Kinetics study on melt grafting copolymerization of LLDPE with acid monomers using reactive extrusion method

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetics studies on reactive extrusion were carried out for the difficulties as expected. In this work, the macromolecular peroxide-induced grafting of acrylic acid and methyl methacrylate onto linear low density polyethylene by reactive extrusion was chosen as the model system for the kinetics study; the samples were taken out from the barrel at five ports along screw axis and analyzed by FTIR, H-1 NMR, and ESR. For the first time, the time-evolution of reaction rate, the reaction order, and the activation energy of graft copolymerization and homopolymerization in the twin screw extruder were directly obtained. On the basis of these results, the general reaction mechanism was tentatively proposed. It was demonstrated that an amount of chain propagation free radicals could keep alive for several minutes even the peroxides completely decomposed and the addition of monomer to polymeric radicals was the rate-controlled step for the graft copolymerization.

Activation energy for the reverse eutectoid reaction in hypo-eutectoid Cu-Al alloys

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo de cinética não-isotérmica da reação eutetóide em ligas de 'CU'-'AL' com adições de 'AG'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The dependence of computed tomography number to relative electron density conversion on phantom geometry and its impact on planned dose

A computed tomography number to relative electron density (CT-RED) calibration is performed when commissioning a radiotherapy CT scanner by imaging a calibration phantom with inserts of specified RED and recording the CT number displayed. In this work, CT-RED calibrations were generated using several commercially available phantoms to observe the effect of phantom geometry on conversion to electron density and, ultimately, the dose calculation in a treatment planning system. Using an anthropomorphic phantom as a gold standard, the CT number of a material was found to depend strongly on the amount and type of scattering material surrounding the volume of interest, with the largest variation observed for the highest density material tested, cortical bone. Cortical bone gave a maximum CT number difference of 1,110 when a cylindrical insert of diameter 28 mm scanned free in air was compared to that in the form of a 30 × 30 cm2 slab. The effect of using each CT-RED calibration on planned dose to a patient was quantified using a commercially available treatment planning system. When all calibrations were compared to the anthropomorphic calibration, the largest percentage dose difference was 4.2 % which occurred when the CT-RED calibration curve was acquired with heterogeneity inserts removed from the phantom and scanned free in air. The maximum dose difference observed between two dedicated CT-RED phantoms was ±2.1 %. A phantom that is to be used for CT-RED calibrations must have sufficient water equivalent scattering material surrounding the heterogeneous objects that are to be used for calibration.

Dependence of electron recombination time and light to electricity conversion efficiency on shape of the nanocrystal light sensitizer

Tunability of electron recombination time and light to electricity conversion efficiency to superior values in semiconductor sensitized solar cells via optimized design of nanocrystal light sensitizer shape is discussed here.

Mechanisms and concentrations dependence of up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics

The up-conversion properties of Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation were investigated. Intense blue up-conversion luminescence due to the Tm3+: (1)G(4) -> H-3(6) transition was observed in the glass-ceramics. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The up-conversion mechanism is proposed. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics and the concentrations dependence of upconversion luminescence are also discussed. (c) 2005 Elsevier B.V. All rights reserved.

Preparation of the layered double hydroxide (LDH) LiAl2(OH)(7)center dot 2H(2)O, by gel to crystallite conversion and a hydrothermal method, and its conversion to lithium aluminates

A layered double hydroxide (LDH) with chemical composition LiAl2(OH)(7) . 2H(2)O was prepared via a wet chemical route of gel to crystallite (G-C) conversion at 80 degrees C involving the reaction of hydrated alumina gel, Al2O3.yH(2)O (80 < y < 120) with LiOH (Li2O/Al2O3 greater than or equal to 0.5) in presence of hydrophilic solvents such as ethanol under refluxing conditions. The hydrothermal synthesis was carried out using the same reactants by heating to less than or equal to 140 degrees C in a Teflon-lined autoclave under autogenerated pressure (less than or equal to 20 MPa). Transmission electron microscopy showed needle-shaped aggregates of size 0.04-0.1 mu m for the gel to crystallite conversion product, whereas the hydrothermal products consisted of individual lamellar crystallites of size 0.2-0.5 mu m with hexagonal morphology. The LDH prepared through the gel to crystallite conversion could be converted into LiAl(OH)(4) . H2O or LiAl(OH)(3)NO3 . H2O by imbibition of LiOH or LiNO3, respectively, under hydrothermal conditions. Thermal decomposition of LDH above 1400 degrees C gave rise to LiAl5O8 accompanied by the evaporation of Li2O. LiAl(OH)(4) . H2O and LiAl(OH)(3)NO3 . H2O decomposed in the temperature range 400-1000 degrees C to alpha- or beta-LiAlO2. The compositional dependence of the product, the intermediate phases formed during the heat treatment and the possible reactions involved are described in detail.

Strong visible up-conversion emissions and thermometric applications of Er3+-Yb3+ codoped Al2O3 prepared by the sol-gel method

The Er3+-Yb3+ codoped Al2O3 has been prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)(3)]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)(3) center dot 5H(2)O] and ytterbium nitrate [Yb(NO3)(3) center dot 5H(2)O]. The phase structure, including only two crystalline types of doped Al2O3 phases, theta and gamma, was obtained for the 1 mol% Er3+ and 5 mol% Yb3+ codoped Al2O3 at the sintering temperature of 1,273 K. By a 978 nm semiconductor laser diodes excitation, the visible up-conversion emissions centered at about 523, 545, and 660 nm were obtained. The temperature dependence of the green up-conversion emissions was studied over a wide temperature range of 300-825 K, and the reasonable agreement between the calculated temperature by the fluorescence intensity ratio (FIR) theory and the measured temperature proved that Er3+-Yb3+ codoped Al2O3 plays an important role in the application of high temperature sensor.

