Kinetic analysis of crystallization of zeolite beta synthesized by direct heating

To quantitatively investigate the initial crystallization of zeolite beta synthesized by direct heating, the extent of the reaction was precisely evaluated by X-ray diffraction measurements and Rietveld structural refinement, and a kinetic analysis of crystallization was performed using the Avrami-Erofe'ev equation. The activation energy for crystallization was lower than that for hydrothermal synthesis. Reaction and synthesis time curves revealed that the initial zeolite beta crystallization consisted of three stages. The first was an induction period with nucleation by the generation of building units and the formation of an initial coordinated structure. The second stage was crystal growth by a diffusion-controlled reaction, and the third stage involved slowing down of crystallization by the limitation of dehydrocondensation. These stages could be analyzed by calculation of the rate constant and Avrami exponent for each stage.     

Spiraling elliptic breathers in nonlocal nonlinear media with linear anisotropy

The dynamical properties of spiraling elliptic breathers in nonlocal nonlinear media with linear anisotropy are analytically discussed. Using a two-dimensional asynchronous fractional Fourier transform, the exact analytical solutions of spiraling elliptic breathers are obtained to the nonlocal nonlinear Schrödinger equation with unequal diffraction coefficients in the highly nonlocal limit. It is found that the spiraling elliptic breathers exhibit a kind of molecule-like libration due to the combined effects of the linear anisotropy and the orbital angular momentum. The angular velocity of the spiraling elliptic breathers is discussed, which can be controlled by the linear anisotropy parameter. In the media with linear anisotropy such as uniaxial crystals, the angular velocity of the spiraling elliptic breathers can be controlled by changing the propagation directions of optical beams. Furthermore, the nonlinearity of media is found to enhance the rotation effect of spiraling elliptic breathers.     

Pressureless all-solid-state sodium-ion battery consisting of sodium iron pyrophosphate glass-ceramic cathode and β″-alumina solid electrolyte composite

In recent years, the expansion of demand for lithium ion batteries has resulted in soaring prices of the constituent resources. From the viewpoint of safety, studies on all-solid-state batteries are actively being carried out. In this study, we succeeded in driving all-solid-state batteries derived from nontoxic oxide glasses at room temperature without requiring scarce resources such as lithium and cobalt. The main structure of the ceramic batteries with a simple structure in which Na₂FeP₂O₇ crystallized glass and β″-alumina solid solution are joined by pressureless cofiring at 550°C. During the crystallization of Na₂O-Fe₂O₃-P₂O₅ glass, fusion with the β″-alumina solid solution is achieved. Reversible charge and discharge of 80 mAh/g were achieved at room temperature. It is not necessary to apply pressure during cell preparation or the use of the batteries. Furthermore, the strong junction at the cathode and electrolyte interface does not peel off during charge and discharge over a long period of 623 cycles. Ex situ X-ray photoelectron spectroscopy revealed partial Fe⁴⁺ induction and a reversible charge and discharge reaction even after overcharging to 9 V. It was demonstrated that Na₂FeP₂O₇ is very stable against overcharging to 9 V.     

Nonreciprocal properties of 1D magnetized plasma photonic crystals with the Fibonacci sequence

In this paper, the nonreciprocal properties of a novel kind of 1D magnetized plasma photonic crystals(MPPCs) with the Fibonacci sequence are investigated. The isolation of the proposed 1D MPPCs is also used to analyze the nonreciprocal properties. Compared to the conventional 1D MPPCs with periodic structure, the nonreciprocal performance can be significantly improved.The effects of several parameters of the proposed 1D MPPCs on the nonreciprocal properties are studied by the transfer matrix method, which includes the incident angle, order of the Fibonacci sequence, plasma frequency, plasma cyclotron frequency and plasma filling factor. The obtained results show that the nonreciprocal propagation properties can be improved by increasing the values of the plasma cyclotron frequency and incident angle, but they will worsen by blindly increasing the order of the Fibonacci sequence, plasma frequency and filling factor of plasma.The peaks of transmittance also are obviously reduced. In addition, the value of isolation will increase with increasing the incident angle, order of Fibonacci sequence, plasma frequency and plasma filling factor. However, when the plasma cyclotron frequency is increased, the value of isolation will be increased at lower frequencies, but is almost unchanged at higher frequencies.     

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.     

Aluminum to germanium inversion in mullite-type RAlGeO5: Characterization of a rare phenomenon for R = Y,Sm–Lu

Mullite-type RMn₂O₅ (R = Y, rare-earth element) ceramics are of ongoing research attentions because of their interesting crystal-chemical, physical, and thermal properties. We report a detailed structural, spectroscopic and thermal analysis of the series of mullite-type RAlGeO₅ (R = Y, Sm-Lu) phases. Polycrystalline samples are prepared by solid-state synthesis methods. Each sample is characterized by X-ray powder diffraction followed by Rietveld refinements, showing that they are isotypic and crystallize in the space group Pbam. The change of the metric parameters is explained in term of the lanthanide contraction effect. A rare inversion of Al/Ge between octahedral and pyramidal sites have been observed for these mullite-type so called O10 compounds, and the inversion parameter found to be between 0.22(1) and 0.30(1) for different R-cations. The <Al/Ge–O> bond distances and their bond valence sums (BVSs) support the respective inversions. Density functional theory (DFT) calculated phonon density of states (PDOS) and electronic band structures are compared for the vibrational and electronic band gap features respectively. Analysis of UV/Vis absorption spectra using both derivation of absorption spectra fitting (DASF) and Tauc's methods demonstrates that each of the RAlGeO₅ O10 compounds is high bandgap semiconductor, possessing direct transition between 4.1(1) and 5.4(1) eV. Both Raman and Fourier transform infrared spectra show clear red shift (quasi-harmonic) of the vibrational wavenumbers with respect to the ionic radii of the R-cations. Selective Raman bands at higher wavenumber region further complement the inversion of Al/Ge between two coordination sites. The higher decomposition temperature of the RAlGeO₅ compounds, compared to those of RMn₂O₅ phases, is explained in terms of higher bond strength of Al/Ge-O than those of Mn-O. Irrespective to the inversion between Al- and Ge-sites, the decomposition temperature also depends on the type of R-cation in RAlGeO₅.     

Stimuli-Responsive Dynamic Metaholographic Displays with Designer Liquid Crystal Modulators

Flat optics, realized by the artificially created 2D material platform called optical metasurfaces, is currently undergoing a science-to-technology transition. However, “real-time” active operations of such flat optical devices remain yet unresolved. Here, liquid crystals (LCs)-integrated metaholograms for ultracompact dynamic holographic displays are proposed. The anisotropic nature of the LCs allows facile and repeatable manipulation of the polarization of light. Specifically designed (“designer”) LCs and efficient helicity-encoded metaholograms are combined to realize stimuli-responsive dynamic displays. The designer LC modulators are used as switches that enable a variety of external stimuli (e.g., electric field, heat, surface pressure) to operate holographic images in real-time. Such a dynamic metaholographic platform will provide a path to external stimuli-driven “smart” sensing and display applications such as hologram labels for temperature/pressure/touch monitoring and interactive holographic displays with haptic motion recognition.