Analysis of pentasodium triphosphate hydration kinetics

The present work analyzes the effect of various factors on the hydration of pentasodium triphosphate. The experimental method is based on application of the hydration test. Technical-quality products with different proportions of phase I and phase II have been used. The variables studied are phase I/phase II ratio, initial temperature, particle size, stirring rate and composition of the slurry (presence of hexahydrate crystals and water hardness). The results have been discussed according to a kinetics model that includes a series of stages of a physical nature (dissolution of anhydrous salt and the crystallization of the hexahydrate), as well as of a chemical nature (solvation of the ions in solution). Crystallization of the hexahydrate may be the controlling stage in the process.     

Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.     

Vessel Inspection: A Micro-Aerial Vehicle-based Approach

Vessel maintenance entails periodic visual inspections of the internal and external parts of the hull in order to detect the typical defective situations affecting metallic structures, such as coating breakdown, corrosion, cracks, etc. The main goal of project MINOAS is the automation of the inspection process, currently undertaken by human surveyors, by means of a fleet of robotic agents. This paper overviews an approach to the inspection problem based on an autonomous Micro Aerial Vehicle (MAV) which, as part of this fleet, is in charge of regularly supplying images that can teleport the surveyor from a base station to the areas of the hull to be inspected. The control software approach adopted for the MAV is fully described, with a special emphasis on the self-localization capabilities of the vehicle. Experimental results showing the suitability of the platform to the application are as well reported and discussed.     

Change detection by probabilistic segmentation from monocular view

We present a method for foreground/background video segmentation (change detection) in real-time that can be used, in applications such as background subtraction or analysis of surveillance cameras. Our approach implements a probabilistic segmentation based on the Quadratic Markov Measure Field models. This framework regularizes the likelihood of each pixel belonging to each one of the classes (background or foreground). We propose a new likelihood that takes into account two cases: the first one is when the background is static and the foreground might be static or moving (Static Background Subtraction), the second one is when the background is unstable and the foreground is moving (Unstable Background Subtraction). Moreover, our likelihood is robust to illumination changes, cast shadows and camouflage situations. We implement a parallel version of our algorithm in CUDA using a NVIDIA Graphics Processing Unit in order to fulfill real-time execution requirements.     

Agricultural use of three organic residues: effect on orange production and on properties of a soil of the ‘Comarca Costa de Huelva’ (SW Spain)

Disposal of urban, agricultural and industrial organic residues impliesan increasing problem because of all the economic and environmentalrepercussions involved. One of the most adequate ways of managing this problemis the agricultural use of these wastes as organic amendments. Three organicresidues (AC, olive mill waste water sludge compost; MWC, municipal solid wastecompost; and PS, paper mill sludge) were used in a 3-year field experimentinvolving orange production. The effect of their application on crop productionand on soil quality was investigated. Soil samples (0–20 cm depth)collected 11 months after the last soil amendment were analysed for: pH and EC,Kjeldahl-N, available-P, available-K, total organic carbon, humic substances,dehydrogenase, phosphatase, -glucosidase, urease andbenzoyl-argininamidehydrolysing protease (BAA-protease) activities. Generally, the application of the MWC and PSincreased orange yield when compared to control. Moreover, total organic carbonand humic substances significantly increased in soils treated with all theorganic amendments. Organic fertilisation increased the Kjeldahl-N andavailable-P contents of the soil. The application of the organic residues also causedsignificant increases in dehydrogenase, -glucosidase, urease andBAA-protease activities of the soil. Significant positive correlations (p <0.01) between these enzymatic activities and total organic carbon were foundforall treatments. Significant positive correlation between dehydrogenase, urease,-glucosidase, and BAA-protease and orange yield was also found. However,a clear inhibition of phosphatase activity was observed in soils treated withPS. The results indicate that the repeated application to the soil of moderateamounts of organic amendments has positive effects on the chemical andbiochemical properties of the soil, as well as on the orange yield.     

A New Nonlinear Controller for Trajectory Tracking of the Longitudinal Dynamics of a Small Scale Helicopter

A nonlinear control scheme is proposed for the trajectory tracking problem of a small scale helicopter’s longitudinal dynamics. The control scheme is based on a control design procedure that constructs static feedback regulators for nonlinear systems which are linearizable by dynamic feedback. Besides, the flatness characteristics of the helicopter’s longitudinal dynamics are used to design the desired trajectory. The controller proposed is based on the longitudinal model of the small scale helicopter including the main rotor and stabilizer bar dynamics. Sufficient conditions are given to guarantee asymptotic convergence to zero of the tracking error and to keep the main rotor thrust always negative assuming that all the helicopter’s parameters are known and that all helicopter’s states are measured. Numerical simulations are given to show the performance of the controller in the presence of the main rotor and stabilizer bar dynamics.     

