Performance improvement in direct methanol fuel cell cathode using high mesoporous area catalyst support

Black Pearls 2000 (designated as BP- 2000) and Vulcan XC-72 (designated as XC-72) carbon blacks were chosen as supports to prepare 40 wt % (the targeted value) Pt/C catalysts by a modified polyol process. The carbon blacks were characterized by N-2 adsorption and Fourier tranform infrared spectroscopy. The prepared catalysts were characterized by inductively coupled plasma atomic emission spectroscopy, transmission electron microscopy, scanning electron microscopy (SEM), in situ cyclic voltammetry, and current-voltage curves. On BP- 2000, Pt nanoparticles were larger in size and more unevenly distributed than on XC-72. It was observed by SEM that the corresponding catalyst layer on BP- 2000 was thicker than that of XC-72 based catalyst at almost the identical catalyst loading. And the BP- 2000 supported catalyst gave a better single cell performance at high current densities. These results suggest that the performance improvement is due to the enhanced oxygen diffusion and water removal capability when BP- 2000 is used as cathode catalyst support. (C) 2004 The Electrochemical Society.

Study on the formation of beta-crystal during the crystallization process of polypropylene reactor granule

A notable amount of PP beta-crystal (30%, by X-ray diffraction pattern) has been found in the PP samples as polymerized at normal static isothermal crystallization conditions without using any extra nucleating agents. Existence of catalyst residues in the sample is decisive, which slows down the crystallization rate facilitating the formation of beta-form spherulites. Comparatively, high molecular weight PP favors the formation of beta-form spherulites, deducting from no beta-crystal detected in the degraded samples. Finally, high isotacticity is also required for obtaining qualitative beta-form spherulites, demonstrated by increased beta-crystal content after removal of weak crystalline fraction of the sample.

Investigation of catalyst effects in enantioselective copper- and rhodium-mediated transformations of α-diazocarbonyl compounds

This thesis describes the synthesis and reactivity of a series of α-diazocarbonyl compounds with particular emphasis on the use of copper-bis(oxazoline)-mediated enantioselective C–H insertion reactions leading to enantioenriched cyclopentanone derivatives. Through the use of additives, the enantioselectivity achieved with the copper catalysts for the first time reaches synthetically useful levels (up to 91% ee). Chapter one provides a comprehensive overview of enantioselective C–H insertions with α-diazocarbonyl compounds from the literature. The majority of reports in this section involve rhodium-catalysed systems with limited reports to date of asymmetric C–H insertion reactions in the presence of copper catalysts. Chapter two focuses on the synthesis and C–H insertion reactions of α-diazo-β-keto sulfones leading to α-sulfonyl cyclopentanones as the major product. Detailed investigation of the impact of substrate structure (both the sulfonyl substitutent and the substituent at the site of insertion), the copper source, ligand, counterion, additive and solvent was undertaken to provide an insight into the mechanistic basis for enantiocontrol in the synthetically powerful C–H insertion process and to enable optimisation of enantiocontrol and ligand design. Perhaps the most significant outcome of this work is the enhanced enantioselection achieved through use of additives, substantially improving the synthetic utility of the asymmetric C–H insertion process. In addition to the C–H insertion reaction, mechanistically interesting competing reaction pathways involving hydride transfer are observed. Chapter three reports the extension of the catalyst-additive systems, developed for C–H insertions with α-diazo-β-keto sulfones in chapter two, to C–H insertion in analogous α-diazo-β-keto phosphonate and α-diazo-β-keto ester systems. While similar patterns were seen in terms of ligand effects, the enantiopurities achieved for these reactions were lower than those in the cyclisations with analogous α-diazo-β-keto sulfones. Extension of this methodology to cyclopropanation and oxium ylide formation/[2,3]-sigmatropic rearrangement was also explored. Chapter four contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of chiral stationary phase HPLC analysis and X-ray crystallography are included in the appendix.

Two-stage no-wait scheduling models with setup and removal times separated

This paper studies two models of two-stage processing with no-wait in process. The first model is the two-machine flow shop, and the other is the assembly model. For both models we consider the problem of minimizing the makespan, provided that the setup and removal times are separated from the processing times. Each of these scheduling problems is reduced to the Traveling Salesman Problem (TSP). We show that, in general, the assembly problem is NP-hard in the strong sense. On the other hand, the two-machine flow shop problem reduces to the Gilmore-Gomory TSP, and is solvable in polynomial time. The same holds for the assembly problem under some reasonable assumptions. Using these and existing results, we provide a complete complexity classification of the relevant two-stage no-wait scheduling models.

