A DFT Study of Ethylene Hydrogenation Reaction Mechanisms on Ni13 Nanocluster

Metal nanoclusters can potentially exhibit high catalytic activity and selectivity due to not only a high number of exposed surface atoms but also active sites with different coordination numbers as compared to bulk catalyst surface. In this study ethylene hydrogenation was used as a model reaction in an effort to elaborate reactivity of small Ni nanoclusters and the ethylene hydrogenation reaction mechanism. Two mechanistic pathways; representing Eley–Rideal and Horiuti–Polanyi type of mechanism for ethylene hydrogenation reaction are studied. It has been concluded that Horiuti–Polanyi type is more favorable when compared to Eley–Rideal type.     

A comparison of different activated carbon performances on catalytic ozonation of a model azo reactive dye

The objective of this study is to compare the performances of catalytic ozonation processes of two activated carbons prepared from olive stone (ACOS) and apricot stone (ACAS) with commercial ones (granular activated carbon-GAC and powder activated carbon-PAC) in degradation of reactive azo dye (Reactive Red 195). The optimum conditions (solution pH and amount of catalyst) were investigated by using absorbencies at 532, 220 and 280 nm wavelengths. Pore properties of the activated carbon (AC) such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption. The highest BET surface area carbon (1,275 m(2)/g) was obtained from ACOS with a particle size of 2.29 nm. After 2 min of catalytic ozonation, decolorization performances of ACOS and ACAS (90.4 and 91.3%, respectively) were better than that of GAC and PAC (84.6 and 81.2%, respectively). Experimental results showed that production of porous ACs with high surface area from olive and apricot stones is feasible in Turkey.     

Effect of surface preparation on the durability of NiCoCrAlY coatings for oxidation protection and bond coats for thermal barrier coatings

A principal concern with alumina‐forming coatings for high‐temperature oxidation protection and bond coats (BCs) for ceramic thermal barrier coatings (TBCs) used in gas turbines is the spalling of the alumina scales during service. This paper describes the effects of BC surface preparation on the durability of NiCoCrAlY coatings exposed under thermal cycling conditions. State‐of‐the‐art TBC systems deposited by electron beam physical vapor deposition (EBPVD) with NiCoCrAlY overlay BCs were found to fail as the result of defects which included transient oxides, defects in the BC surface, defects in the as‐deposited microstructure of the TBC, and excessive oxidation of reactive element additions. In some instances, the TBC life was greatly extended by surface treatments, such as fine polishing. The oxidation behavior of NiCoCrAlY coatings, absent a TBC, was found to be sensitive to Y content and to surface preparation. This paper describes how a variety of surface treatments affected coating lives and failure mechanisms.     

Adsorption kinetics of malachite green onto activated carbon prepared from Tunçbilek lignite

Adsorbent (T₃K618) has been prepared from Tunçbilek lignite by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N₂ adsorption isotherm. The N₂ adsorption isotherm of malachite green on T₃K618 is type I. The BET surface area of the adsorbent which was primarily contributed by micropores was determined 1000 m²/g. T₃K618 was used to adsorb malachite green (MG) from an aqueous solution in a batch reactor. The effects of initial dye concentration, agitation time, initial pH and adsorption temperature have been studied. It was also found that the adsorption isotherm followed both Freundlich and Dubinin–Radushkevich models. However, the Freundlich gave a better fit to all adsorption isotherms than the Dubinin–Radushkevich. The kinetics of adsorption of MG has been tested using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. Results show that the adsorption of MG from aqueous solution onto micropores T₃K618 proceeds according to the pseudo-second-order model. The intraparticle diffusion of MG molecules within the carbon particles was identified to be the rate-limiting step. The adsorption of the MG was endothermic (ΔH° = 6.55–62.37 kJ/mol) and was accompanied by an increase in entropy (ΔS° = 74–223 J/mol K) and a decrease in mean value of Gibbs energy (ΔG° = −6.48 to −10.32 kJ/mol) in the temperature range of 20–50 °C.     

Radiation-induced and electroinitiated polymerisation of 1, 2-Epoxy-4-epoxyethylcyclohexane

Liquid state radiation-induced and electroinitiated cationic polymerisation of 1,2-epoxy-4-epoxyethylcyclohexane (EECH) have been investigated. Soluble and cross-linked polymers were obtained during the radiation-induced polymerisation of EECH, depending upon the radiation dose. Electroinitiated polymerisation of the monomer yielded cross-linked polymers on the surface of the anode. The expected polyether structure was observed for i.r. data. The polymerisation propagates via opening of the epoxy rings as indicated by n.m.r. spectra. X-Ray analyses showed that the products obtained by both methods are amorphous.     

