Identification of the state of palladium in various hydrogenation catalysts by XPS

Various commercial supported palladium hydrogenation catalysts were studied by XPS and treated at ambient pressure with hydrogen and air. Unused catalysts exhibit a significant fraction of divalent Pd (oxide) which is reduced by hydrogen treatment at room temperature. Exposure to air in systems with carbonate, alumina, silica or active carbon as support causes the formation of a solid solution of oxygen in Pd characterized by a Pd 3d chemical shift of ca. + 0.4 eV. The absolute binding energy of Pd depends strongly on the matrix, indicating a significant contribution of extra-atomic screening, which prevents a direct comparison of reference samples and supported catalysts. Using the oxidation of CO to CO₂ at 300 K as in situ chemical probe it was confirmed that Pd supported on carbonate, silica and alumina exists in the same metallic state which could be activated for the test reaction irrespective of the variation in XPS binding energies.     

Mechanical Behavior of Several Hybrid Ceramic-Matrix-Composite Laminates

Several different hybrid laminated composites comprised of alternating layers of dense ceramic sheets (either SiC or Si₃N₄) and fiber-reinforced ceramic-matrix-composite (CMC) layers (Nicalon fibers with either glass or glass-ceramic matrices) have been fabricated and characterized. The effects of the reinforcement architecture (unidirectional vs cross-ply) and the relative volume fractions of the phases on the tensile and flexural properties have been examined. Comparisons have been made with the properties of the constituent layers. Rudimentary models have been developed to describe the onset of cracking and for the minimum volume fraction of CMC required to develop multiple cracks and thus obtain a high failure strain.     

Branching-time logics with path relativisation

We define extensions of the full branching-time temporal logic CTL^? in which the path quantifiers are relativised by formal languages of infinite words, and consider its natural fragments obtained by extending the logics CTL and CTL⁺ in the same way. This yields a small and two-dimensional hierarchy of temporal logics parametrised by the class of languages used for the path restriction on one hand, and the use of temporal operators on the other. We motivate the study of such logics through two application scenarios: in abstraction and refinement they offer more precise means for the exclusion of spurious traces; and they may be useful in software synthesis where decidable logics without the finite model property are required. We study the relative expressive power of these logics as well as the complexities of their satisfiability and model-checking problems.     

A Complete and Highly Effective Mothproofing Agent Comprising a Pyrethroid and a Hexahydropyrimidine

Pyrethroids, considered as a general class of compounds, have been shown to provide effective protection from the larvae of the keratin-digesting insects Tineola bisselliella H., Tinea pellionella Linn., Hofmannophila pseudo-spretella Station and Attagenus piceus Oliv. The position regarding the susceptibility of the furniture carpet beetle to pyrethroids is less clear, however. It has been reported that both deltamethrin and permethrin are effective against Anthrenus flavipes Le Conte, whilst permethrin is also reported elsewhere to be effective against the same species. Results obtained in our laboratory, however, have indicated that pyrethroids may offer inadequate protection against Anthrenus vorax Waterh. [1, 2]. This latter species is identical to Anthrenus flavipes var. seminiveus Casey, a colour variety of Anthrenus flavipes Le Conte. The 1,3-disubstituted5-phenylcarbamoyl-2,4,6-trioxo- and 4,6-dioxo-2-thione-hexahydropyrimidine derivatives described in this paper exhibit a surprisingly high and selective toxicity to the Anthrenus species. Thus, a combination of an appropriate hexahydropyrimidine with a suitable pyrethroid, e.g. permethrin, provides complete control of a wide range of commonly encountered textile insect pests. The influence of substituents on the mothproofing activity is discussed.     

High-Strength Zirconia Fibers

Fine-grained polycrystalline zirconia fibers have been formed from an acetate precursor. The fibers contained a Y₂O₃ additive, which inhibited grain growth (grain size ≤0.5 μm) and allowed the tetragonal phase to be retained at room temperature. Fibers with diameters in the range 2 to 5 μm had strengths in the range 1.5 to 2.6 GPa.     

Syntheses and reactions of urethanes of cellobiose and cellulose-containing uretdione groups

Urethanes of cellobiose and cellulose-containing uretdione groups are synthesized by the reaction of aliphatic and aromatic diisocyanate uretdiones with the saccharides. The syntheses are performed as a heterogeneous reaction in dimethyl acetamide using dibutyl tin dilaurate as a catalyst, as well as a homogeneous reaction in dimethyl acetamide-lithium chloride. Thus, Semisynthetic prepolymers are formed that offer the reactivity of (blocked) isocyanate groups. To demonstrate their reactivity, ring opening of the uretdiones is performed by the addition of a secondary amine to yield the corresponding ureas.     

Effect of Zwitterionic Surfactants on Interparticle Forces, Rheology, and Particle Packing of Silicon Nitride Slurries

Phosphocholine (PC) zwitterionic surfactants, with different hydrocarbon chain lengths (C₆C₆PC to C₉C₉PC), were absorbed on the surface of silicon nitride near the isoelectric point (pH 6). Adsorption of the surfactants changed the lateral and normal surface forces, the rheology, and the consolidation behavior of the particles. The normal force between two silicon nitride surfaces as a function of separation and the lateral (friction) forces were measured using an atomic force microscope (AFM). These measurements indicated that surfactant adsorption reduced the magnitude of the long-range attractive van der Waals force and produced a repulsive short-range force. Although the adsorbed layers provided a barrier to particle contact, they could be ejected with a critical force that increased with the hydrocarbon chain length. The effect of an adsorbed layer on the viscosity and consolidation of slurries was also measured. The viscosity of all slurries decreased with increasing shear rate, indicative of attractive particle networks. The highest viscosity was observed for slurries formulated at the isoelectric point without added surfactant. Much lower viscosities were observed when the surfactant concentration was greater than the critical micelle concentration (cmc). A relative density of 0.46 was obtained via pressure filtration at 4 MPa without a surfactant, and between 0.46 to 0.59 (C₆C₆PC to C₉C₉PC, respectively) for surfactant concentrations greater than the cmc. Comparing force measurements with rheology and packing density provides a basis for discussing the role of interparticle forces in ceramic powder processing via colloidal routes.     

Produktionsintegrierter Umweltschutz – Verwertung von Reststoffen

Production-integrated environmental protection – Utilization of residues . Chemical plants as well as coal-fired powerstations utilize chemical reactions in order to produce materials or energy. Most of these reactions additionally produce gaseous, liquid, or solid residues. It is the main objective of production-integrated environmental protection to use these residues as suitable feedstocks in order to reduce environmental pollution and lower the consumption of raw materials. Several examples from the BASF Group will show how, by crossing the borders of the respective plant, reasonable solutions for material, or at least energetic, utilization of residues can be achieved. As a result of permanent efforts in production-integrated environmental protection over many years and despite increasing outputs the emissions of the chemical industry have been continuously reduced.     

13C n.m.r. study of raw materials for carbon black

¹³C n.m.r. spectroscopy has been applied to investigate a number of coal tar and petroleum-derived carbon black feedstocks. Application of the J-modulated spin echo technique is especially rewarding, as this method renders the quaternary carbons directly detectable. Thus the quality of carbon black feedstocks can additionally be gauged on the basis of the contents of quaternary carbons, which is a direct indication of the carbon yield in the carbon black production process.