Surface chemistry and kinetics of the hydrolysis of isocyanic acid on anatase

In order to meet the stricter NO_x and particulate emission limits for commercial vehicles, the selective catalytic reduction (SCR) with urea is currently seen having the highest potential. The conversion of urea into ammonia and carbon dioxide consists of two consecutive reactions, in which isocyanic acid is an intermediate that is hydrolyzed over TiO₂. The intrinsic kinetics and the surface chemistry for this reaction are explored. Up to a temperature of 132 °C the reaction was in the intrinsic kinetic regime (E_A = 73 kJ/mol), while at higher temperatures the reaction was limited by pore and external diffusion constraints, respectively. In the presence of NO, NH₃ and NO₂, the catalytic activity was negatively influenced, increasing in severity in the sequence mentioned indicating that nitrates formed from NO₂ were most effective in blocking cations and anions of TiO₂. IR spectroscopy indicates that dissociative adsorption of HNCO on TiO₂ forms Ti–NCO and hydrogen bonded OH species. In the presence of water, isocyanic acid was so rapidly hydrolyzed that only adsorbed ammonia was observed on the catalyst surface. The presence of NO, NH₃ and NO₂ retards hydrolysis leading to the appearance of isocyanate species on the surface.     

Generation, Characterization, and Impact of Mesopores in Zeolite Catalysts

Amongst the current developments in the field of hierarchical pore structures, the creation of mesopores in zeolite crystals is the most frequently employed way to combine micropores with mesopores in one material. In this review an overview is presented of the different approaches to generate and characterize mesopores in zeolite crystals and establish their impact on the catalytic action. Mesopores can be created via several routes from which steaming and acid leaching are the most frequently applied. Novel approaches using secondary carbon templates that are removed after synthesis have recently been launched. For the characterization of mesopores, nitrogen physisorption and electron microscopy are commonly used. More recently, it was shown that electron tomography, a form of three-dimensional transmission electron microscopy, is able to reveal the three-dimensional shape, size, and connectivity of the mesopores. The effect of the presence of mesopores for catalysis is demonstrated for several industrially applied processes that make use of zeolite catalysts: the cracking of heavy oil fractions over zeolite Y, the production of cumene and hydroisomerization of alkanes over mordenite, and synthesis of fine chemicals over Y, ZSM-5, and Beta. For these processes, the mesopores ensure an optimal accessibility and transport of reactants and products, while the zeolite micropores induce the preferred shape-selective properties.     

Elastic properties of adhesive polymers. II. Polymer films and bond lines by means of nanoindentation

Seven different polymers used frequently as adhesives and/or matrix polymers in wood, wood composites, and natural fiber‐reinforced composites were studied by uniaxial tensile tests and nanoindentation. It was shown that the elastic modulus, the hardness, the creep factor, and the elastic‐, plastic‐, and viscoelastic work of indentation of the seven different polymers is essentially the same regardless whether the polymers were tested in the form of pure films or in situ, i.e., in an adhesive bond line with spruce wood. An excellent correlation was found between the elastic modulus measured by tensile tests and the elastic modulus measured by nanoindentation. In spite of the good correlation, the elastic modulus measured by nanoindentation is significantly higher than the elastic modulus measured by tensile tests. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1234–1239, 2006     

Disposition and fate of cucurbitacin B in five species of diabroticites

Five species of diabroticites with different host-plant preferences produced an essentially identical array of metabolites when fed radiolabeled cucurbitacin B synthesized in vivo and purified fromCucurbita maxima Duchesne seedlings. All species excreted the bulk of the cucurbitacin (67,17-94.59% total dpm), permanently sequestered a small proportion of a cucurbitacin conjugate in the hemolymph (0.98–2.76%), and apportioned the remainder between the gut, the body, and the eggs (when present). Markedly different ratios between the excretory metabolites (i.e., polar vs. unmetabolized cuc) suggest thatDibrotica virgifera virgifera, a grass specialist, andAcalymma vittatum, a cucurbit specialist, have lower rates of metabolic alteration than the polyphagousD. undecimpunctata howardi, D. balteata, andD. cristata, which is associated with relict prairies. Mean life-spans ofD. balteata and D. v. virgifera and maleA. vittatum decreased significantly with continuous feeding onCucurbita fruit containing cucurbitacins (vs. fruit devoid of cucs). The longevity of femaleA. vittatum, however, was unaffected by the presence of cucurbitacins.     

