辽河盆地西部凹陷深部流体的地球化学特征与成藏效应

The main research area of this thesis is the Western Depression in the Liaohe Basin. Based on the drilling core observation and mud logging data, the features of the mantle–derived fluids and their effects on oil/gas generation in the Western Depression of the Liaohe Basin,was studied with comprehensive methods of volcanic petrology, sediment petrology, fluid geochemistry, sedimentlogy, and structural geology, and use of polarized light microscope, fluorescence microscope, electron microscope, fluid and melt inclusion test, and isotopic test of nature gas etc. The observation of drill cores in study area and other studies reveal that the main passageway of the volcanic eruption in the Cenozoic was the Xibaqian-Gaosheng fault, and the volcanic rocks of each stage were distributed around it. Mantle-derived fluid which affected on oil/gas generation formed later than the volcanic spew and those fluids entered into the depression through the Taian-Dawa fault and the Central fault. The volatile fraction analysis of the melt inclusion reveals the presence of two kinds of mantle fluids; they are hydrogen-rich fluid and carbon dioxide-rich fluid. These the two kinds of fluids were mainly distributed in olivine and pyroxene respectively. The hydrothermal veins development have multiple stages, from high temperature quartz vein to low temperature calcite vein and analcime vein, in which the fluid inclusion extremity component are methane and carbon dioxide, which indicate that when mantle-derived fluids ascended and entered into the basin, most of these fluids interacted with the organic matter in the basin even though some of these entered into atmosphere. The present isotopic test of the nature gas reveals the high 3He/4He value between the region of the Taian-Dawa fault and the Central fault, which also imply the feature of origin in mantle. This phenomenon indicates that the Mesozoic basement faults and the main Cenozoic faults had connected crust and the mantle during the basin evolution, so the mantle derived fluids could enter the basin along those faults. The main source rocks of the ES3 and ES4 members of the Shahejie Formation began to expel hydrocarbon at the end period of the ES1 member of the Shahejie Formation, and reached its peak during the period of the Dongying Formation deposition. During these periods, the mantle derived-fluids entered the basin constantly along the main faults, and supplied lots of hydrogen for hydrocarbon generation. Though the volcanic rocks and the mantle-derived fluids in the Eastern Depression were more developed than in the Western Depression, the source rocks and the deep fluids were not interacted better than the Western Depression because of the affection of structural evolution. In the Eocene, the Eastern Depression did not deposit the ES4 member of the Shahejie Formation, furthermore, the mantle-fluid formed in the Fangshengpao stage escaped to the atmosphere, which confined the later stage hydrocarbon generation capability.

