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.     

醇解技术在制备皮革加脂剂方面的研究进展

本文介绍了醇解反应的动力学、影响醇解反应收率的因素以及醇解反应在合成加脂剂方面的应用。     

Rheological cure characterization of phosphazene–triazine polymers

Cyclomatrix phosphazene–triazine network polymers were synthesized by co‐curing a blend of tris(2‐allylphenoxy), triphenoxy cyclotriphosphazene (TAP), and tris(2‐allylphenoxy) s‐triazine (TAT) with bis(4‐maleimido phenyl) methane (BMM). The co‐curing of the three‐component resin was investigated by dynamic mechanical analysis using rheometry. The cure kinetics of the Diels–Alder step was studied by examining the evolution of the rheological parameters, such as storage modulus (G′), loss modulus (G″), and complex viscosity (η*), for resins of varying compositions at different temperatures. The curing conformed to an overall second‐order phenomenological equation, taking into account a self‐acceleration effect. The kinetic parameters were evaluated by multiple‐regression analysis. The absence of a definite trend in the cure process with blend composition ratio was attributed to the occurrence of a multitude of competitive reactions whose relative rates depend on the reactant ratio and the concentration of the products formed from the initial phase of reaction. The cure was accelerated by temperature for a given composition, whereas the self‐acceleration became less prominent at higher temperature. Gelation was accelerated by temperature. The gel conversion decreased with increase in maleimide concentration and, for a given composition, it was independent of the cure temperature. The activation energy for the initial reaction and the crosslinking process were estimated for a composition with a maleimide‐to‐allyl ratio of 2 : 1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 908–914, 2003     

Estimating crystallinity in high density polyethylene fibers using online Raman spectroscopy

Online Raman spectra, obtained at different points along the spin line during pilot‐scale nonisothermal melt spinning of high density polyethylene (HDPE) fibers, are presented for the first time. The fraction of the crystalline phase corresponding to each spectrum was determined from the normalized integrated intensity of the 1418 cm^?1 Raman band. It is well established that this band represents the orthorhombic crystalline phase in polyethylene. The estimates of percent crystallinity obtained from decomposition of the Raman spectrum were compared with the percent crystallinity from differential scanning calorimetry (DSC) measurements. It is concluded that online Raman spectroscopy can be successfully used to monitor the development of crystallinity in HDPE fibers as a function of distance from the spinneret. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 545–549, 2003     

Structural changes in isothermal crystallization process of polyoxymethylene investigated by time-resolved FTIR, SAXS and WAXS measurements

Structural evolution in the isothermal crystallization process of polyoxymethylene from the molten state has been investigated by carrying out the time-resolved measurements of infrared spectra and synchrotron small angle X-ray scattering (SAXS) and wide angle X-ray scattering. In case of isothermal crystallization at 130 °C, for example, the infrared bands intrinsic of folded chain crystal (FCC) morphology appeared at first, and then the bands of extended chain crystal (ECC) morphology were detected with time delay of ca. 150 s. In the SAXS experiment at 130 °C, the lamellar stacking structure of the long period of ca. 15 nm was observed at first, which changed rapidly to ca. 12 nm in a short time. The SAXS peak with the long period of ca. 6 nm started to appear with a time delay of ca. 150 s after the initial lamellae appeared and coexisted with the initially-observed 12 nm peak. Judging from the timing to detect these characteristic infrared and SAXS signals, a good correspondence was found to exist between the stacked lamellar structure of 12 nm long period and FCC morphology and between the structure of 6 nm long period and ECC morphology. The quantitative analysis was made for the SAXS data on the basis of the lamellar insertion model combined with the paracrystalline theory of the second-kind of disorder. The following structural evolution was deduced from all these results. Immediately after the temperature jump from the melt to 130 °C, the stacked lamellar structure of FCC morphology was generated at first. New lamellae were formed from the amorphous region in between the originally-existing lamellae about 150 s later, where the random chain segments bridging the adjacent lamellae were extended to form the taut tie chains, giving infrared bands of ECC morphology. This inserted lamellar structure of 6 nm long period coexisted at a population of ca. 6% with the initially-formed lamellar stacking structure of 12 nm long period. When the experiment was made at 150 °C, only the formation of stacked lamellar structure of FCC morphology was observed and the insertion of new lamella did not occur.     

化学复合镀层激光处理研究

研究了激光处理对Ni-P -SiC化学复合镀层的影响。借助于扫描电镜、能谱仪、X射线衍射、显微硬度计等设备对激光处理后复合镀层的表面形貌、组织结构及性能进行了综合分析。结果表明 ,对复合镀层进行激光处理可以获得与炉内加热同样的镀层硬度 ,且当激光功率 4 0 0W ,扫描速度 1.5m /min时 ,镀层硬度高于炉内加热的硬度     

A closed loop exponential feeding law: Invariance and global stability analysis

This article addresses the computation of invariant control laws [A. Fradkov, I. Miroshnik, V. Nikiforov, Nonlinear and Adaptive Control of Complex Systems, Kluwer, 1999] for fed-batch fermenters represented by two standard models. It will be shown how to derive partial state feedbacks that, assuming ideal conditions and perfect model, keep the specific growth rate μ constant provided the initial conditions are adequate. The invariant control law is the closed loop version of the exponential feeding already suggested in several references as shown later. The paper presents an analysis of invariance and a study of global stability within the framework of partial stability. That is, stability with respect to some of the state variables. This enables us to treat the case with Haldane-like or non-monotonous kinetics.     

Phase behavior,density, and crystallization of polyethylene in n‐pentane and in n‐pentane/CO2 at high pressures

The phase behavior and volumetric properties of polyethylene (PE) in solutions of n‐pentane and n‐pentane/CO₂ were studied in a temperature (T) range of 370–440 K at pressures up to 60 MPa. Measurements were conducted with a variable‐volume view‐cell system equipped with optical sensors to monitor the changes in the transmitted light intensity as the P or the T of the system was changed. Lower‐critical‐solution‐temperature‐type behavior was observed for all of the liquid–liquid (L–L) phase boundaries, which shifted to higher pressures in solutions containing CO₂. The solid–fluid (S–F) phase boundaries were investigated over a P range of 8–54 MPa and took place in a narrow T range, from 374 to 378 K in this P interval. The S–F phase boundary showed a unique feature in that the demixing temperatures showed both increasing and decreasing trends with P depending on the P range. This was observed in both the PE/n‐pentane and PE/n‐pentane/CO₂ mixtures. The density of these solutions were measured as a function of P at selected temperatures or as a function of T at selected pressures that corresponded to the paths followed in approaching the phase boundaries (S–F or L–L) starting from a homogeneous one‐phase condition. The data showed a smooth variation of the overall mixture density along these paths. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2201–2209, 2003