Mössbauer studies on one-dimensional iron phthalocyanines

Summary Magnetic moments and⁵⁷Fe Mössbauer spectra at room temperature and at liquid nitrogen temperature of polynuclear ligand-bridged iron phthalocyanines, FePcL (L = pyrazine and 4,4-bipyridyl), are reported. The experimental data are in agreement with a pseudo-octahedral environment around the iron(II) cation. Partially oxidized derivatives, FePc(pz)I_0.26 and FePc(bipy)I_1.06 have been synthesized and their⁵⁷Fe Mössbauer spectra and magnetic moments within the same temperature range obtained. Oxidation is shown to be metal centred and the iodine is found to be in I^– form for FePc(pz)_0.26 and as both I^– and I ₃ ^– species for FePc(bipy)I_1.06. While the magnetic moment of FePc(pz) increases upon oxidation, the opposite occurs for FePc(bipy).     

Proton related defects in α-BaTiO3:H films based MIM capacitors

Hydrogenated barium titanate film based metal–insulator–metal (MIM) systems show high dielectric constant and have therefore been proposed as solid state supercapacitors. Hydrogen was incorporated in the dielectric layer during the low temperature deposition process. An investigation of the electrical properties has revealed that hydrogen contributes to the conduction process as mobile ionic species as well as donor trap levels.     

Non‐mutagenic organic pigment intermediates. II. Isomorphous 2,2′‐di­chloro‐5,5′‐dipropoxy­benzidine and 2,2′‐di­methyl‐5,5′‐dipropoxy­benzidine

The title compounds, C₁₈H₂₂Cl₂N₂O₂ and C₂₀H₂₈N₂O₂, respectively, are isomorphous. The mol­ecules lie at general positions in the unit cell. In each structure, chemically equivalent but crystallographically inequivalent amine N atoms exhibit different degrees of pyramidalization. The structures exhibit weak N—H⋯N hydrogen bonding, which is influenced by the differences in hybridization around the amine N atoms. The torsion angles across the bi­phenyl linkage for the two compounds are 67.2 (2) and 68.3 (3)°.     

Vapor–liquid equilibrium measurements and modeling of the n-butane + ethanol system from 323 to 423 K

Vapor–liquid equilibrium (VLE) data are presented for the n-butane + ethanol system in the temperature range from 323 to 423 K. Measurements were performed using a “static-analytic” apparatus, equipped with two electromagnetic ROLSI™ capillary samplers, and thermally regulated via an air bath. This work presents vapor compositions which have not been explicitly measured previously. The modeling of the data was performed using two models: the Peng–Robinson equation of state with the Wong and Sandler mixing rule and NRTL excess function (PR/WS/NRTL); and the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state. To assess the effect of dipole–dipole interactions present, a dipolar contribution developed by Jog and Chapman (1999) [20] was tested with the second model. Temperature dependent binary interaction parameters have been adjusted to the new data. The PR/WS/NRTL equation of state shows good correlation with the results, while the PC-SAFT is slightly less accurate.     

Complexes of tetra-tert-butyl-tetraazaporphine with Al(III) and Zr(IV) cations as fluoride selective ionophores

In this work, complexes of Zr(IV) and Al(III) cations with 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraazaporphine (TAP) were tested as ionophores in plasticized PVC membranes of ion-selective electrodes. It was found that both tested ionophores show enhanced affinity towards fluoride anion. High fluoride selectivity was observed in the presence of anionic or cationic additives in the membrane, which indicates that proposed compounds work according to charged or neutral carrier mechanism, depending on membrane composition and pretreatment.tert-Butyl substituents, present in the structure of tested compounds, were supposed to prevent formation of ionophore dimers within the membrane phase. This process was found to be responsible for some unfavorable potentiometric properties of electrodes based on complexes of Zr(IV) and Al(III) cations with porphyrins (compounds closely related to tetra-tert-butyl-5,10,15,20-tetraazaporphine). As it was shown using spectrophotometrical measurements, Al(III)-TAP was not susceptible to dimerization, while dimer formation was observed for Zr(IV)-TAP. In full agreement with these observations, electrodes with membranes containing Al(III)-TAP responded in near-Nernstian and fast manner towards fluoride anion, while the employment of Zr(IV)-TAP as ionophore resulted in super-Nernstian and sluggish response. Plasticized PVC membranes doped with Al(III)-TAP and 20 mol% of lipophilic anionic additives shown remarkable F⁻ selectivity, with selectivity coefficients, , as follows: −4.4 (Y⁻Br⁻), −4.3 (Cl⁻), −4.2 (NO₃⁻), −3.6 (SCN⁻), −2.9 (ClO₄⁻).     

Synthesis and characterization of electrical conducting porous carbon structures based on resorcinol–formaldehyde

Electrical conducting carbon (ECC) porous structures were explored by changing the pyrolysis temperature of organic xerogel compounds prepared by sol–gel method from resorcinol–formaldehyde (RF) mixtures in acetone using picric acid as catalyst. The effect of this preparation parameter on the structural and electrical properties of the obtained ECCs was studied. The analysis of the obtained results revealed that the polymeric insulating xerogel phase was transformed progressively with pyrolysis temperature into carbon conducting phase; this means the formation of long continuous conducting path for charge carriers to move inside the structure with thermal treatment and the samples exhibited tangible percolation behaviour where the percolation threshold can be determined by pyrolysis temperature. The temperature-dependent conductivity of the obtained ECC structures shows a semi-conducting behaviour and the I(V) characteristics present a negative differential resistance. The results obtained from STM micrographs revealed that the obtained ECC structures consist of porous electrical conducting carbon materials.     

Asymptotic analysis of a transport model of organic material through a stratified porous medium: Concentration effect

We consider the transport through capillarity of an organic material inside a porous medium, using Leverett’s model. We first prove an existence result for a weak solution of this nonlinear evolution problem, using a regularization process. We then describe the asymptotic behavior of the solution, when the permeability _kε$k_{\epsilon }$ of the porous medium is associated to a scalar function which only depends on the third variable, assuming that _kε$k_{\epsilon }$ (resp. the inverse of _kε$k_{\epsilon }$) converges to some measure _λ∗${\lambda }_{\ast }$ (resp. λ^∗${\lambda }^{\ast }$). We use Γ-convergence arguments in order to describe this asymptotic behavior. We finally characterize the asymptotic behavior of the problem, considering special choices of the permeability _kε$k_{\epsilon }$, which correspond to stratified porous media, and give a numerical test for a 1D model.     

Multiscale Modeling of Nanocrystalline Materials: A Variational Approach

This paper presents a variational multi-scale constitutive model in the finite deformation regime capable of capturing the mechanical behavior of nanocrystalline (nc) fcc metals. The nc-material is modeled as a two-phase material consisting of a grain interior (GI) phase and a grain boundary (GB) phase. A rate-independent isotropic porous plasticity model is employed to describe the GB phase, whereas a crystal-plasticity model which accounts for the transition from partial dislocation to full dislocation mediated plasticity is employed for the GI phase. Assuming the rule of mixtures, the overall behavior of a given grain is obtained via volume averaging. The scale transition from a single grain to a polycrystal is achieved by Taylor-type homogenization. It is shown that the proposed model is able to capture the inverse Hall-Petch effect. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)