Holmium porphyrin compound liquid crystals: Synthesis and properties

5,10,15,20-Tetra-[(p-alkoxy-m-ethyloxy)phenyl]porphyrin and [5-(p-alkoxy)phenyl-10,15,20-tri-phenyl]porphyrin and their holmium(III) complexes are reported. They display a hexagonal columnar discotic columnar Col(h)) liquid crystal phase and were studied by cyclic voltammetry, surface photovoltage spectroscopy (SPS), electric-field-induced surface photovoltage spectroscopy (EFISPS) and luminescence spectroscopy. Within the accessible potential window, all these compounds exhibit two one-electron reversible redox reactions. Quantum yields of Q band are in the region 0.0045-0.21 at room temperature. The SPS and EFISPS reveal that all the compounds are p-type semiconductors and exhibit photovoltaic response due to pi-pi* electron transitions.

Phase transformation and photoluminescence properties of nanocrystalline ZrO2 powders prepared via the Pechini-type sol-gel process

Nanocrystalline ZrO2 fine powders were prepared via the Pechini-type sol-gel process followed by annealing from 500 to 1000 degrees C. The obtained ZrO2 samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR), and photoluminescence spectra (PL), respectively. The phase transition process from tetragonal (T) to monoclinic (M) was observed for the nanocrystalline ZrO2 powders in the annealing process, accompanied by the change of their photoluminescence properties. The 500 degrees C annealed ZrO2, powder with tetragonal structure shows an intense whitish blue emission (lambda(max) = 425 nm) with a wide range of excitation (230-400 nm). This emission decreased in intensity after being annealed at 600 degrees C (T + M-ZrO2) and disappeared at 700 (T + M-ZrO2), 800 (T + M-ZrO2), and 900 degrees C (M-ZrO2). After further annealing at 1000 degrees C (M-ZrO2), a strong blue-green emission appeared again (lambda(max) = 470 nm).

Order-disorder transition in eicosylated polyethyleneimine comblike polymers

Order-disorder transition (ODT) behavior in eicosylated polyethyleneimine (PEI20C) comblike polymer obtained by grafting n-eicosyl group on polyethyleneimine backbone was systematically investigated by the combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy as well as solid-state high resolution nuclear magnetic resonance (NMR) spectroscopy. DSC investigations showed two obvious transitions, assigned to the transitions (1) from orthorhombic to hexagonal and (2) from hexagonal to amorphous phase, respectively. These transitions are induced by the variations of alkyl side chain conformation and packing structure with temperature changing, which consequently lead to the destruction of original phase equilibrium. The ODT behavior can also be confirmed by spectroscopic methods like WAXD, FTIR and NMR. The ordered structure and the transition behavior of the alkyl side chains confined by the PEI backbone are obviously different from those of pristine normal alkanes. The transition mechanism of ODT and the origin of the phase transition behavior in PEI20C comblike polymer were discussed in detail in this paper.

Liquid-liquid phase behavior of toluene/polyethylene oxide/poly(ethyleneoxide-b-dimethylsiloxane) polymer-containing ternary mixtures

The experimental data of phase diagrams for both polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) binary and toluene/polyethylene oxide/poly(ethylene oxide-b-dimethylsiloxane) ternary polymer-containing systems was obtained at atmosphere pressure by light scattering method. The critical points for some pre-selected compositions and the pressure effect on the phase transition behavior of ternary system were investigated by turbidity measurements. The chosen system is a mixture of ternary which is one of the very few abnormal polymer-containing systems exhibiting pressure-induced both miscibility and immiscibility. This unusual behavior is related to the toluene concentration in the mixtures. The effect of toluene on the phase transition behavior of the ternary polymer-containing mixture was traced. Such behavior can make it possible to process composite materials from incompatible polymers.

Abnormal pressure dependence of the phase boundaries in TL/PEO/P(EO-b-DMS) ternary mixtures

The cloud-point temperatures (T-cl's) of both binary poly(ethylene oxide) (PEO)-poly(ethylene oxide-b-dimethylsiloxane) [P(EO-b-DMS)] and ternary[toluene/PEO/P(EO-b-DMS)] systems were determined by light scattering measurements at atmospheric pressure. The phase separation behavior upon cooling in the ternary system has been investigated at atmospheric pressure and under high pressure and compared to the phase behavior in the binary system. The phase transition temperatures have been obtained for all of the samples. As a result, the pressure induces compatibility in the binary mixtures, but for the ternary system, pressure not only can induce mixing but also can induce phase separation.

