Multiphase coatings from complex radiation curable polyurethane dispersions

The waterborne nature of radiation curable polyurethane dispersions largely respond to the current environmental concerns and do not require any additional coalescent since the film formation (drying) and hardening (photo-curing) take place in distinct steps. It is possible to design aqueous dispersions with distinct polymer particle populations resulting in micro-structured coatings with optimized properties over a wide range of curing conditions. Mixed dispersions based on hard and soft acrylated polyurethane particles were used as model systems for the present study. The minimum film formation temperature has been investigated as a function of the hard:soft polymer ratio. The elastic modulus of the dry coatings shows a reinforcing effect consistent with the inclusion of hard domains in a soft continuous matrix. However, the level of reinforcement is not properly predicted by the usual mechanical models and it is qualitatively accounted for by assuming a composition gradient (interphase) between the hard domains and the matrix. The multiple-phase structure was clearly established by Atomic Force Microscopy in agreement with thermal analysis data. Furthermore the local nanoscale mechanical properties were mapped using a new imaging mode based on real-time force–distance curve analysis. Finally, the coatings prepared using this multiple-phase pattern present a clear benefit over conventional homogeneous coatings by offering an improved balance of chemical and mechanical resistance in pigmented systems applied on melamine-coated MDF panels.     

Evaluation of <Emphasis Type="Italic">Rhizopus oryzae</Emphasis> Lipase for the Determination of Regiodistribution in Triacylglycerols with Medium Chain Fatty Acids

The nutritional profile and rheological behaviors of lipids is both due to fatty acid composition and regiodistribution on external and internal positions of triacylglycerol. Actual methods for regiodistribution analysis having some restrictions, there is still a need for investigating a safe, simple and environmentally friendly method for the sn-2 position analysis that could especially be used for the analysis of fats containing medium and short chain fatty acids. The objective of this study was to evaluate the 1,3-selectivity and typoselectivity of Rhizopus oryzae lipase in the presence of short/medium chain fatty acids in partial hydrolysis conditions used for regiodistribution analysis. Structured triacylglycerols containing eight-carbon-chain length fatty acids in the sn -2 position were chemically synthesized using DCC/DMAP coupling agent and purification steps by flash-chromatography. The final product showed very high purity and was used as the substrate for 1,3-selectivity evaluation. Typoselectivity was assessed by investigating partial hydrolysis of equimolar blends of homogeneous TAG. This study confirmed the 1,3-selectivity of Rhizopus oryzae lipase in the hydrolysis conditions used, and revealed that this lipase was less influenced by fatty acids chain length than pancreatic lipase. Considering this, Rhizopus oryzae lipase appeared to be a good candidate for regiodistribution analysis of fats containing medium and short chain fatty acids.     

Field-scale analysis of water and nutrient use efficiency for vegetable production in a West African urban agricultural system

Urban agriculture increasingly supplies food and non-food services to the rapidly growing West African cities. However, with its typically heavy use of fertilizers and uncontrolled use of water, it bears severe risks of soil and groundwater pollution. This study was carried out in Bobo Dioulasso (Burkina Faso, West Africa) at two commercial gardening sites. It aimed at performing a detailed characterization of farmer’s water and nutrient management strategies. Four vegetable crops were monitored (tomato, cabbage, carrot and lettuce). Water inputs (rainfall and irrigation), nutrient inputs (organic and mineral fertilizers and nutrients in irrigation water) and crop uptake were monitored over a 1–2-year period. In addition, pan lysimeters allowed monitoring drainage. Depending on the site, 3–8% of the input water was lost by drainage, i.e., as much as 293 mm/year at one of the sites. During the dry season, when the farmer has full control over the water supply, water application exceeded plant requirements by as much as 40%, which reveals inefficient water use. Up to 800 kg N ha⁻¹, 140 kg P ha⁻¹ and 500 kg K ha⁻¹ were applied for a single crop cycle. With few exceptions, crops tended to be strongly over-fertilized, except for K at one of the two sites. Nutrient supply exceeded crop requirements by 109 to 2,012 kg N, 66 to 450 kg P and 0 to 393 kg K per year. These results, in combination with the large observed rates of drainage, are indicative of a high risk of nutrient leaching and groundwater contamination. The partial factor productivity of nutrients tended to be low. These results therefore suggested that there is scope to substantially reduce nutrient application rates in these systems without adverse effects on yields, which would be beneficial for groundwater resources and improve the economic returns.     

New transesterification between ester and alkoxysilane groups: application to ethylene-co-vinyl acetate copolymer crosslinking

The transesterification between ester and alkoxysilane groups in the range of temperatures 100-250 °C takes place only in the presence of dibutyltin oxide (DBTO) as efficient catalyst. Without DBTO, no reaction is observed. This interchange reaction has been used to crosslink ethylene-co-vinylacetate copolymer. Kinetic and rheology data have shown that only two alkoxide groups from one tetrafunctional alkoxysilane molecule are involved in the crosslinking reaction.     

