Soot oxidation catalyzed by a Cu/K/Mo/Cl catalyst: evaluation of the chemistry and performance of the catalyst

Several non-supported oxidic compounds potentially present in a Cu/K/Mo/Cl catalyst (copper molybdates, potassium molybdates, and a mixed copper-potassium molybdate (K₂Cu₂(MoO₄)₃)) have been tested individually on their activity in the oxidation of a model soot (Printex-U, which non-catalytically oxidizes at 875 K). These oxidic compounds are active between 665 and 720 K, but only after establishment of ‘tight contact’ between the catalyst and soot in a ball mill. Without the ball mill procedure (‘loose contact’) these oxides are less active (the soot oxidation temperature is shifted to about 790 K), while a ZrO₂ supported Cu/K/Mo/Cl catalyst still shows a high activity around 670 K. Hence, the ‘loose contact’ activity of the supported Cu/K/Mo/Cl catalyst is not explained by the presence of an active oxidic compound. DRIFT and XRD analyses have shown that addition of KCl to CuMoO₄ (two compounds present within the Cu/K/Mo/Cl catalysts) followed by calcination at 950 K in air, eventually results in the formation of a mixed potassium-copper molybdate. Simultaneously several volatile copper, potassium and chlorine containing compounds (e.g. K₂CuCl₄) are formed. These copper and chlorine containing compounds possess a high ‘loose contact’ soot oxidation activity between 600 and 690 K. A catalytic cycle, involving Cu₂OCl₂, is proposed to explain the high ‘loose contact’ activity of copper chlorides and supported Cu/K/Mo/Cl catalysts. The activity of the latter catalyst will be maintained as long as Cu₂OCl₂ can be reformed by reaction of copper molybdates with KCl, which serves as a chlorine supplier.     

Localized measurement of optical attenuation coefficients of atherosclerotic plaque constituents by quantitative optical coherence tomography

Optical coherence tomography (OCT) is a novel, high-resolution diagnostic tool that is capable of imaging the arterial wall and plaques. The differentiation between different types of atherosclerotic plaque is based on qualitative differences in gray levels and structural appearance. We hypothesize that a quantitative data analysis of the OCT signal allows measurement of light attenuation by the local tissue components, which can facilitate quantitative spatial discrimination between plaque constituents. High-resolution OCT images (at 800 nm) of human atherosclerotic arterial segments obtained at autopsy were histologically validated. Using a new, simple analysis algorithm, which incorporates the confocal properties of the OCT system, the light attenuation coefficients for these constituents were determined: for diffuse intimal thickening (5.5 +/- 1.2 mm(-1)) and lipid-rich regions (3.2 +/- 1.1 mm(-1)), the attenuation differed significantly from media (9.9 +/- 1.8 mm(-1)), calcifications (11.1 +/- 4.9 mm(-1) ) and thrombi (11.2 +/- 2.3 mm(-1)) (p < 0.01). These proof of principle studies show that simple quantitative analysis of the OCT signals allows spatial determination of the intrinsic optical attenuation coefficient of atherosclerotic tissue components within regions of interest. Combining morphological imaging by OCT with the observed differences in optical attenuation coefficients of the various regions may enhance discrimination between various plaque types.     

Generality and legibility in mobile manipulation

This article investigates methods for achieving more general manipulation capabilities for mobile manipulation platforms, which produce legible behavior in human living environments. To achieve generality and legibility, we combine two control mechanisms. First of all, experience- and observation-based learning of skills is applied to routine tasks, so that the repetitive and stereotypical character of everyday activity is exploited. Second, we use planning, reasoning, and search for novel tasks which have no stereotypical solution. We apply these ideas to the learning and use of action-related places, to the model-based visual recognition and localization of objects, and the learning and application of reaching strategies and motions from humans. We demonstrate the integration of these mechanisms into a single low-level control system for autonomous manipulation platforms.     

