Catalytic epoxidation of olefins in the presence of a vanadyl porphyrin complex

It was found that vanadyl porphyrin complexes synthesized from petroleum metal porphyrin concentrates stimulated epoxidation during the olefin oxygenation process. The yields of obtained oxiranes turned out to be 38–75%, depending on the olefin structure. An epoxidation mechanism that suggests the formation of a protonated dioxygen adduct as an intermediate during oxygenation of olefins in the presence of vanadyl porphyrin complexes was proposed. An analogy is drawn between the epoxide formation reaction upon the catalytic oxygenation of olefins and the Prilezhaev reaction.     

PETROLEUM MIGRATION, FAULTS AND OVERPRESSURE, PART I: CALIBRATING BASIN MODELLING USING PETROLEUM IN TRAPS — A REVIEW

This paper considers the principles of deciphering basin-scale hydrocarbon migration patterns using the geochemical information which is present in trapped petroleum. Petroleum accumulations in subsiding basins can be thought of as "data archives" within which stored information can help us to understand aspects of hydrocarbon formation and migration. This information can impart a time-resolved picture of hydrocarbon migration in a basin in response to processes associated with progressive burial, particularly in the context of the occurrence and periodic activity of faults.
This review, which includes a series of tentative models of migration-related processes in the extensional Halten Terrace area, offshore mid-Norway, illustrates how we can use information from the migrating mobile hydrocarbon phase to improve our knowledge of the static geological system. Of particular importance is the role of sub-seismic heterogeneities and faults in controlling migration processes. We focus on how the secondary migration process can be enhanced in a multi-source rock basin such as the Halten Terrace, thereby increasing prospectivity.     

MINERALOGICAL, PORE AND PETROPHYSICAL CHARACTERISTICS OF THE DEVONIAN JAUF SANDSTONE RESERVOIR, HAWIYAH FIELD, EASTERN SAUDI ARABIA

Throughout the subsurface of the Arabian Peninsula, the approximately 460ft thick, Devonian Jauf Formation generally consists of well-compacted, low-porosity sandstones and shales, but it also includes friable and highly porous sandstones which form significant gas and condensate reservoir intervals. The mineralogy and pore properties of these reservoir intervals at the Hawiyah field (part of the giant Ghawar structure) were studied by integrating petrographic data with petrophysical measurements of reservoir sandstone samples.
The reservoir sandstones are mainly composed of quartz arenites containing small amounts of altered potassium feldspar grains, authigenic illite and chlorite. Based on the pore types, which reflect the habits of the intergranular clays, three reservoir sandstone types have been defined: Type A, characterized by macroporosity; Type B, with microporosity; and Type C, with combined laminations of Types A and B. The dominance of pore-lining clay (as in Type A) or pore-filling clay (as in Type B) is the principal factor controlling the petrophysical properties of the samples. Types A and C sandstones contain macro pores, but irreducible water saturation is high (25 to 45%) compared to clean samples elsewhere, because of the presence of micropores associated with clay. In Type B sandstones the irreducible water saturation is commonly greater than 40% because all the pores spaces are in the microporosity range. The irreducible water saturation in Type B sandstones increases rapidly as porosity decreases. When porosity is less than 10%, the corresponding permeability is 0.2 mD, but no economic production can be expected because water saturation is as high as 100%. In the producing intervals, authigenic clays result in low electrical resistivity due to high water saturation; however, water-free gas is produced.     

PREDICTING THE TIMING AND CHARACTERISTICS OF PETROLEUM FORMATION USING TAR MATS AND PETROLEUM ASPHALTENES: A CASE STUDY FROM THE NORTHERN NORTH SEA

