Synthesis and properties of a new AB-cross-linked copolymer membrane system

The alcohol permeability and permselectivity properties as well as the morphology of membranes made of a newly developed AB-cross-linked copolymer system composed of elastomeric and glassy components were investigated. The copolymer was synthesized by a hydrosilylation reaction between poly(styrene-stat-isoprenes) (Mn from 40,000 to 100,000 g/mol) with high content in unsaturated side groups (≈ 60% of entire isoprene content) and polyhydrogen polysiloxanes with varying SiH content (0.75 10.7 mol %) and molecular mass, Mn, from 2,500 to 36,000 g/mol. A two-track approach was taken to determine the morphology of the copolymer system. The first employed the usual polymer characterization methods such as electron microscopy, DSC, IR spectroscopy, the density gradient method, and mechanical measurements. For the second approach, different copolymer permeability models were tested so as to give an insight into the copolymer morphology. As a final step, the permeability and permselectivity properties were correlated with the morphological structure of the copolymer system. It was observed that the respective continuous microphase dominated the copolymer's physical properties, as, e.g., permeability, permselectivity, and mechanical properties. The microphase inversion in the copolymer system was proved by the permeability/permselectivity as well as by the mechanical measurements

Recent advances in the formation of phase inversion membranes made from amorphous or semi-crystalline polymers

Structural characteristics in membranes formed by diffusion induced phase separation processes are discussed. Established theories on membrane formation from ternary systems can be extended to describe the effects of high or low molecular weight additives. A mechanism for the formation of nodular structures in the top layer of ultrafiltration membranes is presented. In the last part structures arising from polymer crystallization during immersion precipitation are discussed

Non-aqueous retention measurements: ultrafiltration behaviour of polystyrene solutions and colloidal silver particles

The retention behaviour of polyimide ultrafiltration membranes was investigated using dilute solutions of polystyrene in ethyl acetate as test solutions. It is shown that flow-induced deformation of the polystyrene chains highly affects the membrane retention. This coil-stretch transition is not instantaneous, but gradual. The concept of a deformation resistance has been ontroduced to explain this behaviour. This concept can be applied to describe the flux behaviour of the membranes during the tests as well. Solute deformation allows comparison of the pore size distributions of the membranes qualitatively. Retention measurements were also performed with silver sol particles that were prepared in mixtures of ethanol and water; these sols remain stable as long as the ethanol concentration does not exceed 57 vol%. The sols were completely retained by the membranes, which is probably caused by the fact that the effective diameter of the particles is much larger than that observed by transmission electron microscopy

A Kernel Test of Goodness of Fit

We propose a nonparametric statistical test for goodness-of-fit: given a set of samples, the test determines how likely it is that these were generated from a target density function. The measure of goodness-of-fit is a divergence constructed via Stein's method using functions from a Reproducing Kernel Hilbert Space. Our test statistic is based on an empirical estimate of this divergence, taking the form of a V-statistic in terms of the log gradients of the target density and the kernel. We derive a statistical test, both for i.i.d. and non-i.i.d. samples, where we estimate the null distribution quantiles using a wild bootstrap procedure. We apply our test to quantifying convergence of approximate Markov Chain Monte Carlo methods, statistical model criticism, and evaluating quality of fit vs model complexity in nonparametric density estimation

Characterization of polyacrylonitrile ultrafiltration membranes

Various methods have been used to characterize ultrafiltration membranes, such as gas flux measurements, (field emission) scanning electron microscopy, permporometry and liquid-liquid displacement. Significant differences in the pore size distributions determined from permporometry and liquid-liquid displacement were found

Characterization of morphology controlled polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to the dope and bore liquid solution

The preparation of polyethersulfone (PES) hollow fiber membranes has been studied using N-methylpyrrolidone (NMP) as solvent, polyethylene glycol 400 (PEG 400) as weak nonsolvent and water as strong nonsolvent. When PEG 400 is used as polymeric additive to the spinning dope the viscosity of the PES solution is strongly enhanced. Furthermore, it was observed that PEG 400 could be added to the solution in large amounts without causing phase separation (NMP/PEG ratio 1:9, PES concentration approximately 11 wt.%). Membranes prepared from a solution containing a NMP/PEG ratio of 1:1 results in higher fluxes than when a ratio of 1:4 is used. Similar fluxes were obtained for PES concentrations of 16 and 20 wt.%. Looking at the fiber cross-section it became clear that macrovoid formation could not be suppressed by the addition of PEG 400 alone, not even at concentrations as high as 38 wt.%. Only when relatively large amounts of water were added to the dope solution macrovoids disappeared and nice spongy structures were obtained. Variation of the bore liquid composition using the components NMP, PEG 400 and water showed to be a powerful method to control the pore size of the bore surface. Pores of 5–28 nm were obtained in combination with high pure water fluxes; e.g. a membrane with pores of 7 nm had a pure water flux of 940 l/(m2 h bar) and showed 100% BSA retention. When an air gap larger than 10 mm was applied the shell surface contained relatively large pores. Spinning directly in water (airgap=0) resulted in shell side pores of 8–10 nm, while an air gap of 10 mm resulted in pore sizes of 40–54 nm

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

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