R., E-mail: alan.denton@ndsu.edu [Department of Physics, North Dakota State University, Fargo, North Dakota 58108-6050 (United States)

2014-09-21

Macromolecular crowding can influence polymer shapes, which is important for understanding the thermodynamic stability of polymer solutions and the structure and function of biopolymers (proteins, RNA, DNA) under confinement. We explore the influence of nanoparticle crowding on polymer shapes via Monte Carlo simulations and free-volume theory of a coarse-grained model of polymer-nanoparticle mixtures. Exploiting the geometry of random walks, we model polymer coils as effective penetrable ellipsoids, whose shapes fluctuate according to the probability distributions of the eigenvalues of the gyration tensor. Accounting for the entropic cost of a nanoparticle penetrating a larger polymer coil, we compute the crowding-induced shift in the shape distributions, radius of gyration, and asphericity of ideal polymers in a theta solvent. With increased nanoparticle crowding, we find that polymers become more compact (smaller, more spherical), in agreement with predictions of free-volume theory. Our approach can be easily extended to nonideal polymers in good solvents and used to model conformations of biopolymers in crowded environments.

Polymer crowding and shape distributions in polymer-nanoparticle mixtures

International Nuclear Information System (INIS)

Lim, Wei Kang; Denton, Alan R.

2014-01-01

Macromolecular crowding can influence polymer shapes, which is important for understanding the thermodynamic stability of polymer solutions and the structure and function of biopolymers (proteins, RNA, DNA) under confinement. We explore the influence of nanoparticle crowding on polymer shapes via Monte Carlo simulations and free-volume theory of a coarse-grained model of polymer-nanoparticle mixtures. Exploiting the geometry of random walks, we model polymer coils as effective penetrable ellipsoids, whose shapes fluctuate according to the probability distributions of the eigenvalues of the gyration tensor. Accounting for the entropic cost of a nanoparticle penetrating a larger polymer coil, we compute the crowding-induced shift in the shape distributions, radius of gyration, and asphericity of ideal polymers in a theta solvent. With increased nanoparticle crowding, we find that polymers become more compact (smaller, more spherical), in agreement with predictions of free-volume theory. Our approach can be easily extended to nonideal polymers in good solvents and used to model conformations of biopolymers in crowded environments

Trap Healing for High-Performance Low-Voltage Polymer Transistors and Solution-Based Analog Amplifiers on Foil.

Science.gov (United States)

Pecunia, Vincenzo; Nikolka, Mark; Sou, Antony; Nasrallah, Iyad; Amin, Atefeh Y; McCulloch, Iain; Sirringhaus, Henning

2017-06-01

Solution-processed semiconductors such as conjugated polymers have great potential in large-area electronics. While extremely appealing due to their low-temperature and high-throughput deposition methods, their integration in high-performance circuits has been difficult. An important remaining challenge is the achievement of low-voltage circuit operation. The present study focuses on state-of-the-art polymer thin-film transistors based on poly(indacenodithiophene-benzothiadiazole) and shows that the general paradigm for low-voltage operation via an enhanced gate-to-channel capacitive coupling is unable to deliver high-performance device behavior. The order-of-magnitude longitudinal-field reduction demanded by low-voltage operation plays a fundamental role, enabling bulk trapping and leading to compromised contact properties. A trap-reduction technique based on small molecule additives, however, is capable of overcoming this effect, allowing low-voltage high-mobility operation. This approach is readily applicable to low-voltage circuit integration, as this work exemplifies by demonstrating high-performance analog differential amplifiers operating at a battery-compatible power supply voltage of 5 V with power dissipation of 11 µW, and attaining a voltage gain above 60 dB at a power supply voltage below 8 V. These findings constitute an important milestone in realizing low-voltage polymer transistors for solution-based analog electronics that meets performance and power-dissipation requirements for a range of battery-powered smart-sensing applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Yield Production of Levulinic Acid from Pretreated Cow Dung in Dilute Acid Aqueous Solution

Directory of Open Access Journals (Sweden)

Jialei Su

2017-02-01

Full Text Available Agricultural waste cow dung was used as feedstock for the production of a high value–added chemical levulinic acid (LA in dilute acid aqueous solutions. A high LA yield of 338.9 g/kg was obtained from the pretreated cow dung, which was much higher than that obtained from the crude cow dung (135 g/kg, mainly attributed to the breakage of the lignin fraction in the lignocellulose structure of the cow dung by potassium hydroxide (KOH pretreatment, and thus enhanced the accessibility of cow dung to the acid sites in the catalytic reaction. Meanwhile, another value-added chemical formic acid could be obtained with a yield of ca. 160 g/kg in the process, implying a total production of ca. 500 g/kg yield for LA and formic acid from the pretreated cow dung with the proposed process. The developed process was shown to be tolerant to high initial substrate loading with a satisfied LA yield. This work provides a promising strategy for the value-increment utilization of liglocellulosic agricultural residues.