生物－热催化过渡带沉积成岩演化及其成烃作用研究

The biothermocatalytic transitional zone gas is a new type of natural gas genetic theory, and also an clean, effective and high quality energy with shallow burial depth, wide distribution and few investment. Meanwhile, this puts biothermocatalytic transitional zone gas in important position to the energy resource and it is a challenging front study project. This paper introduces the concept, the present situation of study and developmental trend about biothermocatalytic transitional zone gas in detail. Then by using heat simulating of source rocks and catalysis mechanism analysis in the laboratory and studying structural evolution, sedimentation, diagenesis and the conditions of accumulation formation and so on, this paper also discusses catalytic mechanism and evolutionary model of the biothermocatalytic transitional zone gas formation, and establishes the methods of appraisal parameter and resources prediction about the biothermocatalytic transitional zone gas. At last, it shows that geochemical characteristics and differentiated mark of the biothermocatalytic transitional zone gas, and perfect natural gas genetic theory, and points out the conditions of accumulation formation, distribution characteristics and potential distribution region on the biothermocatalytic transitional zone gas m China. The paper mainly focuses on the formation mechanism and the resources potential about the biothermocatalytic transitional zone gas. Based on filed work, it is attached importance to a combination of macroscopic and microcosmic analysis, and the firsthand data are obtained to build up framework and model of the study by applying geologic theory. Based on sedimentary structure, it is expounded that structural actions have an effect on filling space and developmental cource of sediments and evolution of source rocks. Carried out sedimentary environment, sequence stratigraphy, sedimentary system and diagenesis and so on, it is concluded that diagenesis influences developmental evolution of source rocks, and basic geologic conditions of the biothermocatalytic transitional zone gas. Applying experiment simulating and catalytic simulating as well as chemical analysis, catalytic mechanism of clay minerals is discussed. Combined diagenecic dynamics with isotope fractionation dynamics, it is established that basis and method of resource appraisal about the biothermocatalytic transitional zone gas. All these results effectively assess and predict oil&gas resources about the biothermocatalytic transitional zone gas-bearing typical basin in China. I read more than 170 volumes on the biothermocatalytic transitional zone gas and complete the dissertation' summary with some 2.4 ten thousand words, draw up study contents in some detail and set up feasible experimental method and technologic course. 160 pieces of samples are obtained in oilfield such as Liaohe, Shengli, Dagang and Subei and so on, some 86 natural gas samples and more than 30 crude oil samples. Core profiles about 12 wells were observed and some 300 geologic photos were taken. Six papers were published in the center academic journal at home and abroad. Collected samples were analysised more than 1000 times, at last I complete this dissertation with more than 8 ten thousand words, and with 40 figures and 4 plates. According to these studies, it is concluded the following results and understandings. 1. The study indicates structural evolution and action of sedimentary basin influence and control the formation and accumulation the biothermocatalytic transitional zone gas. Then, the structural action can not only control accommodation space of sediments and the origin, migration and accumulation of hydrocarbon matters, but also can supply the origin of energy for hygrocarbon matters foramtion. 2. Sedimentary environments of the biothermocatalytic transitional zone gas are lake, river and swamp delta- alluvial fan sedimentary systems, having a warm, hot and humid climate. Fluctuation of lake level is from low to high., frequency, and piling rate of sedimentary center is high, which reflect a stable depression and rapidly filling sedimentary course, then resulting in source rocks with organic matter. 3. The paper perfects the natural gas genetic theory which is compound and continuous. It expounds the biothermocatalytic transitional zone gas is a special gas formation stage in continuous evolutionary sequence of organic matter, whose exogenic force is temperture and catalysis of clay minerals, at the same time, having decarbxylation, deamination and so on. 4. The methodology is established which is a combination of SEM, TEM and Engery spectrum analysis to identify microstructure of crystal morphology about clay minerals. Using differential thermal-chromatographic analysis, it can understand that hydrocarbon formation potential of different typies kerogens and catalytic method of all kinds of mineral matrix, and improve the surface acidity technology of clay minerals measured by the pyridine analytic method. 5. The experiments confirm catalysis of clay minerals to organic matter hygrocarbon formation. At low temperature (<300 ℃), there is mainly catalysis of montmorillonite, which can improve 2-3 times about produced gas of organic matters and the pyrolyzed temperature decreased 50 ℃; while at the high temperature, there is mainly catalysis of illite which can improve more than 2 times about produced gas of organic matters. 6. It is established the function relationship between organic matter (reactant) concentration and temperature, pressure, time, water and so on, that is C=f (D, t). Using Rali isotope fractionation effect to get methane isotope fractionation formula. According to the relationship between isotope fractionation of diagenesis and depth, and combined with sedimentary rate of the region, it is estimated that relict gas of the biothermocatalytic transitional zone gas in the representative basin. 7. It is revealed that hydrocarbon formation mechanism of the biothermocatalytic transitional zone gas is mainly from montmorillonite to mixed minerals during diagenesis. In interlayer, a lot of Al~(3+) substitute for Si~(4+), resulting in a imbalance between surface charge and interlayer charge of clay minerals and the occurrence of the Lewis and Bronsted acid sites, which promote to form the carbon cation. The cation can form alkene or small carbon cation. 8. It is addressed the comprehensive identification mark of the biothermo - catalytic transitional zone gas. In the temproal-spatial' distribution, its source rocks is mainly Palaeogene, secondly Cretaceous and Jurassic of Mesozoic, Triassic, having mudy rocks and coal-rich, their organic carbon being 0.2% and 0.4% respectively. The vitrinite reflection factor in source rocks Ro is 0.3-0.65%, a few up to 0.2%. The burial depth is 1000-3000m, being characterized by emerge of itself, reservoir of itself, shallow burial depth. In the transitional zone, from shallow to deep, contents of montmorillonites are progressively reduced while contents of illites increasing. Under SEM, it is observed that montmorillonites change into illite.s, firstly being mixed illite/ montmorillonite with burr-like, then itlite with silk-like. Carbon isotope of methane in the biothermocatatytic transitional zone gas , namely δ~(13)C_1-45‰- -60 ‰. 9. From the evolutionary sequence of time, distribution of the biothermocatalytic transitional zone gas is mainly oil&gas bearing basin in the Mesozoic-Neozoic Era. From the distribution region, it is mainly eastern stuctural active region and three large depressions in Bohaiwang basin. But most of them are located in evolutionary stage of the transitional zone, having the better relationship between produced, reservoir and seal layers, which is favorable about forming the biothermocatalytic transitional zone gas reservoir, and finding large gas (oil) field.

断陷湖盆缓坡带成藏模式研究

Halfgraben-like depressions have multiple layers of subtle traps, multiple coverings of oil-bearing series and multiple types of reservoirs. But these reservoirs have features of strong concealment and are difficult to explore. For this reason, many scholars contribute efforts to study the pool-forming mechanism for this kind of basins, and establish the basis for reservoir exploration and development. However, further study is needed. This paper takes HuiMin depression as an example to study the pool-forming model for the gentle slope belts of fault-depression lake basins. Applying multi-discipline theory, methods and technologies including sedimentary geology, structural geology, log geology, seismic geology, rock mechanics and fluid mechanics, and furthermore applying the dynamo-static data of oil reservoir and computer means in maximum limitation, this paper, qualitatively and quantitatively studies the depositional system, structural framework, structural evolution, structural lithofacies and tectonic stress field, as well as fluid potential field, sealing and opening properties of controlling-oil faults and reservoir prediction, finally presents a pool-forming model, and develops a series of methods and technologies suited to the reservoir prediction of the gentle slope belt. The results obtained in this paper richen the pool-forming theory of a complex oil-gas accumulative area in the gentle slope belt of a continental fault-depression basin. The research work begins with the study of geometric shape of fracture system, then the structural form, activity stages and time-space juxtaposition of faults with different level and different quality are investigated. On the basis of study of the burial history, subsidence history and structural evolution history, this paper synthesizes the studied results of deposition system, analyses the structural lithofacies of the gentle slope belt in the HuiMing Depression and its controlling roles to oil reservoir in the different structural lithofacies belts in time-space, and presents their evolution patterns. The study of structural stress field and fluid potential field indicates that the stress field has a great change from the Dong Ying stages to nowadays. One marked point among them is that the Dong Ying double peak- shaped nose structures usually were the favorable directional area for oil and gas migration, while the QuDi horst became favorable directional area since the GuanTao stage. Based on the active regular of fractures and the information of crude oil saturation pressure, this paper firstly demonstrates that the pool-forming stages of the LingNan field were prior to the stages of the QuDi field, whici provides new eyereach and thinking for hydrocarbon exploration in the gentle slope belt. The BeiQiao-RenFeng buried hill belt is a high value area with the maximum stress values from beginning to end, thus it is a favorable directional area for oil and gas migration. The opening and sealing properties of fractures are studied. The results obtained demonstrate their difference in the hydrocarbon pool formation. The seal abilities relate not only with the quality, direction and scale of normal stress, with the interface between the rocks of two sides of a fault and with the shale smear factor (SSF), but they relate also with the juxtaposition of fault motion stage and hydrocarbon migration. In the HuiMin gentle slope belt, the fault seal has difference both in different stages, and in different location and depth in the same stage. The seal extent also displays much difference. Therefore, the fault seal has time-space difference. On the basis of study of fault seal history, together with the obtained achievement of structural stress field and fluid potential field, it is discovered that for the pool-forming process of oil and gas in the studied area the fault seal of nowadays is better than that of the Ed and Ng stages, it plays an important role to determine the oil column height and hydrocarbon preservation. However, the fault seal of the Ed and Ng stages has an important influence for the distribution state of oil and gas. Because the influential parameters are complicated and undefined, we adopt SSF in the research work. It well reflects synthetic effect of each parameter which influences fault seal. On the basis of the above studies, three systems of hydrocarbon migration and accumulation, as well as a pool-forming model are established for the gentle slope belt of the HuiMin depression, which can be applied for the prediction of regular patterns of oil-gas migration. Under guidance of the pool-forming geological model for the HuiMin slope belt, and taking seismic facies technology, log constraint evolution technology, pattern recognition of multiple parameter reservoir and discrimination technology of oil-bearing ability, this paper develops a set of methods and technologies suited to oil reservoir prediction of the gentle slope belt. Good economic benefit has been obtained.