Teleoperated 3-D Force Feedback From the Nanoscale With an Atomic Force Microscope

In this study, 3-D experimental teleoperated force feedback during contact with nanoscale surfaces is demonstrated using an atomic force microscope (AFM) on the slave side and a haptic device on the master side. To achieve 3-D force feedback, coupling between one of the horizontal forces and the vertical force is a crucial bottleneck. To solve this coupling issue, a novel force decoupling algorithm is proposed. This algorithm uses local surface slopes, an empirical friction force model, and the haptic device motion angle projected onto the surface to estimate the friction value during experiments. With this estimation, it is possible to decouple the three orthogonal forces acting on the tip of the AFM cantilever. Moreover, using an adaptive observer, parameters of the friction model can be changed online, removing the necessity to calibrate the friction model initially. Finally, a modified passivity-based bilateral control is used to reflect the scaled nanoscale forces to the master side and the operator. The performance of the system is demonstrated on experimental results for flat and non-flat, and hard and soft surfaces.      

A serial CT scan and MRI verification of diffuse cerebrospinal gliomatosis: a case report with stereotactic diagnosis and radiological confirmation

The purpose of this work was to study H2/CO2-utilizing acetogenic population in the colons of non-methane-producing individuals harboring low numbers of methanogenic archaea. Among the 50 H2-consuming acetogenic strains isolated from four fecal samples and an in vitro semi-continuous culture enrichment, with H2/CO2 as sole energy source, 20 were chosen for further studies. All isolates were Gram-positive strict anaerobes. Different morphological types were identified, providing evidence of generic diversity. All acetogenic strains characterized used H2/CO2 to form acetate as the sole metabolite, following the stoichiometric equation of reductive acetogenesis. These bacteria were also able to use a variety of organic compounds for growth. The major end product of glucose fermentation was acetate, except for strains of cocci that mainly produced lactate. Yeast extract was not necessary, but was stimulatory for growth and acetogenesis from H2/CO2.     

Fuzzy AHP approach for supplier selection in a washing machine company

Supplier selection process has gained importance recently, since the cost of raw materials and component parts constitutes the main cost of a product and most of the firms have to spend considerable amount of their revenues on purchasing. Supplier selection is one of the most important decision making problems including both qualitative and quantitative factors to identify suppliers with the highest potential for meeting a firm’s needs consistently and at an acceptable cost. In this study, supplier selection problem of a well-known washing machine company in Turkey is investigated and a fuzzy analytic hierarchy process based methodology is used to select the best supplier firm providing the most customer satisfaction for the criteria determined. After the main attributes and sub-attributes for supplier selection are defined to design the hierarchy structure, the weights of them and alternatives are calculated using fuzzy analytic hierarchy process approach. The supplier with the highest priority weight is selected as the best supplier. Macros in MS Excel are written to calculate the priority weights of the alternatives based on the questionnaire forms used to facilitate comparisons of main attributes, sub-attributes and alternatives.     

Modelling and performance evaluation of explosive storage policies in internet fulfilment warehouses

Internet Fulfilment Warehouses (IFWs) are designed to exclusively process online retail orders. An observational study reveals that IFW operating and design attributes are significantly different from traditional warehouses in their storage and fulfilment policies. Specifically, we identify six IFW differentiators: explosive storage, very large number of beehive storage locations, bins with commingled SKUs, immediate fulfilment, short picking routes with single unit picks and high transactions with total digital control. Explosive storage of incoming bulk allows for faster fulfilment of customer orders often within a few hours. A new IFW control model is developed. This describes the associated receiving and fulfilment flows. Two decision algorithms for generating (i) a stocking list and (ii) an order picking list are presented. A simulation model was built to evaluate the fulfilment performance of the explosive policy. Experimental runs on a problem with 400 SKUs, 3240 bins and 22,000 customer orders over nine days are reported. Results show that increasing levels of explosion reduce the linear fulfilment time by as much as 16%, confirming the IFW storage policy is advantageous. The results also show that fulfilment time behaviour is convex as a function of the maximum number of stops allowed by the picking algorithm parameter.     

The effect of additives and drawing temperature on gamma- or ultraviolet-radiation induced oxidative degradation of drawn high density polyethylene

The effects of drawing temperature and the presence of various types of additives on gamma and ultraviolet radiation induced oxidative degradation of high density polyethylene have been studied. Uniaxial drawing of the polymer was conducted at 60, 80, and 100°C. The additives were an antioxidant, light stabilizer, and carbon black, used in various combinations, Oxidative degradation was followed from carbonyl formation by IR spectroscopy. It is found that at a given draw ratio, the oxidative degradation is retarded when the drawing temperature is increased, irrespective of whether or not the polymer contains any additives in any combination. This is due to the decrease of the surface and/or bulk microcracks formed during the drawing process at high temperature. Carbon black/antioxidant mixtures were shown to be antagonistic, while a carbon black/light stabilizer mixture resulted in a synergetic effect in drawn or undrawn materials.