Evaluation of two different HEDP content kits: Stability study against dilution both in vivo and in vitro

International Nuclear Information System (INIS)

Inoue, O.; Ikeda, I.; Kurata, K.

1982-01-01

Two different HEDP content kits (Kit A, HEDP: 1 mg, SnCl 2 x 2H 2 O: 0.5 mg; and Kit B, HEDP: 10 mg, SnCl 2 x 2H 2 O: 0.5 mg) were evaluated for their stability against dillution. Sup(99m)Tc-HEDP solutions prepared from these two kits were diluted from 10 to 6000 fold with 0.9% NaCl solution just before evaluation both in vivo and in vitro. In the case of Kit A, significant soft tissue uptake in vivo and released free pertechnetate in vitro were observed by diluting the sup(99m)Tc-HEDP solution. On the other hand, sup(99m)Tc-HEDP prepared from Kit B was found to be sufficiently stable against dilution. The stability after preparation of each diluted sup(99m)-HEDP was also greatly affected by its HEDP concentration. Preliminary analysis of absorption spectra for each 99 Tc-HEDP indicated the possibility of two different sup(99m)Tc-HEDP complex formation by varied HEDP concentration. These results indicated that a cold reagent like Kit A might cause a higher soft tissue uptake due to its dilution in vivo during a clinical study for bone scanning. (orig.) [de

Self-association of caffeine in aqueous solution. Study of dilute solutions by normal and second derivative UV absorption spectroscopy.

Science.gov (United States)

Iza, N.; Gil, M.; Montero, J. L.; Morcillo, J.

1988-05-01

The concentration dependence of the spectral parameters of caffeine bands at ˜205 and 273 nm has been studied in aqueous solution by normal and second derivative spectroscopy. The concentration range was 5 x 10 -6 - 5 x 10 -3 M and thirty-five different concentrations were used. Discontinuities in parameter variation of these two bands at ˜7.5 x 10 -5, ˜2 x 10 -4, and ˜1 x 10 -3M were observed as concentration was increased. These "limiting" concentrations define three quite differenciated hyper- or hipochromic effects: the first one can be explained as caffeine-water molecule interaction and the second and third as dimer and (dimer + polymer) stacking, respectively. Apparent self-association constants using the isodesmic model have been obtained K= 160 M -1 (for the second hypochromic effect) and K= 13.6 M -1 (for the third hypochromic effect), for the 273 nm band. It is noteworthy that the three "limiting" concentrations coincide with changes in DNA-caffeine interaction modes (H. Lang , 1976) and biological activity (I.B. Syed , 1976).

Interaction of derived polymers from pyrrole with biocompatible solutions

International Nuclear Information System (INIS)

Lopez G, O. G.

2010-01-01

This work presents a study about the synthesis by plasma, the electric properties and superficial interaction of polymers derived from pyrrole doped with Iodine with potential use as bio material. Poly-pyrrole is a semiconductor and biocompatible polymer with potential application in the development of artificial muscles and implants where the electric interaction between cells and material is an important variable. The syntheses were made at 13.5 MHz in a glass tubular reactor of 1500 cm 3 with electrodes of 6.5 cm diameter and stainless steel flanges. An electrode was connected to the RF terminal of the power supply that is combined with a matching coupling resistance. The monomer and dopant used in this work were pyrrole and Iodine respectively, in closed containers. They were vaporized and injected separately into the reactor at room temperature and 0.1 mbar. The vapors of the reagents mixed freely in the reactor. The synthesis time was 240 min at 40, 60, 80 and 100 W. The polymers were obtained as thin films adhered to the reactor walls. The films were washed and swollen with distilled water and removed from the reactor walls with a small spatula. The polymers were irradiated with gamma rays at 18 and 22 KGy. Due to the fact that the doses are cumulative, the final dose applied was 40 KGy. The polymers characterization was carried out by Fourier Transform Infrared Spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy, contact angle, electrical conductivity and X-ray diffraction. The analyses indicates that the polymers have very similar structure in almost the entire power range, showing C-O, C=C, C-H, O-H, N-H bonds with a predominantly amorphous structure. The TGA analyses showed that the material has 4 or 5 loses of material. The first one starts after that 115 C except for the material irradiated at 40 KGy, this one begins in 87 C, the second one is in the interval of 196 and 295 C, the third one between 311 and 500 C, and the last