准噶尔盆地中拐东北斜坡油气成藏条件研究——西部压性盆地含油气系统理论的研究与实践

This paper builds the model of oil accumulation and achieves the prediction of exploration goal. It uses multiple subject means, the ways of synthetic research and the viewpoint of analyzing genesis, with the academic guidance of sedimentology, structural geology, petroleum geology and geochemistry, the basis of strata sequence frame and structural frame, the frame of "four history" - the burying history, the structural history, the filling history and the evolving history of oil, the masterstroke of hydrocarbon's generation, migration and accumulation, the aim of revealing the genetic relation between mature source rock and oil reservoir in space and time. Some achievements and viewpoints in this study are following. 1. It is proposed that the structural evolution in this area had many periods, and the structural movement of the Xiazijie group telophase formed the structural pattern for the first time. 2. The character of strata sequence in this area is divided by the character of episodic cycle firstly. The study of dividing the facies of single well and the facies of well tie is based on the data of single well. The character of sedimentary facies is con-structed initially. 3. It is believed that Jiamuhe group is the main source rock, which can supply considerable oil and gas resources for the first time. Some criterions of source rock such as the type ,the abundance in Jiamuhe group are analysed. Using the thermal history of source rock, we drawn a conclusion that the original type of source rock in Jiamuhe group is II_1-III, and the abundance achived the level of good source rock, and this set of source rock had contributed to this area. 4. The reservoir strata in this area are assessed and analysed with the reservoir evaluation. There are multi-type reservoirs, such as volcanic lava facies, sedimentary clast facies, continental belch facies. The physical property in reservoir strata is characterized by low porosity and low permeability. The study of diagenetic stage show that the diageneses in Jiamuhe group is A-Bsubage, and the reservoir room is mainly secondary corroded hollow and cleft. 5. The synthetic research on oil system in Jiamuhe group is made for the first time. The type of petroleum system is divided , and we consider that the petroleum system of Jiamuhe group is at the reliable rank. There are two critical time in oil accumulation through studying the critical time of oil accumulation : the early generation of hydrocarbon is oil, and the later is gas. 6. The mechanism of accumulation is analysed. We consider that the accu-mulation of oil in this area has many periods, and the early generated hydrocarbon is expeled by the later , and formed the character of zonal distribution in planar. 7. A bran-new model of oil and gas is proposed. Beneficial enrichment area of oil and gas is analyzed, which can be divided into three sections: Section I can be divided into two sections: I_1 and I_2. The lower subgroup of Jiamuhe is covered by the triassic layer of I_1 section. Fault zone and near the foot wall of fault are charactered with thick phase belt. Then the cover capability in this area is relatively poor, oil can migrate into triassic layer by vertical or lateral migration , and forms I_1 Kelamayi triassic oil pool consequently. The lower subgroup of Jiamuhe is covered by the triassic layer of I_2 section ,which is charactered with thin phase belt. Then the cover capability in this area is relatively good, and forms I_1 Kelamayi triassic oil pool consequently. Section II can be divided into two sections: II_1-I_(I~2). The cover of Jiamuhe group in section II_1 is the low resistivity segment in Wuerhe group, which has thin lithology and poor porosity and permeability. Oil and gas in Jiamuhe group can be covered to form beneficial accumulation area. There are some wells in this area, such as Ke 007 well, 561 well. The thick phase belt layer of Wuerhe high resistivity segment in section II_2 has unconformable relation with Jiamuhe group. The cover ability of the high resistivity segment is poor, petroleum in Jiamuhe can migrate into Wuerhe layer vertically. This area is the beneficial area for accumulating petroleum in Wuerhe layer. there are some wells in this area, such as Ke 75 well, Ke 76 well, Ke 77 well, Ke 78 well, Ke 79 well. Section III can also be divided into two sections: III_1 and III_2. Wuerhe group in section III_1 has unconformable relation with Jiamuhe group. There is thick lithology and poor cover in Wuerhe group, but the strata sequence evolution character of upper subgroup in Jiamuhe group has determined that it has lateral and vertical cover ability. thus, this area is petroleum abundant belt of jiamuhe group, which has the trap. Section III_2 is an area controled by wedgeout of Fengcheng group, Fengcheng group in this area has quite thick lithology so that It has beneficial resevoir phase belt. It can accumulate oil in itself or accept some oil in Jiamuhe group. Jiamuhe group has some oil accumulation condition in this area. Thus, section III_2 is jiamuhe-Fengcheng multiple petroleum accumulation belt, such as Ke 80 well. 8. The goal of exploration is suggested: Depositional trap or combination trap is the important aspect in later exploration. Both types of traps are the goal of the next drilling: Fault block trap in the east of 576 well and the NO. 2 fault block trap in the north of Ke 102 well It is suggested that we should study the law of oil and gas in Jiamuhe group and enhance the study of combination in forming reservoir and trap scale. We do some lithology forecast and reservoir diatropic forecast in order to know the area of oil and gas.