Mixed-layer water oscillations in tropical Pacific for ENSO cycle

The main modes of interannal variabilities of thermocline and sea surface wind stress in the tropical Pacific and their interactions are investigated, which show the following results. (1) The thermocline anomalies in the tropical Pacific have a zonal dipole pattern with 160 W as its axis and a meridional seesaw pattern with 6-8 degrees N as its transverse axis. The meridional oscillation has a phase lag of about 90 to the zonal oscillation, both oscillations get together to form the El Nino/La Nina cycle, which behaves as a mixed layer water oscillates anticlockwise within the tropical Pacific basin between equator and 12 degrees N. (2) There are two main patterns of wind stress anomalies in the tropical Pacific, of which the first component caused by trade wind anomaly is characterized by the zonal wind stress anomalies and its corresponding divergences field in the equatorial Pacific, and the abnormal cross- equatorial flow wind stress and its corresponding divergence field, which has a sign opposite to that of the equatorial region, in the off-equator of the tropical North Pacific, and the second component represents the wind stress anomalies and corresponding divergences caused by the ITCZ anomaly. (3) The trade winds anomaly plays a decisive role in the strength and phase transition of the ENSO cycle, which results in the sea level tilting, provides an initial potential energy to the mixed layer water oscillation, and causes the opposite thermocline displacement between the west side and east side of the equator and also between the equator and 12 degrees N of the North Pacific basin, therefore determines the amplitude and route for ENSO cycle. The ITCZ anomaly has some effects on the phase transition. (4) The thermal anomaly of the tropical western Pacific causes the wind stress anomaly and extends eastward along the equator accompanied with the mixed layer water oscillation in the equatorial Pacific, which causes the trade winds anomaly and produces the anomalous wind stress and the corresponding divergence in favor to conduce the oscillation, which in turn intensifies the oscillation. The coupled system of ocean-atmosphere interactions and the inertia gravity of the mixed layer water oscillation provide together a phase-switching mechanism and interannual memory for the ENSO cycle. In conclusion, the ENSO cycle essentially is an inertial oscillation of the mixed layer water induced by both the trade winds anomaly and the coupled ocean-atmosphere interaction in the tropical Pacific basin between the equator and 12 degrees N. When the force produced by the coupled ocean-atmosphere interaction is larger than or equal to the resistance caused by the mixed layer water oscillation, the oscillation will be stronger or maintain as it is, while when the force is less than the resistance, the oscillation will be weaker, even break.

Two-Phase Flow In Fuel Cells In Short-Term Microgravity Condition

A visual observation of liquid-gas two-phase flow in anode channels of a direct methanol proton exchange membrane fuel cells in microgravity has been carried out in a drop tower. The anode flow bed consisted of 2 manifolds and 11 parallel straight channels. The length, width and depth of single channel with rectangular cross section was 48.0 mm, 2.5 mm and 2.0 mm, respectively. The experimental results indicated that the size of bubbles in microgravity condition is bigger than that in normal gravity. The longer the time, the bigger the bubbles. The velocity of bubbles rising is slower than that in normal gravity because buoyancy lift is very weak in microgravity. The flow pattern in anode channels could change from bubbly flow in normal gravity to slug flow in microgravity. The gas slugs blocked supply of reactants from channels to anode catalyst layer through gas diffusion layer. When the weakened mass transfer causes concentration polarization, the output performance of fuel cells declines.

Two-phase Flow in Fuel Cells in Short-term Microgravity Condition

A visual observation of liquid-gas two-phase flow in anode channels of a direct methanol proton exchange membrane fuel cells in microgravity has been carried out in a drop tower. The anode flow bed consisted of 2 manifolds and 11 parallel straight channels. The length, width and depth of single channel with rectangular cross section was 48.0 mm, 2.5 mm and 2.0 mm, respectively. The experimental results indicated that the size of bubbles in microgravity condition is bigger than that in normal gravity. The longer the time, the bigger the bubbles. The velocity of bubbles rising is slower than that in normal gravity because buoyancy lift is very weak in microgravity. The flow pattern in anode channels could change from bubbly flow in normal gravity to slug flow in microgravity. The gas slugs blocked supply of reactants from channels to anode catalyst layer through gas diffusion layer. When the weakened mass transfer causes concentration polarization, the output performance of fuel cells declines.

Characteristics of flow fields induced by interfacial waves in two-layer fluid

When designing deep ocean structures, it is necessary to estimate the effects of internal waves on the platform and auxiliary parts such as tension leg, riser and mooring lines. Up to now, only a few studies are concerned with the internal wave velocity fields. By using the most representative two-layer model, we have analyzed the behavior of velocity field induced by interfacial wave in the present paper. We find that there may exist velocity shear of fluid particles in the upper and lower layers so that any structures in the ocean are subjected to shear force nearby the interface. In the meantime, the magnitude of velocity for long internal wave appears spatially uniform in the respective layer although they still decay exponentially. Finally, the temporal variation for Stokes and solitary waves are shown to be of periodical and pulse type.