Studies on extraction behaviour of U (VI) and Pu (IV) by Aliquat-336 encapsulated in microporous polymer beads

International Nuclear Information System (INIS)

Parikh, K.J.; Kedari, C.S.; Pandit, S.S.; Tripathi, S.C.; Dwivedi, C.; Singh, K.K.; Kumar, M.; Bajaj, P.N.

2009-01-01

Aliquat-336 encapsulated microporous polymeric beads (AEPB) were prepared to investigate their applicability for the solid-liquid extraction Pu (IV) from nitric acid solutions. Batch equilibration studies on the extractions of U (VI) and Pu (IV) from aqueous solutions using AEPB have been carried out at different concentrations of nitric acid and sodium nitrate. Extraction of Pu (IV) increases with increasing concentration of nitrate ions in the aqueous phase where as extraction of U (VI) remains less than 5% for all the aqueous conditions studied. Polymeric beads appeared to be less stable at higher nitric acid concentrations as the extraction of Pu (IV) was found to be lowered above 4 M HNO 3 concentration. The maximum Pu (IV) uptake by AEPB was 0.84 μg per mg of beads. Pu (IV)from loaded polymer can be back extracted using dilute nitric acid or ascorbic acid solution. (author)

Effect of solution processed and thermally evaporated interlayers on the performance of backgrated polymer solar cells

Energy Technology Data Exchange (ETDEWEB)

Jayawardena, K.D.G.I.; Amarasinghe, K.M.P.; Nismy, N.A. [Advanced Technology Institute, Department of Electronic Engineering, University of Surrey, Guildford GU2 7XH (United Kingdom); Mills, C.A. [Advanced Technology Institute, Department of Electronic Engineering, University of Surrey, Guildford GU2 7XH (United Kingdom); Advanced Coatings Group, Surface Engineering Department, Tata Steel Research Development and Technology, Swinden Technology Centre, Rotherham, S60 3AR (United Kingdom); Silva, S.R.P., E-mail: s.silva@surrey.ac.uk [Advanced Technology Institute, Department of Electronic Engineering, University of Surrey, Guildford GU2 7XH (United Kingdom)

2015-09-30

Polymer solar cells are fast gaining momentum as a potential solution towards low cost sustainable energy generation. However, the performance of architectures is known to be limited by the thin film nature of the active layer which, although required due to low charge carrier mobilities, limits the optical coupling to the active layer. The formation of periodic backgratings has been proposed as a solution to this problem. Here, we investigate the effect of solution processed and thermally evaporated interlayers on the performance of backgrated polymer solar cells. Analysis of device performance under standard conditions indicates higher power conversion efficiencies with the incorporation of the evaporated interlayer (5.7%) over a sol–gel processed interlayer (4.9%). This is driven by a more conformal coating as evidenced through two orders of magnitude higher electron mobilities (10{sup −5} versus 10{sup −7} cm{sup 2} V{sup −1} s{sup −1}) as well as the balanced electron and hole transport observed for the former architecture. It is believed that these results will catalyse further development of such device engineering concepts for improved optical coupling in thin film photovoltaics. - Highlights: • Effect of interlayers on backgrated photovoltaic devices is tested. • Evaporated interlayers lead to better device performance. • Better charge extraction is observed for evaporated interlayers.

Dilution Ratios for HB Line Phase I Eductor System

International Nuclear Information System (INIS)

Steimke, J.L.