断层封闭性及其与油气成藏的关系研究-以沾化凹陷孤岛地区为例

Godao area, located in the east of the Zhanhua depression of Jirang sag in Bohai Bay Basin, is the studying area in my dissertation. It is first time that fault sealing properties and the related relationship with the pool forming are studied in Gudao area. On the base of the analysis of the regional tectonics, the author has studied the tertiary structural evolution of the Gudao area and distinguished the fault's level and put forward the distinguishing principle. The geometrical feature, mechanical characters, developmental mechanism and history of the boundary faults in the tectonic unit of this area are all studied and emphasized especially. The buried history of oil-generating depression (that is Gudao depression) and the history of oil and gas migration simultaneously are discussed, the juxtaposition relationship between boundary fault evolutionary history and oil and gas migrated history are expatiated. To the geological condition of the Gudao area, three level faults sealing properties of this area were discussed in detail. Their characteristics of behavior and the intrinsic relationship between their sealing and oil and gas migrated reservoir are elucidated. The pool-forming models related to fault seal are exposed. The author has studied the lithologies of different order of faults, the relationship of occurrence assemblage analysis, normal stress of fault plane in different depth and shale smear factor faults. Then analysis their role in the various faults sealing and confirms fault sealing marks of three different orders faults and exposes the mechanism of fault sealing. Shale smear zone formed by first order fault in lasting activities is one different type of fault breccia and mainly controlled factor to its entrapment of petroleum. Effective sealing threshold value and fault displacement is ascertained. Mainly controlled factor of second fault sealing is bigger compressive stress loaded on fault plane. According to this, quantitatively evaluated index is given. Shale smear zone is necessary condition for second fault stress entrapment. The juxtaposed relationship between the different lithologies within third order faults is most important controlled factor for its sealing. Based on various order of fault sealing features and mechanism in Gudao area, the author proposed three orders of fault sealing models. Shale smear zone sealing model, normal stress sealing model and lithologies juxtaposed sealing model are suggested to first, second and third order fault respectively. The conclusion of this studying has not only the very important theoretical significance and practical value in Gudo area but also the very important guiding role for other areas of related aspects.

沾化凹陷泥质岩油气藏成藏特征研究

Mudstone reservoir is a subtle reservoir with extremely inhomogeneous, whose formation is greatly related to the existence of fracture. For this kind of reservoir, mudstone is oil source rock, cover rock and reservoir strata, reservoir type is various, attitude of oil layer changes greatly, and the distribution of oil and gas is different from igneous or clastic rock reservoir as well as from carbonate reservoir of self-producing and self-containing of oil and gas. No mature experience has been obtained in the description, exploration and development of the reservoir by far. Taking Zhanhua depression as an example, we studied in this thesis the tectonic evolution, deposit characteristics, diagenesis, hydrocarbon formation, abnormal formation pressure, forming of fissure in mudstone reservoir, etc. on the basis of core analysis, physical simulation, numerical simulation, integrated study of well logging and geophysical data, and systematically analyzed the developing and distributing of mudstone fissure reservoir and set up a geological model for the formation of mudstone fissure reservoir, and predicted possible fractural zone in studied area. Mudstone reservoir mainly distributed on the thrown side of sedimentary fault along the sloping area of the petroleum generatiion depression in Zhanhua depression. Growing fault controlled subsidence and sedimentation. Both the rate of subsidence and thickness of mudstone are great on the thrown side of growing fault, which result in the formation of surpressure in the area. The unlocking of fault which leads to the pressure discharges and the upward conduct of below stratum, also makes for the surpressure in mudstone. In Zhanhua depression, mudstone reservior mainly developed in sub-compacted stratum in the third segment of Shahejie formation, which is the best oil source rock because of its wide spread in distribution, great in thickness, and rich in organic matter, and rock types of which are oil source mudstone and shale of deep water or semi-deep water sediment in lacustrine facies. It revealed from core analysis that the stratum is rich in limestone, and consists of lamina of dark mudstone and that of light grey limestone alternately, such rock assemblage is in favor of high pressure and fracture in the process of hydrocarbon generation. Fracture of mudstone in the third segment of Shahejie formation was divided into structure fracture, hydrocarbon generation fracture and compound fracture and six secondary types of fracture for the fist time according to the cause of their formation in the thesis. Structural fracture is formed by tectonic movement such as fold or fault, which develops mainly near the faults, especially in the protrude area and the edge of faults, such fracture has obvious directivity, and tend to have more width and extension in length and obvious direction, and was developed periodically, discontinuously in time and successively as the result of multi-tectonic movement in studied area. Hydrocarbon generation fracture was formed in the process of hydrocarbon generation, the fracture is numerous in number and extensively in distribution, but the scale of it is always small and belongs to microfracture. The compound fracture is the result of both tectonic movement and hydrocarbon forming process. The combination of above fractures in time and space forms the three dimension reservoir space network of mudstone, which satellites with abnormal pressure zone in plane distribution and relates to sedimentary faces, rock combination, organic content, structural evolution, and high pressure, etc.. In Zhanhua depression, the mudstone of third segment in shahejie formation corresponds with a set of seismic reflection with better continuous. When mudstone containing oil and gas of abnormal high pressure, the seismic waveform would change as a result of absorb of oil and gas to the high-frequency composition of seismic reflection, and decrease of seismic reflection frequency resulted from the breakage of mudstone structure. The author solved the problem of mudstone reservoir predicting to some degree through the use of coherent data analysis in Zhanhua depression. Numerical modeling of basin has been used to simulate the ancient liquid pressure field in Zhanhua depression, to quantitative analysis the main controlling factor (such as uncompaction, tectonic movement, hydrocarbon generation) to surpressure in mudstone. Combined with factual geologic information and references, we analyzed the characteristic of basin evolution and factors influence the pressure field, and employed numerical modeling of liquid pressure evolution in 1-D and 2-D section, modeled and analyzed the forming and evolution of pressure in plane for main position in different periods, and made a conclusion that the main factors for surpressure in studied area are tectonic movement, uncompaction and hydrocarbon generation process. In Zhanhua depression, the valid fracture zone in mudstone was mainly formed in the last stage of Dongying movement, the mudstone in the third segment of Shahejie formation turn into fastigium for oil generation and migration in Guantao stage, and oil and gas were preserved since the end of the stage. Tectonic movement was weak after oil and gas to be preserved, and such made for the preserve of oil and gas. The forming of fractured mudstone reservoir can be divided into four different stages, i.e. deposition of muddy oil source rock, draining off water by compacting to producing hydrocarbon, forming of valid fracture and collecting of oil, forming of fracture reservoir. Combined with other regional geologic information, we predicted four prior mudstone fracture reservoirs, which measured 18km2 in area and 1200 X 104t in geological reserves.

