NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.     

The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene

The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002     

Engineering plastics from lignin. XVI. Starlike macromers with propylene oxide

Starlike macromers were prepared from hydroxypropyl organosolv lignin by reaction with propylene oxide, and they were analyzed by a combination of conventional analysis techniques. The average number of arms per macromer was controlled by partial capping with an alkoxy group; and the average length of arms by the degree of chain extension with propylene oxide. Analysis methods included treatment with hydriodic acid followed by gas chromatographic separation of alkyl iodides (HI/GC), UV spectroscopy, H-NMR spectroscopy, and thermal analysis. The results were consistent with a hypothetical pentameric model structure having between two and six radiating arms, each with a length of between 1 and 4 propylene oxide units. The UV method was best qualified to determine degree of chain extension, while HI/GC was best suited for analyzing average number of arms per macromer fragment. The synthesis and analysis of starlike macromers from lignin is viewed as an important stepping stone for the formulation of lignin-based engineering plastics and multiphase materials.     

Engineering plastics from lignin. XV. Polyurethane films from chain-extended hydroxypropyl lignin

A series of polyurethane (PU) films was prepared from chain-extended hydroxypropyl lignins (CEHPL). In appearance, these films ranged from brittle and dark brown to rubbery and bronze. The thermal, mechanical, and network properties of these PUs were investigated by DMTA and DSC analysis. All films exhibited single T_g's which varied between ?53° and 101°C, depending on lignin content. From swelling experiments, molecular weight between crosslinks (M _c) was determined and found to vary over 2.5 orders of magnitude. The M _c's were related to the change in T_g that accompanied network formation. Stress–strain experiments showed a variation in Young's modulus between 7 and 1300 MPa. Most of the variation in material properties was related to lignin content and to a lesser extent to diisocyanate type, hexamethylene diisocyanate, or toluene diisocyanate. The source of the CEHPL had no effect on the observed properties. From these results it was concluded that the properties of PUs can be controlled and engineered for a wide variety of practical uses.     

Propene and 1-Octene Hydroformylation with Silica-Supported, Ionic Liquid-Phase (SILP) Rh-Phosphine Catalysts in Continuous Fixed-Bed Mode

Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], on a silica support. The catalysts were active in continuous gas- and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h^-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.     

Bleaching of indigo-dyed denim fabric by electrochemical formation of hypohalogenites in situ

The use of hypochlorite, formed in situ by anodic oxidation of sodium chloride solution, for bleaching indigo-dyed denim has been studied at room temperature and at 50 °C. A direct relationship between the charge flow applied and the bleaching effect was observed. This enables consistent oxidative bleaching to be achieved by controlling the electrochemical process. The use of mixed anolytes containing small concentrations of bromide ions enhanced the bleaching effect considerably, even after lowering the temperature to room temperature. The molar concentration of bromide ions required was much lower than that of chloride in the anolyte.     

Toughness Optimization of SBR Elastomers – Use of Fracture Mechanics Methods for Characterization

Elastomer materials are used in a wide application range and subjected to different loading from which failure of the material results. Because this failure is caused by initiation and propagation of cracks, the application of fracture mechanics methods for the assessment of the material is obvious. A short summary of the methods of technical fracture mechanics including possibilities of determination of crack resistance curves is given. Vulcanizates on the basis of SBR 1500 with various sulfur and carbon black contents were investigated. For describing the crack initiation and crack propagation behavior, several fracture mechanics examination methods were applied. Tear‐analyzer results were used to assess the crack propagation behavior under fatigue‐like loading conditions. Furthermore, for the characterization of the crack resistance of the materials under impact‐like loading conditions, instrumented tensile‐impact tests were performed. To obtain information about the initiation and propagation of a stable crack, quasi‐static fracture mechanics tests were applied. The results of the several tests are discussed in dependence on sulfur and carbon black contents. We found a non‐monotonous behavior of the toughness as a function of carbon black loading. An explanation is given in connection with a percolation‐like transition in filler morphology on larger length scales.

Schematic crack propagation curve for characterizing the fatigue behavior of the vulcanizates recorded in a TFA test.     

Tailoring of Surfaces with Ultrathin Layers for Controlled Binding of Biopolymers and Adhesion and Guidance of Cells

Various strategies are described for the bio-functionalization of solid substrates by design of interfacial architectures. The first approach is based on the self-assembly process of long-chain thiol molecules from solution to a (noble) metal surface. If some of these building blocks carry a binding site (ligand) for proteins (receptors, antibodies, etc.) the metal surface can be tailored for maximum specific binding while simultaneously minimizing nonspecific adsorption. The second concept is based on polymers that are covalently attached to (oxide) surfaces. The preparation of these (end-) grafted functional polymers involves either the binding of preformed macromolecules to corresponding sites at the surface of the support or the recently introduced “grafting-from” method, by which an initiator molecule is first covalently bound to the surface and then activated — either by heat or light — in the presence of suitable monomer units such that a polymer chain grows from the solid/solution interface. Finally, the functionalization of patterned surfaces by peptide chains that mimic the binding domains of cell adhesion proteins is summarized. It is demonstrated that not only the selective adhesion of neuronal cells can then be controlled, but also their development with the outgrowth of dendrites and axons.     

Depletion of Grain-Boundary Phase and Elastic Creep Deformation Upon Ultra-Long Flexural Stress Rupture Experiments of NC-132 Silicon Nitride

A unique grain-boundary structure evolution was observed in two MgO-doped silicon nitride specimens (Norton, NC-132) that were tested in ultra-long flexure stress rupture experiments with an applied stress of 266 MPa and fractured at 14 941 and 17 376 h. Transmission electron microscopy showed that, although the starting material had a secondary glass phase both at multi-grain junctions and along grain boundaries, the tested specimens contained no residual glass phase. Concurrent with the elimination of the secondary glass phase, a continuous network of cracked grain boundaries was observed after long-term flexure testing consistent with the concept of elastic creep. It is, therefore, concluded that at ultra-long annealing times, this material is affected by creep deformation via microcrack nucleation and growth due to the depletion of the amorphous siliceous grain-boundary phase, which is seen as a truly transient, fugitive secondary phase.