Strong overtones and combination bands in ultraviolet resonance Raman spectroscopy

Ultraviolet resonance Raman spectroscopy is carried out using a continuous wave frequency-doubled argon ion laser operated at 229, 244, and 257 nm in order to characterize the overtones and combination bands for several classes of organic compounds in liquid solutions. Contrary to what is generally anticipated, for molecules such as pyrene and anthracene, strong overtones and combination bands can show up; it is demonstrated that their intensity depends critically on the applied laser wavelength. If the excitation wavelength corresponds with a purely electronic transition--this applies to a good approximation for 244-nm excitation in the case of pyrene and for 257-nm excitation in the case of anthracene--mostly fundamental vibrations (up to 1700 cm(-1)) are observed. Overtones and combination bands are detected but are rather weak. However, if the laser overlaps with the vibronic region--as holds for 229- and 257-nm excitation for pyrene and 244-nm excitation for anthracene--very strong bands are found in the region 1700-3400 cm(-1). As illustrated for pyrene at 257 nm, all these bands can be assigned to first overtones or binary combinations of fundamental vibrations. Their intensity distribution can roughly be simulated by multiplying the relative intensities of the fundamental bands. Significant bands can also be found in the region 3400-5000 cm(-1), corresponding with second overtones and ternary combinations. It is shown that these findings are not restricted to planar and rigid molecules with high symmetry. Substituted pyrenes exhibit similar effects, and relatively strong overtones are also observed for adenosine monophosphate and for abietic acid. The reasons for these observations are discussed, as well as the potential applicability for analytical purposes.     

Grip to the Colon by Means of Macroscopic Adhesion-Controlled Friction

Manipulating friction without applying high normal forces is important for an intestine inspection and intervention device in order to eliminate the risk of tissue damage. One possible solution is to generate friction by means of adhesive forces. The adhesive forces should be high to offer sufficient grip without needing high normal forces. The generated friction is then called adhesion-controlled and depends on the size of the area in contact. Adhesion-controlled friction is well known to be dominant at microscopic and molecular levels. According to this paper, adhesion-controlled friction can be applicable on the macroscopic scale as well and, more specifically, within a range of forces in which friction is usually considered to be load-controlled. The intestine inspection and intervention device manipulates the friction with the colonic wall by means of mucoadhesive films. In this way, grip with high static friction is achieved without the need to apply high normal forces and friction is altered by changing the size of the area of the mucoadhesive film. Friction theories on different scales are revisited and considered in order to understand the dominant phenomena and the principles associated with this macroscopic adhesion-controlled friction.     

The pressure drop experiment to determine slug lengths in multiphase monoliths

The length of the liquid slugs, that separate the elongated bubbles in Taylor flow, is an important parameter for mass transfer, flow stability and pressure drop in capillary microchannels. In this work, pressure drop measurements are used to determine the length of slug in Taylor flow in downflow monoliths. The method is sensitive if the slugs are relatively short, less than 10 times the channel diameter. The pressure drop measurements are a cheap and fast alternative to tomographic or electric methods. Experiments using different distributors indicate that the slug length varies significantly with changes in the hydrodynamics in the feed section of the monoliths. Slug length correlations that are based on parameters inside the channels can therefore not safely be used for a different setup. As a result, the slug length should be measured in each experimental setup, which makes a inexpensive and robust method to do so very welcome.     

CO2 gasification of carbon catalysed by alkali metals: Reactivity and mechanism

A systematic study of the catalytic activity of alkali metal carbonates on the CO₂ gasification of activated carbon revealed the following order: Li < Na < K < Rb < Cs. Outgassing in an inert gas results in a pronounced activity decrease for Cs, whereas the other alkali metals show a slight increase. The activated carbon itself is unaffected. Apparent activation energies for the CO₂ gasification are also changed by outgassing and decrease from Li to Cs. Upon outgassing of the samples, CO₂ and CO are released in five distinguishable temperature regions, arising from decomposition of surface complexes and carbonate-like species, gasification phenomena and reduction of oxidic species. Outgassing patterns of all alkali metals are quite similar. During alkali-metal-catalysed gasification in CO₂ two types of oxidic species are present: surface bonded -OM species of high stability and oxidic species having less interaction with the carbon surface.     

CARBON-BASED MONOLITHIC STRUCTURES

The interest in using monolithic structures for chemical conversion and adsorption processes is increasing. A relatively new type of monolith is based on carbon. The combined favorable properties of carbon and monolithic structures create a support with great potential in catalytic and adsorption processes. This review describes the current state of the art of carbon-based monolithic structures with respect to preparation, obtained support properties, and application in catalytic and adsorption processes, and it evaluates upcoming application areas.