Frequency up-conversion properties of Er3(+)-doped TeO2-ZnO-PbCl2 oxyhalide tellurite glasses

This paper reports on the successful preparation and a detailed study on the up-conversion properties of Er3+ -doped TeO2-ZnO-PbCl2 oxylialide tellurite glasses. Three intense emissions centered at around 527, 549 and 666 nm have been clearly observed under 977 nm excitation and the involved mechanisms have been explained. The green emissions centered at 527 and 549 nin are due to the H-2(11/2 ->) I-4(15/2) and S-4(3/2) -> I-4(15/2) transitions, and the red up-conversion emission centered at 666 nm is associated with the F-4(9/2) -> I-4(15/2) transitions of Er3+ ions, respectively. The quadratic dependence of fluorescence on excitation laser power confirm that two-photons contribute to up-conversion of the green-red emissions. (c) 2005 Elsevier B.V. All rights reserved.

Intense blue up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics containing beta-PbF2 nanocrystals

Up-conversion luminescence properties of a Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980nm excitation are investigated. Intense blue emission centered at 476nm, corresponding to (1)G(4) -> H-3(6) transitions of Tm3+ was simultaneously observed in the transparent oxyfluoride glass ceramics at room temperature. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The reason for the intense TM3+ up- conversion luminescence in the oxyfluoride glass-ceramics is discussed. The dependence of up-conversion intensities on excitation power and possible up-conversion mechanism are also evaluated. (c) 2005 Elsevier B.V. All rights reserved.

Up-conversion luminescence analysis in ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses

Ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses have been synthesized by conventional melting method. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2) and F-4(9/2) -> I-4(15/2), respectively, were simultaneously observed at room temperature in these glasses. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. Tellurite glass showed a weaker up-conversion emission than germanate-niobic-lead glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate-mobic-lead glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. Our results reveal that the phonon density and the maximum phonon energy of host glasses are both important factors in determining the up-conversion efficiency. (c) 2005 Elsevier B.V. All rights reserved.

Chirp limitation on high-speed wavelength conversion using semiconductor optical amplifiers

The cross-gain-saturation effect in SOAs, has been shown to enable robust high-speed wavelength conversion. Under strong electrical and optical pumping, conversion speeds in excess of 20 Gbit/s have been illustrated. However, the effect of chirp on transmission distance at such ultrahigh bit rates has not been studied theoretically in detail. This paper considers the chirp introduced on conversion, employing cross-gain saturation, and studies its dependence on amplifier drive current and signal power. It further shows how an increase in injected cw optical power can reduce chirp while improving conversion speed.

Enhanced down conversion of photons emitted by photoexcited Er xY2-xSi2O7 films grown on silicon

Photon cutting with efficiencies up to 400% is demonstrated in Erx Y2-x Si2 O7 films grown on Si and its concentration dependence is analyzed. The cutting is the result of cross-energy-transfer processes occurring within a single rare earth (Er3+) acting as both sensitizer and activator. Similarities with upconversion are revealed and possible applications in solar cells are discussed. © 2010 The American Physical Society.

Dependence of dye regeneration and charge collection on the pore-filling fraction in solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells rely on effective infiltration of a solid-state hole-transporting material into the pores of a nanoporous TiO 2 network to allow for dye regeneration and hole extraction. Using microsecond transient absorption spectroscopy and femtosecond photoluminescence upconversion spectroscopy, the hole-transfer yield from the dye to the hole-transporting material 2,2′,7,7′-tetrakis(N,N-di-p- methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) is shown to rise rapidly with higher pore-filling fractions as the dye-coated pore surface is increasingly covered with hole-transporting material. Once a pore-filling fraction of ≈30% is reached, further increases do not significantly change the hole-transfer yield. Using simple models of infiltration of spiro-OMeTAD into the TiO2 porous network, it is shown that this pore-filling fraction is less than the amount required to cover the dye surface with at least a single layer of hole-transporting material, suggesting that charge diffusion through the dye monolayer network precedes transfer to the hole-transporting material. Comparison of these results with device parameters shows that improvements of the power-conversion efficiency beyond ≈30% pore filling are not caused by a higher hole-transfer yield, but by a higher charge-collection efficiency, which is found to occur in steps. The observed sharp onsets in photocurrent and power-conversion efficiencies with increasing pore-filling fraction correlate well with percolation theory, predicting the points of cohesive pathway formation in successive spiro-OMeTAD layers adhered to the pore walls. From percolation theory it is predicted that, for standard mesoporous TiO2 with 20 nm pore size, the photocurrent should show no further improvement beyond an ≈83% pore-filling fraction. Solid-state dye-sensitized solar cells capable of complete hole transfer with pore-filling fractions as low as ∼30% are demonstrated. Improvements of device efficiencies beyond ∼30% are explained by a stepwise increase in charge-collection efficiency in agreement with percolation theory. Furthermore, it is predicted that, for a 20 nm pore size, the photocurrent reaches a maximum at ∼83% pore-filling fraction. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theory and experiment of two-photon 'direct' interference for type-II spontaneous parametric down-conversion with an ultrafast pulse laser pump

Fourth-order spatial interference of entangled photon pairs generated in the process of spontaneous parametric down-conversion pumped by a femtosecond pulse laser has been performed for the first time. In theory, it takes into account the transverse correlation between the two photons and is used to calculate the dependence of the visibility of the interference pattern obtained in Young's double-slit experiment. In this experiment, a short focal length tens and two narrow band interference filters were adopted to eliminate the effects of the broadband pump laser and improve the visibility of the interference pattern under the condition of nearly collinear light and degenerate phase matching.