2002-01-01

HB Line Phase I product transfer includes an eductor which transfers liquid from Product Hold Tank (PHT) RT-33 or RT-34 to Tank 11.1. The eductor also dilutes the liquid from the PHT with eductant. Dilution must be reliably controlled because of criticality concerns with H Canyon Tanks. The eductor system, which contains a 1 inch Model 264 Schutte and Koerting eductor, was previously modeled [1] in 1998 and dilution ratios were calculated for different flow restrictors, eductant pressures and densities for the eductant and the contents of the PHT. The previous calculation was performed using spreadsheet software no longer supported at SRS. For the previous work dilution ratio was defined as the volume of eductant consumed divided by volume of PHT contents transferred. Since 1998 HB Line Engineering has changed the definition of dilution ratio to the total volume of liquid, eductant consumed plus the volume of PHT liquid transferred, divided by the volume of PHT liquid transferred. The 1998 base case calculation was for a restrictor diameter of 0.334 inches, an eductant supply pressure of 15 psig, full PHT, an eductant specific gravity of 1.385 and a PHT density of 1.015. The base case dilution ratio calculated in 1998 using the current definition was 3.52. After accounting for uncertainty the minimum dilution ratio decreased to 3.23. In 2001 HB Line Engineering requested that the calculation be repeated for a manganous nitrate solution eductant and also a process water eductant. The other conditions were the same as for the 1998 calculation. The objective of this report is to document the calculations and the results

Selective on site separation and detection of molecules in diluted solutions with super-hydrophobic clusters of plasmonic nanoparticles

KAUST Repository

Gentile, Francesco T.; Coluccio, Maria Laura; Proietti Zaccaria, Remo; Francardi, Marco; Cojoc, Gheorghe; Perozziello, Gerardo; Raimondo, Raffaella; Candeloro, Patrizio; Di Fabrizio, Enzo M.

2014-01-01

Super-hydrophobic surfaces are bio-inspired interfaces with a superficial texture that, in its most common evolution, is formed by a periodic lattice of silicon micro-pillars. Similar surfaces reveal superior properties compared to conventional flat surfaces, including very low friction coefficients. In this work, we modified meso-porous silicon micro-pillars to incorporate networks of metal nano-particles into the porous matrix. In doing so, we obtained a multifunctional-hierarchical system in which (i) at a larger micrometric scale, the super-hydrophobic pillars bring the molecules dissolved in an ultralow-concentration droplet to the active sites of the device, (ii) at an intermediate meso-scale, the meso-porous silicon film adsorbs the low molecular weight content of the solution and, (iii) at a smaller nanometric scale, the aggregates of silver nano-particles would measure the target molecules with unprecedented sensitivity. In the results, we demonstrated how this scheme can be utilized to isolate and detect small molecules in a diluted solution in very low abundance ranges. The presented platform, coupled to Raman or other spectroscopy techniques, is a realistic candidate for the protein expression profiling of biological fluids. © 2014 the Partner Organisations.

Rheological behavior and non-enzymatic degradation of a sulfated galactan from Halymenia durvillei (Halymeniales, Rhodophyta).

Science.gov (United States)

Fenoradosoa, Taratra André; Laroche, Céline; Delattre, Cedric; Dulong, Virginie; Le Cerf, Didier; Picton, Luc; Michaud, Philippe

2012-07-01

The rheological behavior of a sulfated galactan extracted from Halymenia durvillei, a red seaweed collected in the coastal waters of a small island of Madagascar (Nosy-be in Indian Ocean), was investigated in dilute and semi-dilute solutions. In dilute solution with NaCl at 0.3 M, the polysaccharide adopted a coil conformation whereas, at higher concentrations, the polymer had the behavior of shear-thinning fluid, typical of polymer with high molar mass or semi-rigid conformation. Degradations of this lambda carrageenan-like, using radical depolymerization, and high-pressure homogenization led to several samples of various and controlled molar masses. The measure of their intrinsic viscosities permitted the determination of the relationship of Mark-Houwink-Sakurada.

Driving High-Performance n- and p-type Organic Transistors with Carbon Nanotube/Conjugated Polymer Composite Electrodes Patterned Directly from Solution

KAUST Repository

Hellstrom, Sondra L.; Jin, Run Zhi; Stoltenberg, Randall M.; Bao, Zhenan

2010-01-01

We report patterned deposition of carbon nanotube/conjugated polymer composites from solution with high nanotube densities and excellent feature resolution. Such composites are suited for use as electrodes in high-performance transistors

Molar mass, radius of gyration and second virial coefficient from new static light scattering equations for dilute solutions: application to 21 (macro)molecules.