黄土高原粉尘堆积源区环境及风化历史初步研究

In this study, we examined the surface features of quartz grains, the quartz oxygen isotopic ratios and the mineralogical compositions of the loess - paleosol - red clay sediments systematically. The surface features of quartz grains do not show significant changes of the dust deposits through the past seven million years. The particles were mainly created in the process of glacial and frost weathering of high mountains. Then the surfaces were altered in some degree by the flood and wind abrasion. The surface features registered all these processes. The assemblages of surface features changed for four times in the past seven million years, the occurrence ages are: 5.0~4.2MaBP, about 3.6MaBP, about 2.6MaBP and about 0.9MaBP, respectively. This may indicate that there were uplift events of the Tibetan Plateau during those times. The oxygen isotopic compositions of quartz in the sediments represent the oxygen isotopic compositions of the initial dusts because of the stable properties of quartz both physically and chemically. The oxygen isotopic compositions of 4~16um quartz changed significantly at about 2.6MaBP, decreasing from about 19.5%o to about 18.5%o. This decrease of quartz oxygen isotopic ratio suggests that the environments of the dust source areas changed at that time, or the range of dust source area changed at that time. The environmental change may result from the structural evolution of the Tibetan Plateau and global cooling at that time. The coarse fractions (>30μm) of the dust deposits were examined using the EDXA device for mineral identification. The quartz content has a decrease trend during 7~2MaBP, then increase rapidly at about 2MaBP. After 2MaBP, quartz content continues to decrease. The Ca-plagioclase content / quartz content ratio increase at about 3.6MaBP. The ratio shows a peak of 3-6 fold values at about 2.5~1.8MaBP, the cause of this is still unknown. The Ca-plagioclase content / quartz content ratio continues to increase after 1 MaBP. The flowing can be regarded as the conclusion remarks of this study: Some of the red clay sediment of the Chinese Loess Plateau (at least Lingtai and Jingchuan red clays) is eolian in origin. The quartz grains from dust deposits throughout the past seven million yeas showed the clues of glacial and frost processes. This indicates that the high mountains of western China reached a certain altitude to favor the glacial and/or frost processes at least seven millions years before. The weathering intensities of the past seven nnillion yeas have a decreasing trend. In about 5~4.5MaBP, the weathering is relatively weak, and the dust supply is relatively low. At about 3.6MaBP and 2.6MaBP, the dust supply increased significantly. The mineralogical composition, the quartz surface feature and the quartz oxygen isotope composition were influenced by the uplift of the Tibetan Plateau. The Plateau may have reached a certain altitude to generate the arid regions of inland China and favor the glacial and frost weathering. And it underwent a phased uplift, which have uplift events at about 3.6MaBP and 2.6MaBP.

库车坳陷-南天山盆山系统第三纪脆性构造研究

Study on the structural coupling relationship between basin and range is not only helpful to recognize the basin formation and evolution systematically, but also to guide petroleum exploration in the basin. As a late Paleozoic Orogen, the South Tianshan Mountains reactivated and uplifted rapidly during the Cenozoic, and led to the Mesozoic-Cenozoic considerable thick deposits in the Kuqa Depression. The researches of the dissertation were carried out in the Kuqa depression-South Tianshan M ountain s ystem, a nd t he b rittle m icrotectonics w. ere c hosen as t he m ost important object. Based on observations and measurements of the field, we made detailed investigations on the geometry and kinematics of this area, and analyzed the abutting and cutting relationships and relative sequence of many brittle structures, such as joint, shear fractures, faults and some small-scale structures related to them closely. According to those brittle fractures' relationships with stress, the nature and variation of regional palaeostress field during the Cenozoic were studied through inversion of fault slip data and inferring stress state from joint sequences. And the deformation time was estimated primarily via ESR dating of faulting. Results show that the stress field varies as well in times as in space. The maximal principal stress direction shifted from the vertical to the horizontal, and stress regime from weak extension to strong compression from the Paleogene to the Neogene regionally. During the late Neogene, the structural deformation of the South Tianshan and the basin-range boundary was dominated by near N-S extension, while near N-S compressive deformation in the interior of the Kuqa Depression. There exits obvious differential stress state from the north to the south. ESR dating of the faulting during the Cenozoic indicates that, the normal faulting in the north edge of the Kuqa Depression have been active all along from the Miocene to the early Pleistocene, but the thrusting and reverse faulting in the interior only been active from the Pliocene to the early Pleistocene. On the base of those geological data and some geophysical information and theoretical calculation results, we infer that, the different stress regime the basin-range system is ascribed to the vertical uplift of the Tianshan Mountain. It was the vertical uplift that lead to the gravity-driven gliding of thick layers lying on the faulted basement from the South Tianshan Mountain to the Kuqa depression, and to folding and thrusting in the interior and frontal of the Kuqa depression. Combining the structural evolution with petroleum geological conditions of the Kuqa Depression, we think that the strong compressive deformation of the Kuqa Depression during rapid uplifting of the Tianshan Mountains from the Pliocene to the early Pleistocene play crucial role in the structural trap formation and proliferous gas accumulation.

