Free volume in C60 modified PPO polymer membranes by positron annihilation lifetime spectroscopy

PPO (poly(2,6-dimethyl-1,4-phenylene oxide)) is a well-known membrane material showing good gas separation properties. The incorporation of nanoparticles can enhance or deteriorate the performance of composite membranes, sometimes depending only on the way of the composite preparation. We have modified the PPO polymer with C60 fullerenes up to a content of 2 wt %. Previous investigations showed a strong dependence of permeability on whether the C60 is simply dispersed in the polymer or chemically bonded to the polymer chains. Free volume effects were suggested as an explanation but not experimentally confirmed. Here, we present free volume studies by positron annihilation lifetime spectroscopy. An additional long positron lifetime shows the increased free volume of composite samples, while the high electron affinity of C60 helps to indicate the homogeneity of the samples. Combining the presented results with permeability measurements refines the understanding of this promising membrane material.     

Single‐crystal sapphire microstructure for high‐resolution synchrotron X‐ray monochromators

We report on the growth and characterization of sapphire single crystals for X‐ray optics applications. Structural defects were studied by means of laboratory double‐crystal X‐ray diffractometry and white‐beam synchrotron‐radiation topography. The investigations confirmed that the main defect types are dislocations. The best quality crystal was grown using the Kyropoulos technique. Therein the dislocation density was 10²–10³ cm⁻² and a small area with approximately 2*2 mm² did not show dislocation contrast in many reflections. This crystal has suitable quality for application as a backscattering monochromator. A clear correlation between growth rate and dislocation density is observed, though growth rate is not the only parameter impacting the quality.     

Issues arising in the construction of QSSA mechanisms: the case of reduced n-heptane/air models for premixed flames

A model reduction methodology, based on the quasi steady-state approximation (QSSA), is employed for the construction of reduced mechanisms in the case of an n-heptane/air premixed flame. Several issues related to the construction of these reduced mechanisms are discussed; such as the influence of the size of the starting skeletal mechanism, the stiffness reduction, and the truncation/simplification of (i) the expressions of the global rates and (ii) the steady-state relations. The starting point for the reduction is two skeletal mechanisms that involve 177/768 and 66/326 species/reactions, respectively [J. Prager, H.N. Najm, M. Valorani, and D.A. Goussis, Skeletal mechanism generation with CSP and validation for premixed n-heptane flames, Proc. Combust. Inst. 32 (2009), pp. 509–517] and which were derived from the detailed mechanism of Curran et al. [H.J. Curran, P. Gaffuri, W.J. Pitz, and C.K. Westbrook, A comprehensive modeling study of iso-octane oxidation, Combust. Flame 129 (2002), pp. 253–280], which involves 561/2538 species/reactions. From these two skeletal mechanisms, a number of reduced mechanisms of various sizes are produced and analysed. The validity of the reduced mechanism with the minimum size is demonstrated by considering its accuracy regarding the mass fractions of major and minor species, the temperature, and the flame speed, over a wide range of equivalence ratios and pressures.     

Fourier Law,Phase Transitions and the Stationary Stefan Problem

We study the one-dimensional stationary solutions of the integro-differential equation which, as proved in Giacomin and Lebowitz (J Stat Phys 87:37–61, 1997; SIAM J Appl Math 58:1707–1729, 1998), describes the limit behavior of the Kawasaki dynamics in Ising systems with Kac potentials. We construct stationary solutions with non-zero current and prove the validity of the Fourier law in the thermodynamic limit showing that below the critical temperature the limit equilibrium profile has a discontinuity (which defines the position of the interface) and satisfies a stationary free boundary Stefan problem. Under-cooling and over-heating effects are also studied: we show that if metastable values are imposed at the boundaries then the mesoscopic stationary profile is no longer monotone and therefore the Fourier law is not satisfied. It regains its validity however in the thermodynamic limit where the limit profile is again monotone away from the interface.     

Classification of cracking mode in concrete by acoustic emission parameters

The study occupies with acoustic emission monitoring of several types of concrete during bending. The signals emitted at the different fracturing stages exhibit distinct signatures. Specifically, frequency and shape parameters of the acquired waveforms shift during the experiment, closely following the sequence of fracture mechanisms from tensile micro-cracking to brittle macro-cracking and fiber pull out. A number of AE indices are proposed, the use of which will enable classification of the cracks according to their mode. The study sheds light to the fracture process of cementitious materials, and enables a warning against the final failure. The simplicity of the scheme renders it applicable in situ.     

Strengthening Erdös–Pósa property for minor‐closed graph classes

Let ?? and ?? be graph classes. We say that ?? has the Erd?s–Pósa property for ?? if for any graph G ∈??, the minimum vertex covering of all ??‐subgraphs of G is bounded by a function f of the maximum packing of ??‐subgraphs in G (by ??‐subgraph of G we mean any subgraph of G that belongs to ??). Robertson and Seymour [J Combin Theory Ser B 41 (1986), 92–114] proved that if ?? is the class of all graphs that can be contracted to a fixed planar graph H, then ?? has the Erd?s–Pósa property for the class of all graphs with an exponential bounding function. In this note, we prove that this function becomes linear when ?? is any non‐trivial minor‐closed graph class. © 2010 Wiley Periodicals, Inc. J Graph Theory 66:235‐240, 2011     

Probing the electronic structure,chemical bonding,and excitation spectra of [CuE]+/0/− (E = 14 group element) diatomics employing DFT and ab initio methods

The electronic structure, chemical bonding, and excitation spectra of neutral, cationic, and anionic diatomic molecules of Cu and 14 group elements formulated as [CuE]^+/0/? (E = C, Si, Ge, Sn, Pb) were investigated by density functional theory (DFT) and time‐dependent (TD)‐DFT methods. The electronic and bonding properties of the diatomics analyzed by natural bond orbital (NBO) analysis approch revealed a clear picture of the chemical bonding in these species. The spatial organization of the bonding between Cu and E atoms in the [CuE]^+/0/? (E = Si, Ge, Sn, Pb) molecules can easily be recognized by the cut‐plane electron localization function representations. Particular emphasis was given on the absorption spectra of the [CuE]^+/0/? which were simulated using the results of TD‐DFT calculations employing the hybrid Coulomb‐attenuating CAM‐B3LYP functional. The absorption bands have thoroughly been analyzed and assignments of the contributing principal electronic transitions associated to individual excitations have been made. © 2012 Wiley Periodicals, Inc.     

All-electron scalar relativistic basis sets for the 6p elements

New segmented all-electron relativistically contracted (SARC) basis sets have been developed for the elements ₈₁Tl–₈₆Rn, thus extending the SARC family of all-electron basis sets to include the 6p block. The SARC basis sets are separately contracted for the second-order Douglas–Kroll–Hess and the zeroth-order regular approximation scalar relativistic Hamiltonians. Their compact size and segmented construction are best suited to the requirements of routine density functional theory (DFT) applications. Evaluation of the basis sets is performed in terms of incompleteness and contraction errors, orbital properties, ionization energies, electron affinities, and atomic polarizabilities. From these atomic metrics and from computed basis set superposition errors for a series of homonuclear dimers, it is shown that the SARC basis sets achieve a good balance between accuracy and size for efficient all-electron scalar relativistic DFT applications.