Local and chain dynamics in miscible polymer blends: A Monte Carlo simulation study

Local chain structure and local environment play an important role in the dynamics of polymer chains in miscible blends. In general, the friction coefficients that describe the segmental dynamics of the two components in a blend differ from each other and from those of the pure melts. In this work, we investigate polymer blend dynamics with Monte Carlo simulations of a generalized bond-fluctuation model, where differences in the interaction energies between non-bonded nearest neighbors distinguish the two components of a blend. Simulations employing only local moves and respecting a non-bond crossing condition were carried out for blends with a range of compositions, densities, and chain lengths. The blends investigated here have long-chain dynamics in the crossover region between Rouse and entangled behavior. In order to investigate the scaling of the self-diffusion coefficients, characteristic chain lengths $N_\mathrm{c}$ are calculated from the packing length of the chains. These are combined with a local mobility $\mu$ determined from the acceptance rate and the effective bond length to yield characteristic self-diffusion coefficients $D_\mathrm{c}=\mu/N_\mathrm{c}$. We find that the data for both melts and blends collapse onto a common line in a graph of reduced diffusion coefficients $D/D_\mathrm{c}$ as a function of reduced chain length $N/N_\mathrm{c}$. The composition dependence of dynamic properties is investigated in detail for melts and blends with chains of length twenty at three different densities. For these blends, we calculate friction coefficients from the local mobilities and consider their composition and pressure dependence. The friction coefficients determined in this way show many of the characteristics observed in experiments on miscible blends.Comment: 12 pages, 13 figures, editorial change

Modeling electrodialysis and a photochemical process for their integration in saline wastewater treatment.

Oxidation processes can be used to treat industrial wastewater containing non-biodegradable organic compounds. However, the presence of dissolved salts may inhibit or retard the treatment process. In this study, wastewater desalination by electrodialysis (ED) associated with an advanced oxidation process (photo-Fenton) was applied to an aqueous NaCl solution containing phenol. The influence of process variables on the demineralization factor was investigated for ED in pilot scale and a correlation was obtained between the phenol, salt and water fluxes with the driving force. The oxidation process was investigated in a laboratory batch reactor and a model based on artificial neural networks was developed by fitting the experimental data describing the reaction rate as a function of the input variables. With the experimental parameters of both processes, a dynamic model was developed for ED and a continuous model, using a plug flow reactor approach, for the oxidation process. Finally, the hybrid model simulation could validate different scenarios of the integrated system and can be used for process optimization

Transitions of tethered polymer chains: A simulation study with the bond fluctuation lattice model

A polymer chain tethered to a surface may be compact or extended, adsorbed or desorbed, depending on interactions with the surface and the surrounding solvent. This leads to a rich phase diagram with a variety of transitions. To investigate these transitions we have performed Monte Carlo simulations of a bond-fluctuation model with Wang-Landau and umbrella sampling algorithms in a two-dimensional state space. The simulations' density of states results have been evaluated for interaction parameters spanning the range from good to poor solvent conditions and from repulsive to strongly attractive surfaces. In this work, we describe the simulation method and present results for the overall phase behavior and for some of the transitions. For adsorption in good solvent, we compare with Metropolis Monte Carlo data for the same model and find good agreement between the results. For the collapse transition, which occurs when the solvent quality changes from good to poor, we consider two situations corresponding to three-dimensional (hard surface) and two-dimensional (very attractive surface) chain conformations, respectively. For the hard surface, we compare tethered chains with free chains and find very similar behavior for both types of chains. For the very attractive surface, we find the two-dimensional chain collapse to be a two-step transition with the same sequence of transitions that is observed for three-dimensional chains: a coil-globule transition that changes the overall chain size is followed by a local rearrangement of chain segments.Comment: 17 pages, 12 figures, to appear in J. Chem. Phy

Characterization of G-protein α subunits in the Gq class: expression in murine tissues and in stromal and hematopoietic cell lines

Murine Gα14 and Gα15 cDNAs encode distinct α subunits of heterotrimeric guanine nucleotide-binding proteins (G proteins). These alpha subunits are related to members of the Gq class and share certain sequence characteristics with Gαq, Gα11, and Gα16, such as the absence of a pertussis toxin ADP-ribosylation site. Gα11 and Gαq are ubiquitously expressed among murine tissues but G alpha 14 is predominantly expressed in spleen, lung, kidney, and testis whereas Gα15 is primarily restricted to hematopoietic lineages. Among hematopoietic cell lines, Gα11 mRNA is found in all cell lines tested, Gαq is expressed widely but is not found in most T-cell lines, Gα15 is predominantly expressed in myeloid and B-cell lineages, and Gα14 is expressed in bone marrow adherent (stromal) cells, certain early myeloid cells, and progenitor B cells. Polyclonal antisera produced from synthetic peptides that correspond to two regions of Gα15 react with a protein of 42 kDa expressed in B-cell membranes and in Escherichia coli transformed with Gα15 cDNA. The expression patterns that were observed in mouse tissues and cell lines indicate that each of the alpha subunits in the Gq class may be involved in pertussis toxin-insensitive signal-transduction pathways that are fundamental to hematopoietic cell differentiation and function

Conformational Mechanics of Polymer Adsorption Transitions at Attractive Substrates