Synthesis of deuterated cyclopropene fatty esters structurally related to palmitic and myristic acids

To develop a synthesis of tritiated cyclopropene fatty acids (CPFA), compounds that should prove useful for affinity labeling of desaturases in insect pheromone biosynthetic studies, a series of novel, selectively deuterated CPFA analogues was prepared and characterized. In methyl [16-²H]12,13-methylene-12-hexadecenoate, the incorporation of deuterium was achieved by treatment of the corresponding ω-chloro derivative with sodium borodeuteride in dimethylsulfoxide at 70°C for 24 h (67% yield) following conventional procedures. Alkylation of the tetrahydropyranyl derivative of 13-tridecynol in the presence of lithium diisopropylamide in tetrahydrofuran at −20°C with 1-chloro-3-iodopropane in hexamethylphosphoramide, followed by Jones oxidation of the crude product, yielded 16-chloro-12-hexadecynoic acid (54%), which was esterified to the corresponding methyl ester by treatment with potassium carbonate and methyl iodide in dimethylformamide. Treatment of this acetylenic ester with ethyldiazoacetate in the presence of activated copper-bronze as catalyst followed by hydrolysis in KOH solution at room temperature yielded 16-chloro-12,13-(carboxymethylene)-12-hexadecenoic acid. This diacid was treated with excess oxalyl chloride to give the corresponding diacyl chloride, which was decarbonylated in a diethyl ether solution with zinc chloride, and the cyclopropenium ions thus formed were added at −40°C to a methanolic sodium hydroxide solution of sodium borohydride to give methyl 16-chloro-12,13-methylene-12-hexadecenoate. Analogous procedures were followed to prepare methyl [17-²H]10,11-methylene-10-hexadecenoate, methyl [17-²H]11,12-methylene-11-hexadecenoate and methyl [17-²H]12,13-methylene-12-hexadecenoate from the corresponding diacids using sodium borodeuteride in the reduction of the cyclopropenium ions. Alternatively, methyl [2,2,3,3-²H₄]hexadecynoate, prepared by reaction of methyl 2,11-hexadecadiynoate with magnesium in deuterated methanol at room temperature, was submitted to the above cyclopropenylation and reductive decarbonylation sequence to give methyl [2,2,3,3,17-²H₅]-11,12-methylene-11-hexadecenoate. In summary, complementary methods for the selective incorporation of one to five deuterium atoms into cyclopropene fatty acids, at different sites, in moderate to high yields have been developed. The methods should easily be applicable to the preparation of the corresponding tritiated analogues.     

Comparative study of the physical aging of the epoxy systems BADGE n = 0/m‐XDA and BADGE n = 0/m‐XDA/PEI

The physical aging of the epoxy network consisting of a diglycidyl ether of bisphenol A, m‐xylylenediamine, and polyetherimide was studied by differential scanning calorimetry. The glass transition temperature and the variation of the specific heat capacities have been calculated using the method, based on the intersection of both enthalpy–temperature lines for glassy and liquid states. The apparent activation energy (E_H) was calculated using a single method that involved separate temperature and excess enthalpy dependency. All calorimetric data were compared with those obtained for the epoxy network without thermoplastic. thermoplastic. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3931–3935, 2006     

The effect of nanoclays on the nucleation,crystallization, and melting mechanisms of isotactic polypropylene

The influence of organomodified nanoclay (montmorillonite) on the crystallization and melting mechanisms of isotactic polypropylene (iPP) was studied. Films of both neat polymer and clay nanocomposites were prepared after molecular weight optimization through melt extrusion. Products exhibited the tactoidlike morphology since no compatibilizers were used. The effect of introduction of nanoclay within the polymer was studied through isothermal crystallization and linear heating. The results indicated that low nanoclay concentrations induce the formation of the β‐crystalline structure, its formation being inhibited with high nanoclay contents. Dynamic nonisothermal bulk crystallization experiments indicated that nanoclays act as nucleating agents of iPP. Isothermal, bulk crystallization studies indicated that the crystallization process (induction time and crystallization kinetics) is proportionally accelerated by the nanoclay presence. There was also an accelerated formation of secondary crystallization when nanoclays were present in high concentrations. POLYM. ENG. SCI., 47:1889–1897, 2007. © 2007 Society of Plastics Engineers