Dynamical Systems in the Sensorimotor Loop: On the Interrelation Between Internal and External Mechanisms of Evolved Robot Behavior

Huelse, M., Wischmann, S., Manoonpong, P., Twickel, A.v., Pasemann, F.: Dynamical Systems in the Sensorimotor Loop: On the Interrelation Between Internal and External Mechanisms of Evolved Robot Behavior. In: M. Lungarella, F. Iida, J. Bongard, R. Pfeifer (Eds.) 50 Years of Artificial Intelligence, LNCS 4850, Springer, 186 - 195, 2007.

Synthesis and characterization of oxide materials

Nanostructured materials are central to the evolution of future electronics and biomedical applications amongst other applications. This thesis is focused on developing novel methods to prepare a number of nanostructured metal oxide particles and films by a number of different routes. Part of the aim was to see how techniques used in nanoparticle science could be applied to thin film methods to develop functional surfaces. Wet-chemical methods were employed to synthesize and modify the metal oxide nanostructures (CeO2 and SiO2) and their structural properties were characterized through advanced X-ray diffraction, electron microscopy, photoelectron spectroscopy and other techniques. Whilst particulates have uses in many applications, their attachment to surfaces is of importance and this is frequently challenging. We examined the use of block copolymer methods to form very well defined metal oxide particulate-like structures on the surface of a number of substrates. Chapter 2 describes a robust method to synthesize various sized silica nanoparticles. As-synthesized silica nanoparticles were further functionalized with IR-820 and FITC dyes. The ability to create size controlled nanoparticles with associated (optical) functionality may have significant importance in bio-medical imaging. Thesis further describes how non-organic modified fluorescent particles might be prepared using inorganic oxides. A study of the concentrations and distributions of europium dopants within the CeO2 nanoparticles was undertaken and investigated by different microscopic and spectroscopic techniques. The luminescent properties were enhanced by doping and detailed explanations are reported. Additionally, the morphological and structural evolution and optical properties were correlated as a function of concentrations of europium doping as well as with further annealing. Further work using positron annihilation spectroscopy allowed the study of vacancy type defects formed due to europium doping in CeO2 crystallites and this was supported by complimentary UV-Vis spectra and XRD work. During the last few years the interest in mesoporous silica materials has increased due to their typical characteristics such as potential ultra-low dielectric constant materials, large surface area and pore volume, well-ordered and uniform pores with adjustable pores between 2 and 50 nm. A simple, generic and cost-effective route was used to demonstrate the synthesis of 2D mesoporous silica thin films over wafer scale dimensions in chapter 5. Lithographic resist and in situ hard mask block copolymer followed by ICP dry etching were used to fabricate mesoporous silica nanostructures. The width of mesoporous silica channels can be varied by using a variety of commercially available lithographic resists whereas depth of the mesoporous silica channels can be varied by altering the etch time. The crystal structure, morphology, pore arrangement, pore diameters, thickness of films and channels were determined by XRD, SEM, ellipsometry and the results reported. This project also extended work towards the study of the antimicrobial study of nanopatterned silver nanodot arrays formed using the block copolymer approach defined above. Silver nanodot arrays were successfully tested for antimicrobial activity over S. aureus and P. aeruginosa biofilms and results shows silver nanodots has good antimicrobial activity for both S. aureus and P. aeruginosa biofilms. Thus, these silver nanodot arrays shows a potential to be used as a substitute for the resolution of infection complications in many areas.

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

Galvanic replacement is a versatile synthetic strategy for the synthesis of alloy and hollow nanostructures. The structural evolution of single crystalline and multiply twinned nanoparticles <20 nm in diameter and capped with oleylamine is systematically studied. Changes in chemical composition are dependent on the size and crystallinity of the parent nanoparticle. The effects of reaction temperature and rate of precursor addition are also investigated. Galvanic replacement of single crystal spherical and truncated cubic nanoparticles follows the same mechanism to form hollow octahedral nanoparticles, a mechanism which is not observed for galvanic replacement of Ag templates in aqueous systems. Multiply twinned nanoparticles can form nanorings or solid alloys by manipulating the reaction conditions. Oleylamine-capped Ag nanoparticles are highly adaptable templates to synthesize a range of hollow and alloy nanostructures with tuneable localised surface plasmon resonance.

Atomic ordering in nano-layered FePt

Monte Carlo simulation of chemical ordering kinetics in nano-layered L1₀ AB binary intermetallics was performed. The study addressed FePt thin layers considered as a material for ultra-high-density magnetic storage media and revealed metastability of the L1₀ c-variant superstructure with monoatomic planes parallel to the surface and off-plane easy magnetization. The layers, originally perfectly ordered in a c-variant of the L1₀ superstructure, showed homogeneous disordering running in parallel with a spontaneous re-orientation of the monoatomic planes leading to a mosaic microstructure composed of a- and b-L1₀-variant domains. The domains nucleated heterogeneously on the surface of the layer and grew discontinuously inwards its volume. Finally, the domains relaxed towards an equilibrium microstructure of the system. Two “atomistic-scale” processes: (i) homogeneous disordering and (ii) nucleation of the a- and b-L1₀-variant domains showed characteristic time scales. The same was observed for the domain microstructure relaxation. The discontinuous domain growth showed no definite driving force and proceeded due to thermal fluctuations. The above complex structural evolution has recently been observed experimentally in epitaxially deposited thin films of FePt.

