A Novel Porous Tube Reactor for Nanoparticle Synthesis with Simultaneous Gas-Phase Reaction and Dilution

A novel porous tube reactor that combines simultaneous reactions and continuous dilution in a single-stage gas-phase process was designed for nanoparticle synthesis. The design is based on the atmospheric pressure chemical vapor synthesis (APCVS) method. In comparison to the conventional hot wall chemical vapor synthesis reactor, the APCVS method offers an effective process for the synthesis of ultrafine metal particles with controlled oxidation. In this study, magnetic iron and maghemite were synthesized using iron pentacarbonyl as a precursor. Morphology, size, and magnetic properties of the synthesized nanoparticles were determined. The X-ray diffraction results show that the porous tube reactor produced nearly pure iron or maghemite nanoparticles with crystallite sizes of 24 and 29 nm, respectively. According to the scanning mobility particle sizer data, the geometric number mean diameter was 110 nm for iron and 150 nm for the maghemite agglomerates. The saturation magnetization value of iron was 150 emu/g and that of maghemite was 12 emu/g, measured with superconducting quantum interference device (SQUID) magnetometry. A computational fluid dynamics (CFD) simulation was used to model the temperature and flow fields and the decomposition of the precursor as well as the mixing of the precursor vapor and the reaction gas in the reactor. An in-house CFD model was used to predict the extent of nucleation, coagulation, sintering, and agglomeration of the iron nanoparticles. CFD simulations predicted a primary particle size of 36 nm and an agglomerate size of 134 nm for the iron nanoparticles, which agreed well with the experimental data.

Copyright 2015 American Association for Aerosol Research     

Adhesion of extrusion‐coated polymer sealing layers to a fiber‐based packaging material with an atomic layer deposited aluminum oxide surface coating

Adhesion of extrusion‐coated polymer sealing layers on an atomic layer deposited (ALD) aluminum oxide (Al₂O₃) surface coating was investigated with a view to gain information on the applicability of ALD deposited barrier layers in fiber‐based packaging materials. The polymers used for the sealing layer were low density polyethylene (LDPE), polyethylene terephthalate (PET), and polylactide (PLA). They were extrusion‐coated onto the ceramic side of paper/PET/Al₂O₃ substrates, where the Al₂O₃ layer was a few tens of nanometers thick. According to the results, good adhesion was obtained for LDPE coating, whereas the other coatings showed a considerable lack of adhesion. Presumably, the oxidation faced by LDPE in the air gap of the extrusion‐coating process was able to create an extensive number of reactive sites that strongly bonded with the hydroxyl groups on the oxide surface of the substrate. With the PET and PLA coatings, such oxidation did not occur and the adhesion obtained remained at a relatively poor level. With all of the coatings, the adhesion levels were improved using corona discharge equipment as a pretreatment prior to the extrusion‐coating process. POLYM. ENG. SCI., 52:1985–1990, 2012. © 2012 Society of Plastics Engineers     

Alteration of product specificity of Aeropyrum pernix farnesylgeranyl diphosphate synthase (Fgs) by directed evolution

Directed evolution of the C25 farnesylgeranyl diphosphate synthase of Aeropyrum pernix (Fgs) was carried out by error-prone PCR with an in vivo color complementation screen utilizing carotenoid biosynthetic pathway enzymes. Screening yielded 12 evolved clones with C20 geranylgeranyl diphosphate synthase activity which were isolated and characterized in order to understand better the chain elongation mechanism of this enzyme. Analysis of these mutants revealed three different mechanisms of product chain length specificity. Two mutants (A64T and A64V) have a single mutation at the 8th amino acid upstream of a conserved first aspartate-rich motif (FARM), which is involved in the mechanism for chain elongation reaction of all prenyl diphosphate synthases. One mutant (A135T) carries a single mutation at the 7th amino acid upstream of another conserved region (141GQ142), which was recently found to be another important region controlling chain elongation of a type III C20 geranylgeranyl diphosphate synthase and Escherichia coli C15 farnesyl diphosphate synthase. Finally, one mutant carrying four mutations (V84I, H88R, I177 M and M191V) is of interest. Molecular modeling, site-directed mutagenesis and in vitro assays of this mutant suggest that product chain-length distribution can be also controlled by a structural change provoked by a cooperative interaction of amino acids.     

Flavonoid Metabolites in the Hemolymph of European Pine Sawfly (Neodiprion sertifer) Larvae

Flavonoids in the hemolymph of European pine sawfly (Neodiprion sertifer) larvae that were feeding on Pinus sylvestris needles were identified. HPLC-ESI-MS analysis revealed that the main components in the hemolymph were flavonol di- and triglucosides and a catechin monoglucoside. These compounds were isolated from the larval hemolymph and their structures were established by HPLC-MS, GC-MS, and NMR spectroscopy. The isolated flavonoids were identified as (+)-catechin 7-O-β-glucoside, isorhamnetin 3,7,4'-tri-O-β-glucoside, kaempferol 3,7,4'-tri-O-β-glucoside, and quercetin 3,7,4'-tri-O-β-glucoside. The combined concentration of these four compounds in the hemolymph was 3.7 mg/ml. None of these compounds was present in the needles of P. sylvestris. Therefore, we propose that the flavonoid glucosides were produced by the larvae from flavonoid monoglucosides and (+)-catechin obtained from the pine needles.     

