Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

Managing Fashion Goods Inventories: Dynamic Recourse for Retailers with Outlet Stores

The proliferation of both online and bricks and mortar outlet stores underscores the observation that secondary markets are readily accessible to retailers of short-life-cycle products. These secondary markets provide recourse channels for retailers to sell excess inventory of out-of-favor items at reduced prices when overstocking occurs in a primary market. We study the problem of determining when a retailer should terminate its primary selling season by selling remaining inventory on a secondary market. The retailer has a single opportunity to procure prior to a primary selling season consisting of multiple periods. Demand in each period is random, but correlated. At the end of each period, any remaining inventory incurs a holding cost. Then, based upon the current level of inventory and the cumulative demand-to-date, the retailer decides either to terminate the primary selling season by selling all or part of the remaining inventory on a secondary market, or to extend the current primary selling season by another period. We develop structural properties of the optimal policy for determining when to terminate the primary selling season, and we develop corresponding implications for procurement.     

State of polarization changes: Classification and measurement

We propose a standardization procedure that provides a convenient, quantitative and reproducible laboratory-based method for measuring the state of polarization (SOP) fluctuations produced by polarization varying devices. This method is based on the SOP distributions generated by commercial polarization scramblers. We show that these devices generate distributions of the maximum change of the SOP (in a given sample time) that follow Rayleigh statistics, which scale linearly with scrambling frequency and the sample time. We use this procedure to measure the SOP fluctuations in a short length of coiled fiber subject to mechanical perturbations.     

Oligo(ethylene oxide) side‐chain steric screening effects on conductimetric properties of grafted poly(4‐vinylpyridinium) salts in aqueous solutions

A set of poly[N‐oligo(ethylene oxide)yl 4‐vinylpyridinium tosylate] (P4VOEOOTs) has been prepared by spontaneous polymerization of 4‐vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on every backbone pyridinic moiety. The P4VP15Ts, P4VP164Ts, P4VP350Ts and P4VP750Ts aqueous solution conductivities were determined in the concentration range from 6 × 10^?4 to 10^?2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits typical polyelectrolyte behaviour. The polyelectrolyte mobility was found to be dependent on the oligo(ethylene oxide) (OEO) side‐chain length. Manning's rod‐like model fails to describe these results. A simple steric effect is proposed to explain the influence of the OEO length. Copyright © 2003 Society of Chemical Industry     

Effects of surface charge, micro-bubble size and particle size on removal efficiency of electro-flotation.

Flotation is a water treatment alternative to sedimentation, and uses small bubbles to remove low-density particles from potable water and wastewater. The effect of zeta potential, bubble size and particle size on removal efficiency of the electro-flotation process was investigated because previous model-simulations indicated that these attributes are critical for high collision efficiency between micro-bubbles and particles. Solutions containing Al3+ as the metal ion were subjected to various conditions. The zeta potentials of bubbles and particles were similar under identical conditions, and their charges were influenced by metal ion concentration and pH. Maximum removal efficiency was 98 and 12% in the presence and absence of flocculation, respectively. Removal efficiency was higher when particle size was similar to bubble size. These results agree with modelling simulations and indicate that collision efficiency is greater when the zeta potential of one is negative and that of the other is positive and when their sizes are similar.     

Untersuchung der Verteilung und Intensität filamentierter Barrierenplasmen für die Behandlung von Oberflächen

The application of barrier discharges at atmospheric pressure in air expands on the market of plasma technology, because it is an ecological and cost‐effective alternative to other processes of surface treatment. These plasmas usually consist of a multitude of spatially and temporally localized filaments, whose distribution should be as even as possible for homogeneous treatment. This holds especially for the plasma treatment of sensitive goods such as wool or other textiles. In equipment for continuous pass of material the barrier arrangements often consist of a system cylinder – cylinder or cylinder – plane, whereby the gap width changes locally. Space distribution and intensity of filaments has been investigated by means of short‐time photography and spatially resolved measurement of current distribution and energy distribution derived from it. The local dependency found can be explained by means of a capacitive equivalent circuit.     

On the linear correlation between microhardness and mechanical properties in polar polymers and blends

The tensile elastic modulus (E), yield stress (σ_Y) and microhardness (MH) of neat and binary and ternary blends of glassy semicrystalline ethylene–vinyl alcohol copolymer (EVOH), a glassy amorphous polyamide and a semicrystalline nylon‐containing ionomer covering a broad range of properties were examined. The tests were carried out on dry and water‐equilibrated samples to produce stiffer and softer materials, respectively. From the results, more accurate linear correlations were found to describe adequately the microhardness, modulus and yield stress of these strongly self‐associated polymers through hydrogen bonding. Copyright © 2003 Society of Chemical Industry     

Co-digestion of manure and biowaste according to the EC animal by-products regulation and Finnish national regulations.

The objective of this study was to compare methane production and characteristics of digested material in anaerobic digestion concepts according to the Animal By-Products Regulation (ABP-Regulation) of the EC (hygienisation of biowaste for 1 hour at 70 degrees C, particle size < 12 mm) and Finnish national regulations (treatment temperature 55 degrees C, feeding interval 24 h, hydraulic retention time (HRT) 20 d, particle size < 40 mm) and with small variations in treatment methods for treating manure and biowaste. Moreover, the survival of three different salmonella bacteria in these processes was studied. Hygienisation of biowaste prior to digestion at 35 degrees C enhanced methane production by 14-18% compared to similar treatment without hygienisation. The differences in treatment temperature, HRT and hygienisation of biowaste prior to digestion did not significantly affect the characteristics of digested material. The concepts according to the ABP-Regulation and Finnish national regulations were effective in destroying salmonella bacteria to an undetectable level.     

Effect of surface waxes on the persistence of chlorpyrifos-methyl in apples, strawberries and grapefruits

The effects of the cuticle and epicuticular waxes of grapefruit, strawberry and apple on the photodegradation and penetration of chlorpyrifos-methyl were studied. Photodegradation experiments were conducted by exposing the insecticide to the light of a xenon lamp in the presence of a film of wax extracted from the fruit surface. The half-life of chlorpyrifos-methyl irradiated in absence of waxes was 9.6 min. The half-lives of pesticide irradiated in the presence of wax extracts of apple, grapefruit and strawberry were 83, 34 and 26 min, respectively. In penetration studies, fruit with and without wax layers were treated with an aqueous suspension of pesticide. The penetration of the pesticide from the cuticle to the pulp was measured after 24 h. Samples without wax contained a higher total amount of insecticide than those with wax. No pesticide was detected in samples of apple and grapefruit pulp. Residues were detected in all fractions of strawberry. The waxes and cuticle appear to have some effect on the photodegradation and penetration of chlorpyrifos-methyl in fruit samples.     

Catalytic aminolysis of epoxide by alumina prepared from amine-protected Al precursor

The catalytic activities of alumina prepared from an Al alkoxide-amine adduct monomer for the reaction of cyclopentene oxide with piperidine was determined after various pretreatments, including calcination and exposure to moisture. They were compared with the activity of alumina prepared by the conventional hydrolysis method. It was found that the as-prepared sample from the alkoxide-amine monomer preparation was five times more active than a conventional preparation, suggesting that it has a higher density of surface Lewis acid sites. However, its activity was much more severely suppressed by exposure to moisture.