Ferroelectricity and pressure-induced phenomena driven by neutral ionic valence instability of acid-base supramolecules

Supramolecular ferroelectric cocrystals of phenazine (Phz) with chloranilic acid (H(2)ca), bromanilic acid (H(2)ba), and fluoranilic acid (H(2)fa) have been characterized by the interplay between their structural transformations and solid-state acid-base (proton transfer) reactions. At ambient pressure, the Phz-H(2)ca, Phz-H(2)ba, and their deuterated crystals exhibit incomplete proton displacement, which transforms the neutral molecules into semi-ionic at low temperatures below the Curie point (T(c)(IC) < T < T(c)(I)). For the cocrystal of the less acidic H(2)fa, the ferroelectric phase is induced only by applying hydrostatic pressure above ~0.6 GPa. According to the combined studies of temperature-dependent dielectric permittivity and synchrotron X-ray diffraction, it was proved that the ferroelectric (FE-I) phase is always accompanied at lower temperatures by successive phase transitions to the lattice modulated phases with incommensurate periodicities (IC phase, T(c)(II) < T < T(c)(IC)) and with commensurate (2- or 3-fold) periodicities (FE-II or FE-III phase, T < T(c)(II)). Whereas the ground-state structures at ambient pressure are different from one another among the Phz-H(2)ca (FE-II form), Phz-H(2)ba (FE-III form), and Phz-H(2)fa (paraelectric form), their systematic changes under pressure depict a universal pressure-temperature phase diagram. The possible origins of structural changes are assigned to the valence instability and the frustrated Coulomb interactions that induce the charge disproportionation (coexisting neutral ionic) states with the staging spatial orders.     

An analytical solution to non-axisymmetric heat transfer with viscous dissipation for non-Newtonian fluids in laminar forced flow

Forced convection heat transfer in a non-Newtonian fluid flow inside a pipe whose external surface is subjected to non-axisymmetric heat loads is investigated analytically. Fully developed laminar velocity distributions obtained by a power-law fluid rheology model are used, and viscous dissipation is taken into account. The effect of axial heat conduction is considered negligible. The physical properties are assumed to be constant. We consider that the smooth change in the velocity distribution inside the pipe is piecewise constant. The theoretical analysis of the heat transfer is performed by using an integral transform technique – Vodicka’s method. An important feature of this approach is that it permits an arbitrary distribution of the surrounding medium temperature and an arbitrary velocity distribution of the fluid. This technique is verified by a comparison with the existing results. The effects of the Brinkman number and rheological properties on the distribution of the local Nusselt number are shown.     

Tensile and Tensile-Mode Fatigue Testing of Microscale Specimens in Constant Humidity Environment

A tensile and tensile-mode-fatigue tester has been developed for testing microscale specimens in high humidity environments in order to investigate the fracture mechanisms of microelectromechanical materials. A humidity control system was installed on a tensile-mode fatigue tester equipped with an electrostatic force grip. A specimen and a griping device were inserted into a small chamber and the humidity was controlled by air flow from a temperature and humidity chamber. The humidity stability was within ±2%RH for humidities in the range 25–90%RH for eight hours of testing. Fatigue tests were performed on single-crystal silicon (SCS) specimens in constant humidity environments and laboratory air for up to 10⁶ cycles. The gauge length, width, and thickness of the SCS specimens were 100 or 500 μm, 13.0 μm, and 3.3 μm, respectively. The average tensile strength was 3.68 GPa in laboratory air; this value decreased in high humidity environments. Fatigue failure was observed during cyclic loading at stresses lower than the average strength. A reduction in the fatigue strength was observed at high relative humidities. Different fracture origins and fracture behaviors were observed in tensile tests and fatigue tests, which indicates that the water vapor in air affects the fatigue properties of SCS specimens.     

Gold nanoparticles located at the interface of anatase/rutile TiO2 particles as active plasmonic photocatalysts for aerobic oxidation

Visible-light irradiation (λ > 450 nm) of gold nanoparticles loaded on a mixture of anatase/rutile TiO(2) particles (Degussa, P25) promotes efficient aerobic oxidation at room temperature. The photocatalytic activity critically depends on the catalyst architecture: Au particles with <5 nm diameter located at the interface of anatase/rutile TiO(2) particles behave as the active sites for reaction. This photocatalysis is promoted via plasmon activation of the Au particles by visible light followed by consecutive electron transfer in the Au/rutile/anatase contact site. The activated Au particles transfer their conduction electrons to rutile and then to adjacent anatase TiO(2). This catalyzes the oxidation of substrates by the positively charged Au particles along with reduction of O(2) by the conduction band electrons on the surface of anatase TiO(2). This plasmonic photocatalysis is successfully promoted by sunlight exposure and enables efficient and selective aerobic oxidation of alcohols at ambient temperature.     

Extension to velocity dependent gauge transformations

In previous papers it was shown that in phase space a generator of gauge transformations for a singular Lagrangian \(L(q,\dot q)\) is given byG[ε^α]=ε _k ^α φ _α ^k (q,p,t) where φ _α ^k are first class constraints andG is subjected to a stationarity condition. A non-trivial extension from velocity (or momentum) independent gauge transformations to velocity dependent ones is realized, by replacing gauge functions ε^α(t) with momentum dependent functions ε^α(q,p,t), as long asG satisfies the stationarity condition. Inversely, it is proved in a classical framework that, within velocity dependent gauge transformations, all generators of gauge transformations can be expressed in terms of the linear combinations of φ _α ^k .     

P 3-factorization of complete multipartite graphs

In this paper, it is shown that a necessary and sufficient condition for the existence of aP ₃-factorization ofK _m ⁿ is (i)mn 0(mod 3) and (ii) (m – 1)n 0(mod 4).