Science.gov (United States)

Illien, Bertrand; Ying, Ruifeng

2009-05-11

New static light scattering (SLS) equations for dilute binary solutions are derived. Contrarily to the usual SLS equations [Carr-Zimm (CZ)], the new equations have no need for the experimental absolute Rayleigh ratio of a reference liquid and solely rely on the ratio of scattered intensities of solutions and solvent. The new equations, which are based on polarizability equations, take into account the usual refractive index increment partial differential n/partial differential rho(2) complemented by the solvent specific polarizability and a term proportional to the slope of the solution density rho versus the solute mass concentration rho(2) (density increment). Then all the equations are applied to 21 (macro)molecules with a wide range of molar mass (0.2equations clearly achieve a better agreement with supplier M values. For macromolecules (M>500 kg mol(-1)), for which the scattered intensity is no longer independent of the scattering angle, the new equations give the same value of the radius of gyration as the CZ equation and consistent values of the second virial coefficient.

Radiolysis of paracetamol in dilute aqueous solution

International Nuclear Information System (INIS)

Szabó, László; Tóth, Tünde; Homlok, Renáta; Takács, Erzsébet; Wojnárovits, László

2012-01-01

Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O 2 is c.a. 10%. The efficiency is 2–3 times higher in the presence of O 2 due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily. - Highlights: ► Paracetamol is easily degraded in aqueous solution by low dose irradiation. ► Main degradation products are hydroxylated molecules, acetamide and hydroquinone. ► Toxicity of solutions goes through a maximum as a function of dose.

Radiolysis of paracetamol in dilute aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Szabo, Laszlo [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Budapest University of Technology and Economics, Budapest (Hungary); Toth, Tuende [Budapest University of Technology and Economics, Budapest (Hungary); Homlok, Renata [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Takacs, Erzsebet [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Wojnarovits, Laszlo [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary)

2012-09-15

Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O{sub 2} is c.a. 10%. The efficiency is 2-3 times higher in the presence of O{sub 2} due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily. - Highlights: Black-Right-Pointing-Pointer Paracetamol is easily degraded in aqueous solution by low dose irradiation. Black-Right-Pointing-Pointer Main degradation products are hydroxylated molecules, acetamide and hydroquinone. Black-Right-Pointing-Pointer Toxicity of solutions goes through a maximum as a function of dose.

Crystal Fields in Dilute Rare-Earth Metals Obtained from Magnetization Measurements on Dilute Rare-Earth Alloys

DEFF Research Database (Denmark)

Touborg, P.; Høg, J.

1974-01-01

Crystal field parameters of Tb, Dy, and Er in Sc, Y, and Lu are summarized. These parameters are obtained from magnetization measurements on dilute single crystals, and successfully checked by a number of different methods. The crystal field parameters vary unpredictably with the rare-earth solute....... B40, B60, and B66 are similar in Y and Lu. Crystal field parameters for the pure metals Tb, Dy, and Er are estimated from the crystal fields in Y and Lu....

Comparative study of hydro soluble polymers solutions and surfactants aiming the polymer-rock interactions in consolidated sandstone; Estudo comparativo de solucoes de polimeros hidrossoluveis e tensoativos visando as interacoes polimero-rocha em arenito consolidado

Energy Technology Data Exchange (ETDEWEB)

Valentim, Adriano Cesar M.; Marcelino, Cleuton Pereira; Medeiros, Ana Catarina R.; Garcia, Rosangela Balaban [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Lab. de Pesquisa em Petroleo (LAPET)

2004-07-01

The polyacrylamide is one of the main polymers used in the petroleum industry. Among its properties, stands out the capacity to alter the permeability of the rock to water. However, the polyacrylamide presents some limitations, such as low tolerance to the presence of salts, what can promote its precipitation resulting in low oil recovery efficiency. The application of the polymer in emulsion can promote a larger stability, due to the presence of a surfactant, which has the capacity to modify the interfacial tension and to form a film between the phases of the emulsion. Thereby, the injection of a polymer emulsion can promote an increase of oil recovery. In this work, a preliminary study of the effect of a anionic surfactant (SDS) and polyacrylamides (anionic and neutral) on the surface tension and rheology is presented in aqueous solutions contend salt (NaCl). The results showed surface tension of the mixtures had been remained constant and low (around 32 mN/m), independent of the polymer concentration. A viscosity reduction was observed at polymeric solutions as much in presence of salt, as in presence of the surfactant. Both the samples showed a pseudo plastic behavior. (author)

Polymer solar cells with efficiency >10% enabled via a facile solution-processed Al-doped ZnO electron transporting layer