Investigation of wall-slip effect on paste release characteristic in flip-chip stencil printing process

As the trend toward further miniaturisation of pocket and handheld consumer electronic products continues apace, the requirements for even smaller solder joints will continue. With further reductions in the size of solder joints, the reliability of solder joints will become more and more critical to the long-term performance of electronic products. Solder joints play an important role in electronics packaging, serving both as electrical interconnections between the components and the board, and as mechanical support for components. With world-wide legislation for the removal/reduction of lead and other hazardous materials from electrical and electronic products, the electronics manufacturing industry has been faced with an urgent search for new lead-free solder alloy systems and other solder alternatives. In order to achieve high volume, low cost production, the stencil printing process and subsequent wafer bumping of solder paste has become indispensable. There is wide agreement in industry that the paste printing process accounts for the majority of assembly defects, and most defects originate from poor understanding of the effect of printing process parameters on printing performance. The printing of ICAs and lead-free solder pastes through the very small stencil apertures required for flip chip applications was expected to result in increased stencil clogging and incomplete transfer of paste to the printed circuit pads. Paste release from the stencil apertures is dependent on the interaction between the solder paste, surface pad and aperture wall; including its shape. At these very narrow aperture sizes the paste rheology becomes crucial for consistent paste withdrawal because for smaller paste volumes surface tension effects become dominant over viscous flow. Successful aperture filling and release will greatly depend on the rheology of the paste material. Wall-slip plays an important role in characterising the flow behaviour of solder paste materials. The wall- slip arises due to the various attractive and repulsive forces acting between the solder particles and the walls of the measuring geometry. These interactions could lead to the presence of a thin solvent layer adjacent to the wall, which gives rise to slippage. The wall slip effect can play an important role in ensuring successful paste release after the printing process. The aim of this study was to investigate the influence of the paste microstructure on slip formation for the paste materials (lead-free solder paste and isotropic conductive adhesives). The effect of surface roughness on the paste viscosity was investigated. It was also found that altering the surface roughness of the parallel plate measuring geometry did not significantly eliminate wall slip as was expected. But results indicate that the use of a relatively rough surface helps to increase paste adhesion to the plates, inducing structural breakdown of the paste. Most importantly, the study also demonstrated on how the wall slip formation in the paste material could be utilised for understanding of the paste microstructure and its flow behaviour

The Development of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications.

This paper describes the development of a two-dimensional transient catalyst model. Although designed primarily for two-stroke direct injection engines, the model is also applicable to four-stroke lean burn and diesel applications. The first section describes the geometries, properties and chemical processes simulated by the model and discusses the limitations and assumptions applied. A review of the modeling techniques adopted by other researchers is also included. The mathematical relationships which are used to represent the system are then described, together with the finite volume method used in the computer program. The need for a two-dimensional approach is explained and the methods used to model effects such as flow and temperature distribution are presented. The problems associated with developing surface reaction rates are discussed in detail and compared with published research. Validation and calibration of the model is achieved by comparing predictions with measurements from a flow reactor. While an extensive validation process, involving detailed measurements of gas composition and thermal gradients, has been completed, the analysis is too detailed for publication here and is the subject of a separate technical paper.

Pilot-scale evaluation of the application of low pH-inducible polyphosphate accumulation to the biological removal of phosphate from wastewaters.

To investigate the possible biotechnological application of the phenomenon of low pH-inducible phosphate uptake and polyphosphate accumulation, previously reported using pure microbial cultures and under laboratory conditions, a 2000 L activated sludge pilot plant was constructed at a municipal sewage treatment works. When operated as a single-stage reactor this removed more than 60% of influent phosphate from primary settled sewage at a pH of 6.0, as opposed to approximately 30% at the typical operational pH for the works of 7.0-7.3-yet without any deleterious effect on other treatment parameters. At these pH values the phosphorus content of the sludge was, respectively, 4.2% and 2.0%. At pH 6.0 some 33.9% of sludge microbial cells were observed to contain polyphosphate inclusions; the corresponding value at pH 7.0 was 18.7%. Such a process may serve as a prototype for the development of alternative biological and chemical options for phosphate removal from wastewaters.