Preparation and surface modification of submicron YAl2 particles by mixed milling with magnesium for fabricating YAl2p/MgLiAl composites

A new process for the preparation and surface modification of submicron YAl2 intermetallic particles was proposed to control the agglomeration of ultrafine YAl2 particles and interface in the fabrication of YAl2p/MgLiAl composites. The morphological and structural evolution during mechanical milling of YAl2 powders (< 30 μm) with magnesium particles (~ 100 μm) has been characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The results show that YAl2 particles are refined to submicron scale and separately cladded in magnesium coatings after mixed milling with magnesium particles for 20 h. Mechanical and metallurgical bonds have been found in YAl2/Mg interfaces without any interface reactions. Both the refining and mechanical activation efficiencies for YAl2 particles are enhanced, which may be related to the addition of magnesium particles leading to atomic solid solution and playing a role as “dispersion stabilizer”.

Novel furan polymer materials based on the reversible Diels-Alder reaction

A futura e inevitável escassez dos recursos fósseis, juntamente com o aumento imprevisível dos seus preços, levou, nas últimas décadas, a um aumento impressionante de iniciativas dedicadas não só à procura de fontes alternativas de fornecedores de energia, mas também de produtos químicos e polímeros a partir de fontes renováveis, em particular da biomassa vegetal. Entre estes, os polímeros derivados de monómeros furânicos constituem uma classe única de materiais cujas estruturas podem, em princípio, simular virtualmente os seus homólogos actualmente derivados de recursos fósseis. O anel furânico é uma estrutura heterocíclica com um carácter diénico pronunciado, o que torna-o um dieno particularmente apropriado para a reacção de Diels-Alder (DA) com dienófilos como a maleimida. Um dos aspectos mais relevantes da reacção de DA é a sua reversibilidade em função da temperatura, a qual permite que os aductos sejam facilmente revertidos nos seus precursores por aumento da temperatura (reacção de retro-DA). No caso específico da combinação furano-maleimida, a formação do aducto predomina até cerca de 60ºC, enquanto a reacção inversa é dominante acima de 100ºC. A combinação desta característica da reacção de DA com a química de compostos furânicos pode abrir um novo caminho para a preparação de materiais macromoleculares funcionais com base em fontes renováveis e com aplicações promissoras como auto-reparação e reciclabilidade. O principal objectivo desta Tese, é a síntese e caracterização de novos materiais poliméricos termo-reversíveis, aplicando a reacção de DA a monómeros complementares com estruturas dos tipos furânico (o dieno, designado por A) e de maleimida (o dienófilo, designado por B). A primeira etapa neste trabalho envolveu a síntese, purificação e caracterização de novos monómeros furânicos e de maleimida do tipo AA, A3, BB, B3, AB, AB2, cada um com diferentes grupos separadores das funções reactivas. Posteriormente, estes monómeros foram polimerizados e despolimerizados por ciclos de DA/retro-DA utilizando diferentes combinações. A formação e dissociação de todos os aductos de DA foram seguidas por ambas espectroscopias de UV e RMN de 1H. O primeiro sistema de DA estudado foi uma combinação modelo entre reagentes mono-funcionais (-A+-B), nomeadamente o acetato furfurílico (FA) e a N-metilmaleimida (MM), ambos comercialmente disponíveis. O objectivo desta abordagem foi estudar a cinética e o equilíbrio da formação/dissociação dos aductos de DA e obter indicações sobre as condições mais adequadas a serem usadas na preparação dos correspondentes novos materiais macromoleculares. Além disso, pretendia-se verificar a presença ou ausência de reacções secundárias que poderiam intervir em ambas as vias directa e inversa das reacções, mesmo após vários ciclos. A espectroscopia de UV forneceu informação quantitativa sobre a cinética de formação do aducto através da diminuição progressiva da absorvência máxima a 293 nm correspondente ao grupo maleimida, a diferentes temperaturas (35, 50, 65 ºC) Reciprocamente, a correspondente reacção de retro-DA foi seguida a 90 ºC através do aumento do mesmo pico. A reversibilidade destes sistemas foi verificada com sucesso após uma sequência de ciclos de DA/retro-DA. Adicionalmente, verificou-se que os espectros originaram um ponto isosbéstico, provando que estes sistemas não envolvem quaisquer reacções secundárias. Uma vez que foi usado um excesso de FA, as reacções de DA modelo apresentaram um comportamento cinético de pseudo-primeira ordem, com a constante de velocidade k mais alta (2.1x10-5 dm3mol-1s-1) para T=65 ºC. A correspondente energia de activação foi de 39.0 kJ.mol-1. A reacção de retro-DA seguiu um comportamento de primeira ordem, com constante de velocidade de 1.6x10-6 s-1. A evolução deste sistema por RMN de 1H a 65ºC deu-nos informações mais detalhadas sobre a sua evolução estrutural, ou seja, à medida que a intensidade dos picos atribuídos à formação do aducto aumentaram progressivamente ao longo do tempo, os pertencentes aos reagentes iniciais diminuiram proporcionalmente. O “rendimento final”, calculado após 20 dias à temperatura ambiente, foi de aproximadamente 70%. A reacção de retro-DA foi depois seguida a 90ºC, observando-se tal como na espectroscopia de UV, o deslocamento da reacção no sentido da regeneração dos reagentes de partida. A viabilidade de múltiplos ciclos de DA/retro-DA estabelecidos pela espectroscopia de UV foi igualmente confirmada por RMN de 1H. O passo seguinte envolveu o estudo de um sistema de