Thermodynamics and activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 1-butyl-1-methylpyrrolidinium tetracyanoborate

The activity coefficients at infinite dilution, , for 45 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, tetrahydrofuran, ethers, acetone, and water, in the ionic liquid 1-butyl-1-methylpyrrolidinium tetracyanoborate, [BMPYR][TCB], were determined by gas–liquid chromatography at temperatures from 318.15 K to 368.15 K. The values of the partial molar excess Gibbs free energy , enthalpy , and entropy at infinite dilution were calculated from the experimental values obtained over the temperature range. The gas–liquid partition coefficients, K_L were calculated for all solutes and the Abraham solvation parameter model was discussed. The values of the selectivity for different separation problems were calculated from and compared to literature values for N-methyl-2-pyrrolidinone (NMP), sulfolane, 1-ethyl-3-methylimidazolium tetracyanoborate, [EMIM][TCB], 1-decyl-3-methylimidazolium tetracyanoborate, [DMIM][TCB], and similar ionic liquids. The densities of [BMPYR][TCB] in temperatures range from 318.15 K to 368.15 K, the temperature of fusion and the enthalpy of fusion were measured.     

Characterization of poly(2-oxazoline) homo- and copolymers by liquid chromatography at critical conditions

In this study liquid chromatography at critical conditions for poly(2-ethyl-2-oxazoline)s (PEtOx) has been performed for the first time in order to analyze functional PEtOx homopolymers and block copolymers. Besides the verification of the critical point of adsorption with two series of ester end group functionalized PEtOx homopolymers, to evaluate the effect of both the chain length dependence and the end group polarity, using a cyano column with a solvent combination of 2-propanol and water, also two-dimensional liquid chromatography (2D-LC) has been applied for a poly(2-oxazoline) block copolymer. The combined characterization techniques provided further information about the polymerization procedure with regard to the formation of side-products by separation of the block copolymer from the corresponding homopolymer impurities. In addition, hyphenation of LCCC with MALDI-TOF MS and ESI-Q-TOF tandem mass spectrometry verified the obtained results.     

Planar Steering of a Single Ferrofluid Drop by Optimal Minimum Power Dynamic Feedback Control of Four Electromagnets at a Distance

Any single permanent magnet or electromagnet will always attract a magnetic fluid. For this reason it is difficult to precisely position and manipulate ferrofluid at a distance from magnets. We develop and experimentally demonstrate optimal (minimum electrical power) 2-dimensional manipulation of a single droplet of ferrofluid by feedback control of 4 external electromagnets. The control algorithm we have developed takes into account, and is explicitly designed for, the nonlinear (fast decay in space, quadratic in magnet strength) nature of how the magnets actuate the ferrofluid, and it also corrects for electromagnet charging time delays. With this control, we show that dynamic actuation of electromagnets held outside a domain can be used to position a droplet of ferrofluid to any desired location and steer it along any desired path within that domain—an example of precision control of a ferrofluid by magnets acting at a distance.     

On a Nirenberg-type problem involving the square root of the Laplacian

Through an Euler–Hopf-type formula, we establish existence result to a Nirenberg-type problem involving the square root of the Laplacian in sphere S²$S^2$.     

Defect-dependent nitride surface layer development upon nitriding of Fe–1 at.% Mo alloy

Upon nitriding of binary Fe–1 at.% Mo alloy in a NH₃/H₂ gas mixture under conditions (thermodynamically) allowing γ′-Fe₄N_{1– x} compound layer growth (nitriding potential: 0.7?atm^?1/2 at 753?K (480?°C) – 823?K (550?°C)), a strong dependency of the morphology of the formed compound layer on the defect density of the specimen was observed. Nitriding of cold-rolled Fe–1 at.% Mo specimens leads to the formation of a closed compound layer of approximately constant thickness, comparable to nitriding of pure iron. Within the compound layer, that is, in the near-surface region, Mo nitrides are present. The growth of the compound layer could be described by a modified parabolic growth law leading to an activation energy comparable to literature data for the activation energy of growth of a γ′-Fe₄N_{1? x} layer on pure iron. Upon low temperature nitriding (i.e. ?793?K (520?°C)) of recrystallized Fe–1 at.% Mo specimens, an irregular, ‘needle-like’ morphology of γ′-Fe₄N_{1? x} nucleated at the surface occurs. This γ′ iron nitride has an orientation relationship (OR) with the matrix close to the Nishiyama–Wassermann OR. The different morphologies of the formed compound layer can be interpreted as consequences of the ease or difficulty of precipitation of Mo as nitride as function of the defect density.     

Investigations of elastic properties at very low frequencies: Method and behaviour of (TMA)2ZnCl4

Abstract

A new apparatus to perform longitudinal elastic strain measurements over a frequency range from 10^?4 Hz to 10¹ Hz is presented. First results of measurements on TMAZC with the prototype of this device are given. These results will be discussed in connection with the new methods.     

Role of an additive in retarding coal oxidation at moderate temperatures

The impact of an additive on coal oxidation process is studied from the mechanistic perspective, aiming at development of a guideline in search of effective inhibitors for controlling the coal self-heating phenomena. The salt Na₃PO₄ was chosen as an additive. Behaviors of samples with/without the additive were examined at temperatures up to 400 °C both in oxidative and inert atmosphere using a TGA instrument, and the compounds on coal surface during oxidation and pyrolysis were monitored by FT-IR technique. The TGA data show that the impact of the additive on coal oxidation process can be directly evaluated using a parameter defined as the percentage of mass increase at ∼265 °C, and the addition of Na₃PO₄ slows down the rates of oxygen uptake and decomposition reactions. FT-IR results also indicate that the additive suppresses both the coal oxidation and pyrolysis processes essentially by accelerating the formation of saturated ether linkages. Further analysis suggests that Na₃PO₄ plays a role in modifying the routes for decomposition of hydroxyl, and subsequently improving the coal thermal stability.     

Suppressing charge recombination by incorporating 3,6‐carbazole into poly[9‐(heptadecan‐9‐yl)‐9H‐carbazole‐2,7‐diyl‐alt‐(5,6‐bis‐(octyloxy)‐4,7‐di(thiophen‐2‐yl)benzo[1,2,5]‐thiadiazole)‐5,5‐diyl]

A series of poly[9‐(heptadecan‐9‐yl)‐9H‐carbazole‐2,7‐diyl‐alt‐(5,6‐bis‐(octyloxy)‐4,7‐di(thiophen‐2‐yl)benzo‐[1,2,5]‐thia‐diazole)‐5,5‐diyl] compositions containing various ratios of 3,6‐carbazole was synthesized for testing in a polymer solar cell. An appropriate amount of 3,6‐carbazole units incorporated into the copolymer improved intermolecular charge transport, whereas excess amount of 3,6‐carbazole units temporarily seized on the partial negative charge generated in the conjugation breaks. We extensively studied the effects of the incorporated 3,6‐carbazole units on the intermolecular interactions, which can affect nongeminated recombination in bulk heterojunction‐polymer solar cells. These properties were investigated using photocurrent‐ and light intensity‐dependent measurements and electrochemical impedance spectroscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2047–2056