Analysis of thermal degradation process of Nafion‐117 with age‐momentum correlation method

The thermal degradation of Nafion membrane was analyzed with age‐momentum correlation (AMOC) measurement and four‐electrode AC impedance measurement. In the heated sample, the decrease in proton conductivity was observed. The lifetimes and corresponding relative intensities showed fairly good agreement between heated and nonheated samples within the experimental error. In the analysis of the photopeak of annihilation γ‐ray, on the other hand, the difference between those two kinds of samples was observed, and this difference was found to be caused by the annihilation of free positrons with low energy electrons by using AMOC method. The decrease in proton conductivity was caused by the low energy electrons, namely sulfonic radicals. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1–7, 2008     

Quantitative investigations of aggregate systems

Nanomaterials with disordered, ramified structure are increasingly being used for applications where low cost and enhanced performance are desired. A particular example is the use in printed electronics of inorganic conducting and semiconducting nanoparticles. The electrical, as well as other physical properties depend on the arrangement and connectivity of the particles in such aggregate systems. Quantification of aggregate structure and development of structure∕property relationships is difficult and progress in the application of these materials in electronics has mainly been empirical. In this paper, a scaling model is used to parameterize the structure of printed electronic layers. This model has chiefly been applied to polymers but surprisingly it shows applicability to these nanolayers. Disordered structures of silicon nanoparticles forming aggregates are investigated using small angle x-ray scattering coupled with the scaling model. It is expected that predictions using these structural parameters can be made for electrical properties. The approach may have wide use in understanding and designing nano-aggregates for electronic devices.     

CP/MAS 13C NMR characterization of the isomeric states and intermolecular packing in tris(8-hydroxyquinoline) aluminum(III) (Alq3)

The isomeric states and intermolecular packing of tris(8-hydroxyquinoline) aluminum(III) (Alq(3)) in the alpha-, gamma-, and delta-crystalline forms and in the amorphous state, which are important for understanding the light-emitting and electron-transport properties, have been analyzed by CP/MAS (13)C NMR. This simple NMR experiment shows that the isomeric state of alpha- and amorphous Alq(3) is meridional, whereas that of gamma- and delta-Alq(3) is facial. In the amorphous Alq(3), the inclusion of facial isomers has been under debate. Our experiments show that meridional isomers are dominant in the amorphous Alq(3), although the existence of facial isomers cannot be completely denied. The local structure of amorphous Alq(3) is similar to that of alpha-Alq(3) and is significantly different from those of gamma- and delta-Alq(3). Among these Alq(3) samples, the effect of intermolecular interaction is not found only for gamma-Alq(3). This finding can explain the good solvent solubility of gamma-Alq(3), compared with the other crystalline forms. It is also shown that the structures are locally disordered not only for amorphous Alq(3) but also for alpha-Alq(3), although clear X-ray diffraction peaks are observed for alpha-Alq(3). In contrast, the local structures of gamma- and delta-Alq(3) are well defined. A clear relation is found between the spectral patterns of CP/MAS (13)C NMR and the fluorescence wavelengths; the samples, which consist of facial isomers, show blue-shifted fluorescence compared with those of meridionals.     

Molecular Rotors of Coronene in Charge‐Transfer Solids

Ten types of neutral charge transfer (CT) complexes of coronene (electron donor; D) were obtained with various electron acceptors (A). In addition to the reported 7,7,8,8‐tetracyanoquinodimethane (TCNQ) complex of 1:1 stoichiometry with a DA‐type alternating π column, TCNQ also afforded a 3:1 complex, in which a face‐to‐face dimer of parallel coronenes ( Cor‐A s) is sandwiched between TCNQs to construct a DDA‐type alternating π column flanked by another coronene ( Cor‐B ). Whereas solid‐state ²H NMR spectra of the 1:1 TCNQ complex formed with deuterated coronene confirmed the single in‐plane 6‐fold flipping motion of the coronenes, two unsynchronized motions were confirmed for the 3:1 TCNQ complex, which is consistent with a crystallographic study. Neutral [Ni(mnt)₂] (mnt: maleonitriledithiolate) as an electron acceptor afforded a 5:2 complex with a DDA‐type alternating π column flanked by another coronene, similar to the 3:1 TCNQ complex. The fact that the Cor‐A s in the [Ni(mnt)₂] complex arrange in a non‐parallel fashion must cause the fast in‐plane rotation of Cor‐A relative to that of Cor‐B . This is in sharp contrast to the 3:1 TCNQ complex, in which the dimer of parallel Cor‐A s shows inter‐column interactions with neighboring Cor‐A s. The solid‐state ¹H NMR signal of the [Ni(mnt)₂] complex suddenly broadens at temperatures below approximately 60 K, indicating that the in‐plane rotation of the coronenes undergoes down to approximately 60 K; the rotational rate reaches the gigahertz regime at room temperature. Rotational barriers of these CT complexes, as estimated from variable‐temperature spin–lattice relaxation time (T₁) experiments, are significantly lower than that of pristine coronene. The investigated structure–property relationships indicate that the complexation not only facilitates the molecular rotation of coronenes but also provides a new solid‐state rotor system that involves unsynchronized plural rotators.     

Doubly nonlinear evolution equations governed by time-dependent subdifferentials in reflexive Banach spaces

We prove the existence of solutions of the Cauchy problem for the doubly nonlinear evolution equation: dv(t)/dt+V_∂φt(u(t))∋f(t), v(t)∈H_∂ψ(u(t)), 0<t<T, where H_∂ψ (respectively, V_∂φt) denotes the subdifferential operator of a proper lower semicontinuous functional ψ (respectively, φt explicitly depending on t) from a Hilbert space H (respectively, reflexive Banach space V) into (−∞,+∞] and f is given. To do so, we suppose that V?H≡H^∗?V^∗ compactly and densely, and we also assume smoothness in t, boundedness and coercivity of φt in an appropriate sense, but use neither strong monotonicity nor boundedness of H_∂ψ. The method of our proof relies on approximation problems in H and a couple of energy inequalities. We also treat the initial-boundary value problem of a non-autonomous degenerate elliptic-parabolic problem.     

Asymptotic behavior of viscosity solutions for a degenerate parabolic equation associated with the infinity-Laplacian

The asymptotic behavior of viscosity solutions to the Cauchy–Dirichlet problem for the degenerate parabolic equation u _t  = Δ_∞ u in Ω × (0,∞), where Δ_∞ stands for the so-called infinity-Laplacian, is studied in three cases: (i) and the initial data has a compact support; (ii) Ω is bounded and the boundary condition is zero; (iii) Ω is bounded and the boundary condition is non-zero. Our method of proof is based on the comparison principle and barrier function arguments. Explicit representations of separable type and self-similar type of solutions are also established. Moreover, in case (iii), we propose another type of barrier function deeply related to a solution of . Goro Akagi was supported by the Shibaura Institute of Technology grant for Project Research (no. 2006-211459, 2007-211455), and the grant-in-aid for young scientists (B) (no. 19740073), Ministry of Education, Culture, Sports, Science and Technology. Petri Juutinen was supported by the Academy of Finland project 108374. Ryuji Kajikiya was supported by the grant-in-aid for scientific research (C) (no. 16540179), Ministry of Education, Culture, Sports, Science and Technology.