Heterogeneous Catalytic Polymerization of Ethylene in Microtubular Reactor Systems

The feasibility of using a microtubular reactor for heterogeneous polymerization of ethylene was investigated experimentally. Chemically inert polymer tubing of 800–2300 μm in inner diameter was fabricated and used as a polymerization reactor. Nonporous silica nanoparticles with a diameter of 400 nm were synthesized and used as support for the high‐activity rac‐ethylene(indenyl)₂ZrCl₂ catalyst with methylaluminoxane as cocatalyst and toluene as diluent. Large‐diameter microtubular reactors were also successfully used to conduct heterogeneous polymerization of ethylene in continuous reaction operations. High initial catalyst activity was obtained and the overall polymerization activity per volume or reactor length was quite high. No particle fragmentation occurred and the polymer particles were covered with small subgrains or nanofibrils with a diameter of 30 nm.     

Heat transfer of bio-oil in a direct contact heat exchanger during condensation

Rapid quenching of volatiles in fast pyrolysis is important for achieving high yield and quality of the bio-oil product, but few studies have examined the condensation of volatiles and their related heat exchangers. Accordingly, we have studied the condensation characteristics of volatiles by varying heat transfer conditions in a direct contact heat exchanger. As the mass flow rate ratio of quenching oil to pyrolysis gas increased, the heat transfer rate and yield of bio-oil increased. The heat transfer rate and yield of bio-oil reached a maximum value at an intermediate air-to-quenching oil mass flow rate ratio. Additionally, the heat transfer rate and yield of bio-oil decreased as the temperature of the quenching oil increased. Experiments were also conducted to derive an empirical relationship for the volumetric heat transfer coefficient for direct contact heat exchangers.     

Discrimination between natural and HPHT-treated type IIa diamonds using photoluminescence spectroscopy

We have performed low-temperature (8 K) photoluminescence (PL) measurements on 71 natural and 12 high-pressure-and-high-temperature (HPHT)-treated type IIa diamonds. The GR1, NV⁰, NV^?, H4, and H3 defect center PL signals are compared. Some distinct differences in the PL lineshape, intensity, and appearance of side-band PL signals are observed. Furthermore, we processed 6 of the natural diamond samples with the HPHT treatment to investigate the effect of the treatment on the PL spectrum. By systematically analyzing the differences in the PL spectra, we developed a scheme to discriminate natural and HPHT-treated diamonds with 99% validity.     

Investigation on the valence state of Te ions in the Bi6Ti5TeO22 thin film using X-ray photoelectron spectroscopy

Bi₆Ti₅TeO₂₂ (BTT) thin films were grown on a Pt/Ti/SiO₂/Si(1 0 0) substrate under various conditions and the valence state of the Te ion was investigated. For the BTT films grown at 300 °C, most of the Te ions existed as Te⁴⁺ ions. However, for the 10 mol% Mn-added BTT films grown at 300 °C, Te⁶⁺ ions were found even in the film grown under low oxygen partial pressure (OPP) and their number increased with increasing OPP. This increase was attributed to the presence of Mn²⁺ ions, which assisted the transition of Te⁴⁺ ions to Te⁶⁺ ions in order to maintain the charge balance of the Ti⁴⁺ sites. Furthermore, in the films grown at 300 °C under a high OPP of 80.0 Pa and subsequently annealed at 600 °C under a high oxygen pressure of 101 kPa, most of the Te ions existed as Te⁶⁺ ions. However, for the film grown at 300 °C under low OPP, even though the film was annealed under a high oxygen pressure of 101 kPa, only a few of Te⁶⁺ ions were formed, whereas most of Te ions remained as the Te⁴⁺ ions.     

Synthesis and nonlinear optical properties of a novel polyurethane containing cyanovinylthiophene with enhanced thermal stability of dipole alignment for electro‐optic applications

Stabilization of electrically induced dipole alignment is one of the important criteria in the development of nonlinear optical (NLO) polymers for electro‐optic device applications. Polyurethanes for NLO applications have attracted attention because of their high thermal stability due to hydrogen bonding. In the work reported here, we designed and synthesized a new type of NLO polyurethane, in which the pendant NLO chromophores are part of the polymer backbone. This mid‐type NLO polymer is expected to have the merits of both main‐chain and side‐chain NLO polymers, namely stable dipole alignment and good solubility. 1‐[3,4‐Di‐(2‐hydroxyethoxy)phenyl]‐2‐(2‐thienyl)ethene was prepared and condensed with 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate to yield a polyurethane. This polyurethane was reacted with tetracyanoethylene to give a novel Y‐type polyurethane (7) containing 1‐(3,4‐dioxyphenyl)‐2‐[5‐(1,2,2‐tricyanovinyl)‐2‐thienyl]ethenes as NLO chromophores, which constitute part of the polymer backbone. Polyurethane 7 is soluble in common organic solvents such as N,N‐dimethylformamide and dimethylsulfoxide. It shows a thermal stability up to 280 °C from thermogravimetric analysis with a glass transition temperature obtained from differential scanning calorimetry of ca 162 °C. The second harmonic generation (SHG) coefficient (d₃₃) of a poled polymer film of he polyurethane at 1560 nm fundamental wavelength is ca 1.11 × 10^?18 C. Polymer 7 exhibits an enhanced thermal stability and no significant SHG decay is observed below 150 °C, which is acceptable for NLO device applications. Copyright © 2009 Society of Chemical Industry     

Closing the ultrafine particle number concentration budget at road-to-ambient scale: Implications for particle dynamics

Freshly emitted vehicle exhaust particles are diluted quickly as they mix into ambient air, but the contribution of evaporation, coagulation, and/or nucleation of new particles to the number concentration has been the subject of some debate. We analyzed one-second time resolution size distribution data from an early morning field campaign, data collected at a time at which dilution has a smaller (but still dominant; ～70?80%) impact on particle concentrations. Because the plume is diluted over an hour, and a distance of 1500 m, we can constrain the processes with higher accuracy. We find that concentrations in the smaller size bins (5.6–23.7 nm) peak further downwind than the reference particles (42.1–562 nm), and decay significantly faster than larger particles particularly in the area 100?400 m downwind. Comparisons of the cumulative contributions of van der Waals enhanced coagulation, dry deposition, and dilution and the observed decay curves, imply that for up to the first 50–100 m there is nucleation and/or growth of particles smaller than 5.6 nm. In contrast, in the ～100–400 m region, some of the smaller particles evaporate. In the further downwind areas (>400 m) the particles all appear to decay at rates consistent with the sum of dilution, coagulation, and deposition. We also find that a dry deposition parameterization at the low end of those available in the literature is most consistent with the observational data.

© 2016 American Association for Aerosol Research