Nickel Nanoparticles Supported on Silica of Low Surface Area. Hydrogen Chemisorption and TPD and Catalytic Properties

Nickel metal nanoparticles supported on silica of low surface area (15 m² g^-1) were prepared by reduction of nickel acetate by hydrazine in aqueous medium. Their gas-phase stability and surface properties depended on thermal pre-treatment under H₂ or air atmosphere. Small nickel particles (<10 nm), in oxidized or reduced state, are strongly resistant to reductive or oxidative treatment respectively. For H₂-treated catalysts, H₂ chemisorption and TPD results suggested the occurrence of spillover hydrogen between the metal nickel phase and silica. For air then H₂ treated catalysts, hydrogen spillover seemed to involve the NiO phase. The activity of the catalysts in gas-phase benzene hydrogenation also depended on the thermal pre-treatment. Pre-calcined then reduced catalysts exhibited higher TOFs than non pre-calcined catalysts, suggesting that the presence of NiO phase may have influenced the hydrogenation process.     

Low-Temperature Chemical Vapor Deposition Tungsten Carbide Coatings for Wear/Erosion Resistance

A new chemical vapor deposition (CVD) process has been developed to deposit hard coatings, containing tungsten carbide, at temperatures below 500°C. These coatings, which have been applied to both ferrous and nonferrous alloys, exhibit excellent resistance to wear and erosion. The coatings comprise a mixture of tungsten and the tungsten carbide, the latter being present as W₂C, W₂C + W₃C, or W₃C. The coatings' composition and properties can be controlled by varying the CVD process parameters. The unique lamellar, fine-grained microstructures of these coatings contribute to their good tribological properties.     

Room temperature molten salts as lithium battery electrolyte

In the present study, are reported investigations obtained with the room temperature molten salt (RTMS) ethyl-methyl-imidazolium bis-(trifluoromethanesulfonyl)-imide (EMI-TFSI) in order to use it as solvent in lithium battery. The thermal stability, viscosity, conductivity and electrochemical properties are presented. A solution of 1m lithium bis-(trifluoromethanesulfonyl)-imide (LiTFSI) in EMI-TFSI has been used to test the electrolyte in a battery with LiCoO₂ and Li₄Ti₅O₁₂ as respectively cathode and anode materials. Cycling and power measurements have been obtained. The results have been compared with those obtained with a molten salt formulated with a different anion, BF₄⁻ and with a conventional liquid organic solvent EC/DMC containing LiTFSI. The 1m LiTFSI/EMI-TFSI electrolyte provides the best cycling performance: a capacity up to 106 mAh g⁻¹ is still delivered after 200 cycles, with 1C rate at 25 °C.     

Pheromone Response Inhibitors of the Corn Stalk Borer Sesamia nonagrioides. Biological Evaluation and Toxicology

The behavioral activity of some trifluoromethyl ketones (TFMKs) as inhibitors of the pheromone activity of the corn stalk borer Sesamia nonagrioides (Lef.) (Lepidoptera: Noctuidae) is reported. The most closely-related analogue to the pheromone tested, (Z)-11-hexadecenyl trifluoromethyl ketone (Z11-16:TFMK), elicited a significant decrease in the number of male catches in traps baited with mixtures with the pheromone in 1:1 and 10:1 ratios in comparison to the pheromone alone. The E isomer of the analogue as well as two highly hydrated ketones, 3-octylthio-1,1,1-trifluoropropan-2-one (OTFP) and 1,1-difluoropentadecyl trifluoromethyl ketone, were inactive. Conversely, the saturated TFMKs n-dodecyl trifluoromethyl ketone and, particularly, n-hexadecyl trifluoromethyl ketone induced a synergistic effect when mixed with the synthetic pheromone in 10:1 ratio. However, in a wind tunnel these chemicals did not elicit any differential effect on flying moths attracted to a source containing a 10:1 blend of the analogue and the pheromone. In a dual choice bioassay with two dispensers, containing the pheromone alone, and mixtures of Z11-16:TFMK and the pheromone and separated 5 cm apart, males showed no particular preference for either dispenser. The ketone mixture, however, induced moths to execute erratic flights with frequent crosswind counter-turns and intersections with plume boundaries. The total number of contacts with the source were reduced when a control dispenser was paired with a dispenser containing Z11-16:TFMK and pheromone. Z11-16:TFMK and OTFP showed little toxicity on mice with a LD₅₀ of 1 g/kg after the 6th day of treatment. For comparitive purposes, the major component of the pheromone, Z11-16:Ac, displayed a LD₅₀ of 5 g/kg 6 days after application. Our results provide additional information about the activity of the TFMKs, which might be useful for the utilization of these chemicals in future pest control studies.