Zertifikat zu Algorithmus 5

Ohne Zusammenfassung     

Aramid pulp treated with imidazolium ionic liquids as a filler in rigid polyurethane bio-foams

This article reports an aramid pulp (AP) treated with two ionic liquids (IL), namely 1-n-butyl-3-methylimidazolium chloride (C₄.Cl) and 1-carboxymethyl-3-methylimidazolium chloride (HO₂C), and its use as a filler in reinforced rigid polyurethane foams (RPUF). The RPUF were incorporated with the treated AP at three weight fractions (c.a. 0.1, 0.5, and 1.0 wt%) and were produced by the free rising method. The results showed that the studied IL promoted a better interaction between the AP and the RPUF system, which increased the overall reactivity, imparting a higher cell anisotropy. This also yielded a positive effect in mechanical properties and thermal stability of the RPUF. Compared to the neat RPUF, outstanding increases of approximately 50 and 20% were achieved in compressive modulus and strength, respectively. In all, the use of IL promoted increased compatibility between matrix and reinforcement, especially that HO₂C IL.     

Detection and evaluation of the fibers' deposition parameters during wet filament winding

Wet filament winding technology has been extensively used for the manufacture of rotationally symmetric parts made of fiber-reinforced plastics (FRP). As the design and modeling of FRP-parts require numerous assumptions, deviations between calculated and achieved mechanical properties are expected. One aspect that contributes to this discrepancy is the assumption of a homogeneous rectangular cross-section of the fiber-band. In this work, the fiber-band geometry in a wet-winding process of carbon fiber cylinders is analyzed. An Infrared-optical system for the detection of the fiber bandwidth and winding-angle is implemented. The influence of the winding speed and the resin temperature is analyzed. An image processing algorithm for the automatic measurement of the fiber's bandwidth and winding-angle is developed. Manual and adaptive gamma corrections are implemented to improve image quality. A parameter study for the suitable selection of image processing parameters is performed.     

3D FE simulation for temperature evolution in the selective laser sintering process

A thermal model of selective laser sintering (SLS) has been developed. The model allows for the non-linear behavior of thermal conductivity and of specific heat due to temperature changes and phase transformations. The temperature evolution and the formation of the sintered part are simulated by a 3D finite element analysis based on continuous media theory. It is shown that the effect of sintering has a strong influence on thermal evolution through changing the thermal properties of the material. The results of the model were experimentally tested and confirmed by temperature measurements.     

Thermodynamic calculation of the O-Ti system

The O-Ti binary system has been assessed to produce Gibbs energy parameters for the condensed phases and were evaluated as representations of thermodynamic models. The liquid phase was described in terms of an association model with one associate, the bcc, A 2; cph, A 3 and fcc, A 1 phases were described as interstitial solid solutions, and the O₂Ti, O₃Ti₅, O₃Ti₂, and OTi oxides were considered to be stoichiometric compounds. The thermodynamic parameters were optimized taking into account experimental phase diagram and thermodynamic values from the literature. The phase diagram and the thermodynamic properties were calculated and compared with experimental data.     

The hydrogen evolution reaction on iron corroded in dilute and very dilute solutions of sulfuric acid

Permeation transients for hydrogen, generated by corrosion of iron in dilute solutions of sulfuric acid, were recorded with an improved electrochemical permeation apparatus.The mechanism of the hydrogen evolution reactions is coupled discharge hydrogen recombination for all methods of hydrogen generation, low current anodic polarization, cathodic polarization and corrosion.The experimental hydrogen transient was compared with that predicted theoretically.It is concluded that electrochemical hydrogen permeation is a sensitive tool for investigating processes on metal surfaces which are of engineering importance.