Anti-icing Behavior of Thermally Sprayed Polymer Coatings

Surface engineering shows an increasing potential to provide a sustainable approach to icing problems. Currently, several passive anti-ice properties adoptable to coatings are known, but further research is required to proceed for practical applications. This is due to the fact that icing reduces safety, operational tempo, productivity and reliability of logistics, industry and infrastructure. An icing wind tunnel and a centrifugal ice adhesion test equipment can be used to evaluate and develop anti-icing and icephobic coatings for a potential use in various arctic environments, e.g., in wind power generation, oil drilling, mining and logistic industries. The present study deals with evaluation of icing properties of flame-sprayed polyethylene (PE)-based polymer coatings. In the laboratory-scale icing tests, thermally sprayed polymer coatings showed low ice adhesion compared with metals such as aluminum and stainless steel. The ice adhesion strength of the flame-sprayed PE coating was found to have approximately seven times lower ice adhesion values compared with metallic aluminum, indicating a very promising anti-icing behavior.     

Novel Online Diagnostic Analysis for In-Flight Particle Properties in Cold Spraying

In cold spraying, powder particles are accelerated by preheated supersonic gas stream to high velocities and sprayed on a substrate. The particle velocities depend on the equipment design and process parameters, e.g., on the type of the process gas and its pressure and temperature. These, in turn, affect the coating structure and the properties. The particle velocities in cold spraying are high, and the particle temperatures are low, which can, therefore, be a challenge for the diagnostic methods. A novel optical online diagnostic system, HiWatch HR, will open new possibilities for measuring particle in-flight properties in cold spray processes. The system employs an imaging measurement technique called S-PTV (sizing-particle tracking velocimetry), first introduced in this research. This technique enables an accurate particle size measurement also for small diameter particles with a large powder volume. The aim of this study was to evaluate the velocities of metallic particles sprayed with HPCS and LPCS systems and with varying process parameters. The measured in-flight particle properties were further linked to the resulting coating properties. Furthermore, the camera was able to provide information about variations during the spraying, e.g., fluctuating powder feeding, which is important from the process control and quality control point of view.     

Ionic Liquids for Chloromethane/Isobutane Distillative Separation: Express Screening

The present study centres on room‐temperature ionic liquids (ILs) as entrainers in extractive distillation of chloromethane/isobutane mixtures. The binary system, chloromethane/isobutene, is an azeotropic system. In this study, IL entrainers are shown to be able to break the azeotrope and, thus, assure the separation in the whole range of chloromethane/isobutane ratios. ILs formed from different cations and anions are considered and their influence on chloromethane/isobutane separation is explored. Among the ILs studied, those containing the trifluoromethanesulfonate ([CF₃SO₃]^–) or tricyanomethanide ([C(CN)₃]^–) anion are demonstrated to exhibit an enhanced potential for chloromethane/isobutane separation compared to the corresponding ILs based on the bis(trifluoromethylsulfonyl)imide ([Tf₂N]^–) anion. Moreover, the ILs enclosing these anions are cheaper than those with the [Tf₂N]^– anion. Thus, the separation ability, solubility of chloromethane/isobutane mixtures, and costs of IL entrainers can be adjusted by the right choice of cations and anions.     

Forestry practices increase mercury and methyl mercury output from boreal forest catchments

We observed significant increases in the runoff output of total mercury (TotHg) and methyl mercury (MeHg) from a small spruce forest catchment (0.071 km2) after clear-cutting and soil treatment. Here we show that forest regeneration practices may act as an important additional source of TotHg and MeHg to forest lakes. TotHg and MeHg in runoff from two small forested catchments were monitored during the period 1994 to 2001. In the autumn of 1997, one of the catchments was clear-cut Soil preparation (mounding) was carried out in the autumn of 1998 and replanting in the summer of 1999. During the 3 years after the silvicultural treatment, medians of monthly flow-weighted TotHg and MeHg concentrations (12.02 ng L(-1) and 0.35 ng L(-1), respectively) and output loads (0.80-0.97 g km(-2) a(-1) and 0.011-0.036 g km(-2) a(-1), respectively) increased significantly compared to the 3 years calibration period (8.13 ng L(-1) and 0.15 ng 1(-1); 2.0-5.3 g km(-2) a(-1) and 0.11-0.16 g km(-2) a(-1), respectively). These results indicate that clear-cutting and/or soil treatment significantly increases the mobility of TotHg and MeHg accumulated in forest soil and may thus be an important factor for the total input of Hg to boreal freshwater ecosystems.     

Changes of the pH value of impregnated wood during exposure to wood-rotting fungi

and Schizophyllum commune). The third species was the brown-rot fungi Antrodia vaillantii, using three different strains of this species. Antrodia vaillantii substantially decreased the pH-value of impregnated and unimpregnated wood before any mass loss appeared. On the other hand, the white-rot fungus T. versicolor and S. commune caused a slight increase of the pH of impregnated and unimpregnated wood. It is suggested that a decrease of pH of wood may indicate early stages of decay by brown rot fungi.