KAUST Repository

Jagadamma, Lethy Krishnan; Al-Senani, Mohammed; Amassian, Aram

2015-01-01

The present work details a facile and low-temperature (125C) solution-processed Al-doped ZnO (AZO) buffer layer functioning very effectively as electron accepting/hole blocking layer for a wide range of polymer:fullerene bulk heterojunction systems

Dynamic proton polarisation on polymers in solution: creating contrast in neutron scattering

International Nuclear Information System (INIS)

Grinten, M.G.D. van der

1995-01-01

Dynamic nuclear polarisation (DNP) as an alternative or additional method to create contrast in neutron small angle scattering has been investigated with emphasis on the study of polymers in solution. The need for high polarisations imposes specific requirements on the sample and its environment. Vitreous beads have been used as samples. Nuclear relaxation times show that they contain dissolved air. Parasitic scattering from the solvent is observed, probably arising from nanometer air bubbles. DNP is shown to be useful, in particular for samples that consist of mixtures of hydrogen-free and hydrogen-rich molecules, where the different molecules can be highlighted by changing the polarisation. ((orig.))

Efficiency of solution-processed multilayer polymer light-emitting diodes using charge blocking layers

Science.gov (United States)

Kasparek, Christian; Rörich, Irina; Blom, Paul W. M.; Wetzelaer, Gert-Jan A. H.

2018-01-01

By blending semiconducting polymers with the cross-linkable matrix ethoxylated-(4)-bisphenol-a-dimethacrylate (SR540), an insoluble layer is acquired after UV-illumination. Following this approach, a trilayer polymer light-emitting diode (PLED) consisting of a blend of poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] (poly-TPD) and SR540 as an electron-blocking layer, Super Yellow-Poly(p-phenylene vinylene) (SY-PPV) blended with SR540 as an emissive layer, and poly(9,9-di-n-octylfluorenyl-2,7-diyl) as a hole-blocking layer is fabricated from solution. The trilayer PLED shows a 23% increase in efficiency at low voltage as compared to a single layer SY-PPV PLED. However, at higher voltage, the advantage in current efficiency gradually decreases. A combined experimental and modelling study shows that the increased efficiency is not only due to the elimination of exciton quenching at the electrodes but also due to suppressed nonradiative trap-assisted recombination due to carrier confinement. At high voltages, holes can overcome the hole-blocking barrier, which explains the efficiency roll-off.

Solution-processed small molecule-polymer blend organic thin-film transistors with hole mobility greater than 5 cm 2/Vs

KAUST Repository

Smith, Jeremy N.; Zhang, Weimin; Sougrat, Rachid; Zhao, Kui; Li, Ruipeng; Cha, Dong Kyu; Amassian, Aram; Heeney, Martin J.; McCulloch, Iain A.; Anthopoulos, Thomas D.

2012-01-01

Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm 2/Vs, current on/off ratio ≥10 6 and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solution-processed small molecule-polymer blend organic thin-film transistors with hole mobility greater than 5 cm 2/Vs

KAUST Repository

Smith, Jeremy N.

2012-04-10

Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm 2/Vs, current on/off ratio ≥10 6 and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers.

Science.gov (United States)

Leng, Chuan; Huang, Hao; Zhang, Kexin; Hung, Hsiang-Chieh; Xu, Yao; Li, Yaoxin; Jiang, Shaoyi; Chen, Zhan

2018-05-07

Interfacial water structure on a polymer surface in water (or surface hydration) is related to the antifouling activity of the polymer. Zwitterionic polymer materials exhibit excellent antifouling activity due to their strong surface hydration. It was proposed to replace zwitterionic polymers using mixed charged polymers because it is much easier to prepare mixed charged polymer samples with much lower costs. In this study, using sum frequency generation (SFG) vibrational spectroscopy, we investigated interfacial water structures on mixed charged polymer surfaces in water, and how such structures change while exposing to salt solutions and protein solutions. The 1:1 mixed charged polymer exhibits excellent antifouling property while other mixed charged polymers with different ratios of the positive/negative charges do not. It was found that on the 1:1 mixed charged polymer surface, SFG water signal is dominated by the contribution of the strongly hydrogen bonded water molecules, indicating strong hydration of the polymer surface. The responses of the 1:1 mixed charged polymer surface to salt solutions are similar to those of zwitterionic polymers. Interestingly, exposure to high concentrations of salt solutions leads to stronger hydration of the 1:1 mixed charged polymer surface after replacing the salt solution with water. Protein molecules do not substantially perturb the interfacial water structure on the 1:1 mixed charged polymer surface and do not adsorb to the surface, showing that this mixed charged polymer is an excellent antifouling material.

