Mechanical properties of anion exchange membranes by combination of tensile stress–strain tests and dynamic mechanical analysis

The thermomechanical properties of anion exchange polymers based on polysulfone (PSU) quaternized with trimethylamine (TMA) or 1,4‐diazabicyclo[2.2.2]octane (DABCO) and containing hydroxide or chloride anions by tensile stress–strain tests and dynamic mechanical analysis (DMA) have been determined. The reported mechanical properties included the Young's modulus, tensile strength, and elongation at break from tensile tests and the storage and loss modulus and glass transition temperature from DMA. The anion exchange membranes behaved as stiff polymers with Young's modulus in the order of 1 GPa, relatively with high strength (about 30 MPa) and low elongation at break (around 10%) was observed. Tensile tests were also made with membranes exchanged with hydrogen‐carbonate and carbonate anions to control the absence of important carbonation of the OH form. The glass transition temperatures were of the order of 150 °C (PSU‐TMA) or 200 °C (PSU‐DABCO) for the hydroxide form, confirmed by differential scanning calorimetry; they increase further by about 50 K, when hydroxide ions are replaced by chloride. This result and the increase of the storage modulus could be interpreted by the higher hydration of hydroxide ions and the plasticizing effect of water, which reduced the Van der Waals interactions between the macromolecular chains. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1180–1187     

Bis-chelate Fe(III) complex of an azomethine at the focal point of a branched ester functionalized with cyclohexylbenzoic acid

A Fe(III) complex with Cl counter ion based on a branched Schiff base has been synthesized and studied. The compound was produced by the reaction of the Schiff base with FeCl₃ at room temperature in benzene–ethanol. The complex is symmetric, i.e., bis-chelate, with an octahedral coordination of Fe. The compound revealed phase transitions of the “solid–solid” type. The complex displayed a temperature-induced spin transition (S?=?1/2???5/2) which was detected by EPR.     

The Hard Rod Fluid in a Uniform Gravitational Field

Abstract

The system of hard rods in an external, uniform gravitational field is studied and exact expressions obtained for the partition functions, and the one- and two-particle distributions. In principle all higher order distributions can be exactly expressed as finite sums and the Laplace transforms of the one-particle density and pressure for a semi-infinite system are reducible to single integrals. Limiting cases of weak field and small rod diameters are examined. In the former case, these results agree with Percus and Lebowitz's local density expansion. In the latter case, corrections to the barometric pressure and density laws are obtained. Finally some mathematical difficulties involved in the calculation of the virial expansion and distribution of roots of the grand partition function are mentioned.     

Revealing sol-gel type main effects by exploring a molecular cluster behavior in model in-plane amphiphilic aggregations

In-plane (bio)matter aggregations of amphiphilic nature are modeled extensively by Monte Carlo simulation in their natural entropic contexts. The modeling starts by designing the aggregations at a molecular level, pointing to its well-known configuration vs conformation character. Then, the conformational behavior is distributed over the aggregations obtained, with the aim of revealing their main sol-gel type (viscoelastic) effects. The passage between the resulting sol and gel phases is not controlled by a scan in the temperature domain, on the contrary, the control parameter is selected to be the hydrophobic-interaction strength while the temperature remains unchanged. The distribution of ordered fringed micelles, and the overall crystalline inclusions of the gel phase, suggested a first-order phase change, reasonably conceivable in terms of Avrami-Kolmogorov formalism for such hydrophobic-force driven and percolation-in-nature systems. A phase transition diagram has been presented as a novel proposition to discern between sol vs gel phases. As specific results, also of high experimental value, a damped-oscillating cluster-involving effect on the resulting hydrophobic-polar matrices has been detected and analysed. Other additional intermolecular-sharing entropy-influenced effects on clustering, as seen in terms of chain-to-chain connectivities, have been addressed as being of sufficient relevance to the gelation mechanism described. The microcrystalline inclusions downgrade to some extent the overall picture of entropy-affected gelation, being all together suitable for experimental check-out.     

Structure of the even-even ~(78-84)Kr isotopes within SD-pair shell model

The collective properties in the even-even 78-84Kr isotopes have been studied within the framework of the SD-pair shell model.It is found that the collectivity of low-lying states in the even-even Kr isotopes can be described very well.     

Structures, phase transition, elastic properties of SnO2 from first-principles analysis

We investigate the structural, phase transition and elastic properties of SnO₂ in the rutile-type, pyrite-type, ZrO₂-type and cotunnite-type phases by the plane-wave pseudopotential density functional theory method. The lattice constants, bulk modulus and its pressure derivative are well consistent with the available experimental and other theoretical data. Also, we find that the rutile→pyrite, pyrite→ZrO₂ and ZrO₂→cotunnite phase transition occur at 12.9, 59.1 and 111.1 GPa, which are in better agreement with the experimental results than those of Gracia et al. (2007). Moreover, we obtain the pressure dependences of elastic constants for the four structures.     

Classicalization times of parametrically amplified “Schrödinger cat” states coupled to phase-sensitive reservoirs

The exact Wigner function of a parametrically excited quantum oscillator in a phase-sensitive amplifying/attenuating reservoir is found for initial even/odd coherent states. Studying the evolution of negativity of the Wigner function we show the difference between the “initial positivization time” (IPT), which is inversely proportional to the square of the initial size of the superposition, and the “final positivization time” (FPT), which does not depend on this size. Both these times can be made arbitrarily long in maximally squeezed high-temperature reservoirs. Besides, we find the conditions when some (small) squeezing can exist even after the Wigner function becomes totally positive.     

A note on a pioneering work in quantitative spectroscopy: UV bands of the hydroxyl radical

The publication by G.H. Dieke and H.M. Crosswhite (JQSRT 1962;2:97-199) is a classic paper detailing the spectroscopy of the A²Σ⁺←X²Π bands of the hydroxyl radical (OH) in the ultraviolet region. It soon became the basis of astrophysical modeling, most subsequent theoretical and laboratory studies of the OH individual line parameters, and a host of other applications.     

Breaking and Making of Carbon–Carbon Bonds by Lanthanides and Third‐Row Transition Metals

Carbon‐atom extrusion from the ipso‐position of a halobenzene ring (C₆H₅X; X=F, Cl, Br, I) and its coupling with a methylene ligand to produce acetylene is not confined to [LaCH₂]⁺; also, the third‐row transition‐metal complexes [MCH₂]⁺, M=Hf, Ta, W, Re, and Os, bring about this unusual transformation. However, substrates with substituents X=CN, NO₂, OCH₃, and CF₃ are either not reactive at all or give rise to different products when reacted with [LaCH₂]⁺. In the thermal gas‐phase processes of atomic Ln⁺ with C₇H₇Cl substrates, only those lanthanides with a promotion energy small enough to attain a 4fⁿ5d¹6s¹ configuration are reactive and form both [LnCl]⁺ and [LnC₅H₅Cl]⁺. Branching ratios and the reaction efficiencies of the various processes seem to correlate with molecular properties, like the bond‐dissociation energies of the C?X or M⁺?X bonds or the promotion energies of lanthanides.