Laser intensity effects in photoemission and photoelectron spectra produced in laser-induced autoionisation

Strong laser-field-induced autoionisation in the presence of both photoionising and radiative decay of the autoionising state (AS) is investigated, focusing on the laser intensity dependence of the photoemission and photoelectron spectra. In contrast to previous predictions, power broadening and increasing reduction of the doublet peak heights with field strength are found in the photoemission spectrum. Similar effects leading to considerable suppression and even complete disappearance of the lowest-order peaks in the photoelectron spectrum, together with peak switching, are also demonstrated, which are closely related to above-threshold ionisation. In addition, it is suggested that the total number of energetic photoelectrons may serve as an alternative to measuring the atomic parameters of the AS. All these effects are attributed to the presence of the strong `probe': laser-induced decay of the AS.

Wavelength dependence of light-induced domain nucleation in MgO-doped congruent LiNbO3 crystal

Within the wavelength range from 351 to 799 nm, the different reductions of nucleation field induced by the focused continuous laser irradiation are achieved in the 5 mol % MgO-doped congruent LiNbO3 crystals. The reduction proportion increases exponentially with decreasing irradiation wavelength and decreases exponentially with increasing irradiation wavelength. At one given wavelength, the reduction proportion increases exponentially with increasing irradiation intensity. An assumption is proposed that the reduction of nucleation field is directly related to the defect structure of crystal lattice generated by the complex coaction of incident irradiation field and external electric field. (c) 2007 American Institute of Physics.

Phase-shifting apodizers for increasing focal depth

We propose the use of a phase-shifting apodizers to increase focal depth, and we study the axial and radial behavior of this kind of apodizer under the condition that the axial intensity distribution is optimized for high focal depth. (C) 2002 Optical Society of America.

Effects of deposition rates on laser damage threshold of TiO2/SiO2 high reflectors

TiO2 single layers and TiO2/SiO2 high reflectors (HR) are prepared by electron beam evaporation at different TiO2 deposition rates. It is found that the changes of properties of TiO2 films with the increase of rate, such as the increase of refractive index and extinction coefficient and the decrease of physical thickness, lead to the spectrum shift and reflectivity bandwidth broadening of HR together with the increase of absorption and decrease of laser-induced damage threshold. The damages are found of different morphologies: a shallow pit to a seriously delaminated and deep crater, and the different amorphous-to-anatase-to-rutile phase transition processes detected by Raman study. The frequency shift of Raman vibration mode correlates with the strain in. film. Energy dispersive X-ray analysis reveals that impurities and non-stoichiometric defects are two absorption initiations resulting to the laser-induced transformation. (C) 2008 Elsevier B. V. All rights reserved.

Effects of external magnetic field on the effective g factor of (Ga,Mn)As

With the help of time resolved magneto-optic Kerr rotation measurements, the optically induced spin precession in heavily doped diluted magnetic semiconductor Ga0.937Mn0.063 As was observed. It was found that the effective g factor increases with increasing magnetic field, which is attributed to the magnetic-field-induced increase of the density of the non-localized holes. Those free holes will couple with the localized magnetic ions by p-d interactions, leading to the formation of spontaneous magnetization in Ga0.937Mn0.063As, which in turn to the enhancement of the effective g factor.

The diphasic nc-Si/a-Si : H thin film with improved medium-range order

A series of silicon film samples were prepared by plasma enhanced chemical vapor deposition (PECVD) near the threshold from amorphous to nanocrystalline state by adjusting the plasma parameters and properly increasing the reactions between the hydrogen plasma and the growing surface. The microstucture of the films was studied by micro-Raman and Fourier transform infrared (FTIR) spectroscopy. The influences of the hydrogen dilution ratio of silane (R-H = [H-2]/[SiH4]) and the substrate temperature (T-s) on the microstructural and photoelectronic properties of silicon films were investigated in detail. With the increase of RH from 10 to 100, a notable improvement in the medium-range order (MRO) of the films was observed, and then the phase transition from amorphous to nanocrystalline phase occurred, which lead to the formation of diatomic hydrogen complex, H-2* and their congeries. With the increase of T-s from 150 to 275 degreesC, both the short-range order and the medium range order of the silicon films are obviously improved. The photoconductivity spectra and the light induced changes of the films show that the diphasic nc-Si/a-Si:H films with fine medium-range order present a broader light spectral response range in the longer wavelength and a lower degradation upon illumination than conventional a-Si:H films. (C) 2004 Elsevier B.V. All rights reserved.