Morphologies and separation characteristics of polyphenyl sulfone-based solvent resistant nanofiltration membranes: Effect of polymer concentration in casting solution and membrane pretreatment condition

Energy Technology Data Exchange (ETDEWEB)

Sani, Nur Aimie Abdullah; Lau, Woei Jye; Ismail, Ahmad Fauzi [Universiti Teknologi Malaysia, Skudai (Malaysia)

2015-04-15

The performance of polyphenylsulfone (PPSU) solvent resistant nanofiltration (SRNF)-based flat sheet membranes prepared from phase inversion method was investigated by varying the concentration of polymer in the dope solution and condition of membrane pretreatment process. The membrane properties were characterized by SEM, FTIR, AFM and contact angle goniometer, while their performance was evaluated by measuring methanol flux and rejection of different molecular weight of dyes (ranging from 269 to 1,470 g/mol) in methanol. The experimental results showed that the polymer concentration has great impact not only on the final membrane morphology but also its separation characteristics. Increasing polymer concentration from 17 to 25wt% tended to suppress finger-like structure and more pear-like pores were developed, causing methanol flux to decrease. This can be explained by the decrease in molecular weight cut off (MWCO) of the membrane prepared at high polymer concentration. With respect to the effect of membrane pretreatment conditions, the rejection of membrane was negatively affected with longer immersion period in methanol solution prior to filtration experiment. The variation in membrane rejection can be attributed to the rearrangement of the polymer chain, which results in membrane swelling and/or change of membrane surface hydrophilicity.

Morphologies and separation characteristics of polyphenyl sulfone-based solvent resistant nanofiltration membranes: Effect of polymer concentration in casting solution and membrane pretreatment condition

International Nuclear Information System (INIS)

Sani, Nur Aimie Abdullah; Lau, Woei Jye; Ismail, Ahmad Fauzi

2015-01-01

The performance of polyphenylsulfone (PPSU) solvent resistant nanofiltration (SRNF)-based flat sheet membranes prepared from phase inversion method was investigated by varying the concentration of polymer in the dope solution and condition of membrane pretreatment process. The membrane properties were characterized by SEM, FTIR, AFM and contact angle goniometer, while their performance was evaluated by measuring methanol flux and rejection of different molecular weight of dyes (ranging from 269 to 1,470 g/mol) in methanol. The experimental results showed that the polymer concentration has great impact not only on the final membrane morphology but also its separation characteristics. Increasing polymer concentration from 17 to 25wt% tended to suppress finger-like structure and more pear-like pores were developed, causing methanol flux to decrease. This can be explained by the decrease in molecular weight cut off (MWCO) of the membrane prepared at high polymer concentration. With respect to the effect of membrane pretreatment conditions, the rejection of membrane was negatively affected with longer immersion period in methanol solution prior to filtration experiment. The variation in membrane rejection can be attributed to the rearrangement of the polymer chain, which results in membrane swelling and/or change of membrane surface hydrophilicity

Activity coefficients at infinite dilution of organic solutes in the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate using gas-liquid chromatography at T = (313.15, 323.15, and 333.15) K

International Nuclear Information System (INIS)

Olivier, Eugene; Letcher, Trevor M.; Naidoo, Paramespri; Ramjugernath, Deresh

2010-01-01

Activity coefficients at infinite dilution were determined for 24 solutes: n-alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, alkylbenzenes and alcohols in the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate, [OMIM][PF 6 ], by gas-liquid chromatography at three different temperatures T = (313.15, 323.15, and 333.15) K. The partial molar excess enthalpy values at infinite dilution were calculated from the experimental data over the same temperature range. Capacities and selectivities at infinite dilution for the systems hexane/benzene and methanol/benzene were determined from the experimental data and compared to the literature values for other ionic liquids, as well as for industrial molecular solvents. The influence of the cation and anion of the ionic liquid on the activity coefficient is discussed, as well as the usefulness of [OMIM][PF 6 ] in separating organic liquids.