The Northern Viking Graben area in the Norwegian North Sea was studied in order to investigate the petroleum formation characteristics of the Upper Jurassic Draupne Formation. In this area, the organofacies of the Draupne Formation, and consequently its petroleum generation characteristics, show significant variations. These variations represent a major risk, particularly in the context of basin modelling studies. Therefore, tar‐mat asphaltenes, oil asphaltenes and source‐rock samples from this area were studied in order to evaluate the use of migrated asphaltenes from petroleum reservoirs and tar mats in basin modelling. The samples were studied using bulk kinetic analysis, open‐system pyrolysis‐gas chromatography and elemental analyses, and the results were integrated into a basin modelling study. The results from these different sample materials were compared both to each other and to natural petroleum, in order to assess their significance for future petroleum exploration activities. We show that in cumulative petroleum systems, the transformation characteristics of the asphaltenes incorporate those of the individual source rock intervals which have contributed to the relevant reservoir system. Thus, the petroleum formation window predicted by the use of asphaltene kinetics is broad, and covers the majority of the formation windows predicted from the individual source rock samples. In addition, the molecular characteristics of asphaltene‐derived hydrocarbons show that compositional characteristics, such as aromaticity, correspond more closely to natural oils than to the respective source‐rock products. Our results confirm that the heterogeneous nature of the Draupne Formation results in a significantly broader petroleum formation window than is conventionally assumed. We propose that oil and tar‐mat asphaltenes from related reservoirs represent macromolecules which account for this heterogeneity in the source rock, since they represent mixtures of charges from the different organofacies. One conclusion is that the use of oil and tar‐mat asphaltenes in kinetic studies and compositional predictions may significantly improve definitions of petroleum formation characteristics in basin modelling.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.     

Encapsulation and Ostwald Ripening of Au and Au–Cl Complex Nanostructures in Silica Shells

We report a general template strategy for rational fabrication of a new class of nanostructured materials consisting of multicore shell particles. Our approach is demonstrated by encapsulating Au or Pt nanoparticles in silica shells. Other superstructures of these hollow shells, like dimers, trimers, and tetramers can also be formed by nanoparticle‐mediated self‐assembly. We have also used the as‐prepared multicore Au–silica hollow particles to perform the first studies of Ostwald ripening in confined microspace, in which chloride was found to be an efficient mediating ligand. After treatment with aqua regia, Au–Cl complex is formed inside the shell, and is found to be very active under in situ transmission electron microscopy observations while confined in a microcell. This aspect of the work is expected to motivate further in situ studies of confined crystal growth.     

Moving the goal posts: a reply to Dawson and Piercey

Berkeley [Minds Machines 10 (2000) 1] described a methodology that showed the subsymbolic nature of an artificial neural network system that had been trained on a logic problem, originally described by Bechtel and Abrahamsen [Connectionism and the mind. Blackwells, Cambridge, MA, 1991]. It was also claimed in the conclusion of this paper that the evidence was suggestive that the network might, in fact, count as a symbolic system. Dawson and Piercey [Minds Machines 11 (2001) 197] took issue with this latter claim. They described some lesioning studies that they argued showed that Berkeley’s (2000) conclusions were premature. In this paper, these lesioning studies are replicated and it is shown that the effects that Dawson and Piercey rely upon for their argument are merely an artifact of a threshold function they chose to employ. When a threshold function much closer to that deployed in the original studies is used, the significant effects disappear.     

Robust nonlinear feedback–feedforward control of a coupled kinetic Monte Carlo–finite difference simulation

Robust nonlinear feedforward–feedback controllers are designed for a multiscale system that dynamically couples kinetic Monte Carlo (KMC) and finite difference (FD) simulation codes. The coupled codes simulate the copper electrodeposition process for manufacturing on-chip copper interconnects in electronic devices. The control objective is to regulate the current density subject to the condition that the steady-state fluctuation of the overpotential remains bounded within ±0.01 V. The controller designs incorporate a low-order stochastic model that captures the input–output behavior of the coupled KMC–FD code. The controllers achieve the objectives and the closed-loop responses implemented on the low-order model and the coupled KMC–FD code match well within stochastic variations. The nonlinear feedforward control reduces the rise time of the controller response while the feedback control ensures robustness in the presence of model uncertainty.     

Development of a simple microsystems membrane probe card

Presented here are details of the development of a novel membrane integrated circuit (IC) probe card structure based on microsystems technology. The device design allows probing of both solder bumps and pads. A self-limiting sensor was integrated to prolong device lifetime. Comparison with and discussion of the use of modelling is made. Possible enhancements to the probing structure are discussed to improve alignment and measurements. Also shown is data using our microsystems probe card to access a simple IC device. Our device has a contact resistance of less than 0.5 Ω for a force of 0.004 N. A method to implement our probing structure for commercial application and the potential developments which can be made to improve its ease of use are then discussed.