Conformational phases of a semiflexible off-lattice homopolymer model near an attractive substrate are investigated by means of multicanonical computer simulations. In our polymer-substrate model, nonbonded pairs of monomers as well as monomers and the substrate interact via attractive van der Waals forces. To characterize conformational phases of this hybrid system, we analyze thermal fluctuations of energetic and structural quantities, as well as adequate docking parameters. Introducing a solvent parameter related to the strength of the surface attraction, we construct and discuss the solubility-temperature phase diagram. Apart from the main phases of adsorbed and desorbed conformations, we identify several other phase transitions such as the freezing transition between energy-dominated crystalline low-temperature structures and globular entropy-dominated conformations.Comment: 13 pages, 15 figure

Josephson tunneling in high-TcT_c superconductors

This article describes the Josephson tunneling from time-reversal symmetry-breaking states and compares it with that from time-reversal invariant states for both twinned and untwinned crystals and for both $c$-axis and basal-plane currents, in a model for orthorhombic YBCO. A macroscopic invariance group describing the superconducting state of a twinned crystal is introduced and shown to provide a useful framework for the discussion of the results for twinned crystals. In addition, a ring geometry, which allows $s$-wave and $d_{x^2-y^2}$-wave superconductivity in a tetragonal superconductor to be distinguished on the basis of symmetry arguments only, is proposed and analyzed. Finally, an appendix gives details of the experimental Josephson tunneling evidence for a superconducting state of orthorhombic $ux^2+vy^2$ symmetry in YBCO.Comment: Latex File, 18 pages, 6 Postscript figures, submitted to Phys. Rev.

Molecular Valves for Controlling Gas Phase Transport Made from Discrete Angstrom-Sized Pores in Graphene

An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale 3D printing, catalysis, and sensor design. Barrier materials containing pores with molecular dimensions have previously been used to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores. Here, we show that gas flux through discrete angstrom-sized pores in monolayer graphene can be detected and then controlled using nanometer-sized gold clusters, which are formed on the surface of the graphene and can migrate and partially block a pore. In samples without gold clusters, we observe stochastic switching of the magnitude of the gas permeance, which we attribute to molecular rearrangements of the pore. Our molecular valves could be used, for example, to develop unique approaches to molecular synthesis that are based on the controllable switching of a molecular gas flux, reminiscent of ion channels in biological cell membranes and solid state nanopores.Comment: to appear in Nature Nanotechnolog

Probing structural relaxation in complex fluids by critical fluctuations

Complex fluids, such as polymer solutions and blends, colloids and gels, are of growing interest in fundamental and applied soft-condensed-matter science. A common feature of all such systems is the presence of a mesoscopic structural length scale intermediate between atomic and macroscopic scales. This mesoscopic structure of complex fluids is often fragile and sensitive to external perturbations. Complex fluids are frequently viscoelastic (showing a combination of viscous and elastic behaviour) with their dynamic response depending on the time and length scales. Recently, non-invasive methods to infer the rheological response of complex fluids have gained popularity through the technique of microrheology, where the diffusion of probe spheres in a viscoelastic fluid is monitored with the aid of light scattering or microscopy. Here we propose an alternative to traditional microrheology that does not require doping of probe particles in the fluid (which can sometimes drastically alter the molecular environment). Instead, our proposed method makes use of the phenomenon of "avoided crossing" between modes associated with the structural relaxation and critical fluctuations that are spontaneously generated in the system.Comment: 4 pages, 4 figure

Low-cost inorganic cation exchange membrane for electrodialysis: optimum processing temperature for the cation exchanger

The optimum temperature for fixing zirconium phosphate, obtained by precipitation, on a low-cost ceramic support was determined in order to obtain an inorganic cation exchange membrane for electrodialysis. Zirconium phosphate ion exchange capacity maximised between 450 and 550°C, thus it was considered the optimum processing temperature. The origin of this maximum was investigated by means of X-ray diffraction and termogravimetry and evolved gas analysis. Zirconium phosphate formation by precipitation in the porous network of the support was verified by scanning electron microscopy and energy dispersive X-ray analysis and mercury intrusion porosimetry. The membrane obtained after thermal treatment at 450°C displayed selectivity to the cations present in the spent rinse water of the chromium plating process. This property allows the recovery of chromium by removing the cations through the cation exchange ceramic membrane.The authors wish to express their gratitude to the Spanish Ministry of Science and Innovation for the support given to the research study (National Basic Research Programme, Ref. CTQ2008-06750-C02-02), as well as for the FPU student grant awarded to one of the authors (Ref.: AP2009-4409).Mestre, S.; Sales, S.; Palacios, M.; Lorente, M.; Mallol, G.; Pérez-Herranz, V. (2013). Low-cost inorganic cation exchange membrane for electrodialysis: optimum processing temperature for the cation exchanger. Desalination and Water Treatment. 51(16-18):3317-3324. https://doi.org/10.1080/19443994.2012.749177S331733245116-18Strathmann, H. (2010). Electromembrane Processes: Basic Aspects and Applications. Comprehensive Membrane Science and Engineering, 391-429. doi:10.1016/b978-0-08-093250-7.00048-7Drioli, E., & Fontananova, E. (s. f.). Integrated Membrane Processes. 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