Comparative experiments on polymer degradation technique of produced water of polymer flooding oilfield

Science.gov (United States)

Chen, Rong; Qi, Mei; Zhang, Guohui; Yi, Chenggao

2018-02-01

The application of polymer flooding technology in oilfields can result in polymer content increased in produced water. This increasing made produced water quality become poor. The efficiency of produced water processing decreased significantly. Processed water quality seriously exceeded criterion’s stipulation. The presence of the polymer in produced water is the main reason for more difficulties in processing of produced water, therefore the polymer degradation technology is a key coefficient in produced water processing for polymer flooding oilfields. We evaluated several physical and chemical polymer degradation methods with the solution of separated water from polymer flooding oilfields and hydrolyzed polyacrylamide. The experiment results can provide a basis for produced water processing technologies application in polymer flooding oilfields.

Structure and dynamics of solvated Ba(II) in dilute aqueous solution - an ab initio QM/MM MD approach

International Nuclear Information System (INIS)

Hofer, Thomas S.; Rode, Bernd M.; Randolf, Bernhard R.

2005-01-01

Structural properties of the hydrated Ba(II) ion have been investigated by ab initio quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations at double zeta HF quantum mechanical level. The first shell coordination number was found to be 9.3, and several other structural parameters such as angular distribution functions, radial distribution functions and tilt- and θ-angle distributions allowed the full characterization of the hydration structure of the Ba(II) ion in dilute aqueous solution. Velocity autocorrelation functions were used to calculate librational and vibrational motions, ion-ligand motions as well as reorientation times. Different dynamical parameters such as water reorientation, mean ligand residence time, the number of ligand exchange processes and rate constants were also analyzed and the ligand exchange rate constant for the first shell was determined as k = 5.3 x 10 10 s -1

Rate constant for reaction of vitamin C with protein radicals in γ-irradiated aqueous albumin solution at 295K

International Nuclear Information System (INIS)

Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami

1995-01-01

When an aqueous solution of albumin (0.1 kg dm -3 ) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 S -1 , which is much smaller than the reported constants (10 6 -10 10 dm 3 mol -1 s -1 ) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils. (author)

Polymers and colloids

International Nuclear Information System (INIS)

Schurtenberger, P.

1996-01-01

A wealth of structural information from colloid and polymer solutions on a large range of length scales can be obtained using small angle neutron scattering (SANS) experiments. After a general introduction to the field of soft condensed matter, I shall give a few selected examples on how SANS combined with suitable contrast variation schemes can be used to extract information on the size and conformation of polymer coils in solution and in the melt, and on the local structure and flexibility of polymerlike micelles and microemulsions. (author) 8 figs., tabs., 44 refs

Polymers and colloids

Energy Technology Data Exchange (ETDEWEB)

Schurtenberger, P [ETH Zurich, Inst. fuer Polymere, Zurich (Switzerland)

1996-11-01

A wealth of structural information from colloid and polymer solutions on a large range of length scales can be obtained using small angle neutron scattering (SANS) experiments. After a general introduction to the field of soft condensed matter, I shall give a few selected examples on how SANS combined with suitable contrast variation schemes can be used to extract information on the size and conformation of polymer coils in solution and in the melt, and on the local structure and flexibility of polymerlike micelles and microemulsions. (author) 8 figs., tabs., 44 refs.

Solution-processed parallel tandem polymer solar cells using silver nanowires as intermediate electrode.

Science.gov (United States)

Guo, Fei; Kubis, Peter; Li, Ning; Przybilla, Thomas; Matt, Gebhard; Stubhan, Tobias; Ameri, Tayebeh; Butz, Benjamin; Spiecker, Erdmann; Forberich, Karen; Brabec, Christoph J

2014-12-23

Tandem architecture is the most relevant concept to overcome the efficiency limit of single-junction photovoltaic solar cells. Series-connected tandem polymer solar cells (PSCs) have advanced rapidly during the past decade. In contrast, the development of parallel-connected tandem cells is lagging far behind due to the big challenge in establishing an efficient interlayer with high transparency and high in-plane conductivity. Here, we report all-solution fabrication of parallel tandem PSCs using silver nanowires as intermediate charge collecting electrode. Through a rational interface design, a robust interlayer is established, enabling the efficient extraction and transport of electrons from subcells. The resulting parallel tandem cells exhibit high fill factors of ∼60% and enhanced current densities which are identical to the sum of the current densities of the subcells. These results suggest that solution-processed parallel tandem configuration provides an alternative avenue toward high performance photovoltaic devices.