policondensação linear baseado no crescimento gradual por reacção de DA entre um monómero bisfurânico A-A e um do tipo bismaleimida B-B, seguindo a mesma abordagem que no sistema modelo. O poliaducto linear foi obtido a partir de soluções equimolares dos monómeros, por reacção de DA a 65ºC. O progresso desta polimerização foi seguido por espectroscopia de UV e RMN de 1H e, mais qualitativamente, pelo aumento da viscosidade do meio. A reacção seguiu um comportamento de segunda ordem, com uma constante de velocidade de 9.4x10-6 dm3mol-1s-1, e observou-se novamente um ponto isosbéstico nos dados de UV. Os espectros de RMN apresentaram o padrão esperado, nomeadamente o aumento progressivo dos sinais associados ao aducto e a correspondente diminuição dos grupos furano e maleimida livres. A despolimerização do poliaducto através da reacção de retro-DA foi seguida a 110ºC usando as mesmas técnicas. Os dados de UV mostraram o retorno progressivo da absorção dos grupos de maleimida, seguindo um comportamento cinético de primeira ordem, com constante de velocidade de 2.5x10-6 s-1, até à completa regeneração de ambos os monómeros. Os espectros de RMN providenciaram mais uma vez informação estrutural sobre o progresso da despolimerização, a qual foi acompanhada por uma diminuição progressiva da viscosidade. Adicionalmente, para seguir a retro- DA, adicionou-se um excesso de composto furânico monofuncional, nomeadamente o 2,5-dimetilfurano (DMFu), ao sistema de modo a bloquear as funções maleimida complementares, evitando assim a repolimerização após arrefecimento. Os productos isolados foram então o monómero bisfurânico AA, DMFu que não reagiu e o bisaducto não-polimerizável de BB com DMFu. Este resultado indicou claramente que o polímero foi de facto revertido nos seus monómeros durante a reacção de retro-DA. O terceiro sistema estudado foi outra polimerização linear, seguindo as mesmas condições experimentais que os anteriores, mas com uma estratégia diferente de modo a contornar o problema clássico de assegurar a estequiometria exacta dos monómeros. As estruturas dos monómeros utilizados incorporam ambos os grupos reactivos, i.e, moléculas do tipo A-B. A polimerização prematura destes monómeros intrinsecamente reactivos foi evitada com a protecção do grupo maleimida na forma de um aducto de DA com furano, até a incorporação do substituinte furânico na outra extremidade. Portanto, a policondensação destes monómeros foi iniciada após a desprotecção in situ deste composto mediante aquecimento, seguido de arrefecimento até à temperatura adequada para polimerizar. Os resultados obtidos por UV e RMN sugerem que de facto o uso de monómeros do tipo A-B oferece um melhor sistema linear. Em seguida, foram estudados sistemas de policondensação não-linear por reacção de DA, entre monómeros (um ou ambos) com funcionalidade superior a dois, nomeadamente sistemas do tipo A3+B-B ou A-A+B3, seguindo mais uma vez as mesmas condições experimentais. Uma vez que utilizam monómeros complementares contendo, em média, mais de duas funcionalidades, estes sistemas conduzem a materiais reticulados. Nestes estudos, foram usadas três razões molares de [maleimida]/[furano], nomeadamente 1.0, 0.75 e 0.5, de modo a estudar ambas as situações de não-gelificação e reticulação. Ambos sistemas apresentaram um comportamento regular e boa reciclabilidade quer para gerar situações que possam conduzir à formação de redes a diferentes graus de conversão, ou que possam parar antes da sua obtenção, conforme previsto pela equação de Flory-Stockmayer. Como esperado, a utilização de grupos complementares em quantidades estequiométricas produziu o espessamento mais rápido e a reticulação quase completa; à medida que a quantidade relativa de monómero trifuncional decresceu, as reacções pararam antes da reticulação, ou seja, originaram meios altamente viscosos contendo polímeros solúveis altamente ramificados. As reacções de retro-DA a 110 ºC conduziram à gradual dissolução das partículas de gel (quando presentes), tendo sido comprovado pelos espectros de UV e de RMN de 1H, evidenciado a regeneração dos monómeros. Tal como no sistema do tipo A-A+B-B, a reacção de retro-DA foi seguida adicionando um excesso de DMFu ao sistema reaccional. Como esperado, os produtos finais foram os monómeros furânicos, o DMFu em excesso e o trisaducto ou o bisaducto maleimida-DMFu, o que confirma a eficiência da despolimerização com regeneração dos monómeros iniciais. O último sistema de policondensação por reacção de DA envolveu um monómero assimetricamente substituído do tipo AB2, capaz de originar estruturas macromoleculares hiper-ramificadas que não reticulam. Este estudo preliminar deste sistema foi seguido nas mesmas condições experimentais que os anteriores, apresentando um comportamento com as características esperadas.

Caratérisation de la surface d’énergie potentielle des matériaux complexes et son application sur la cinétique du SiO2/Si

Dans ce rapport de mémoire, nous avons utilisé les méthodes numériques telles que la dynamique moléculaire (code de Lammps) et ART-cinétique. Ce dernier est un algorithme de Monte Carlo cinétique hors réseau avec construction du catalogue d'événements à la volée qui incorpore exactement tous les effets élastiques. Dans la première partie, nous avons comparé et évalué des divers algorithmes de la recherche du minimum global sur une surface d'énergie potentielle des matériaux complexes. Ces divers algorithmes choisis sont essentiellement ceux qui utilisent le principe Bell-Evans-Polanyi pour explorer la surface d'énergie potentielle. Cette étude nous a permis de comprendre d'une part, les étapes nécessaires pour un matériau complexe d'échapper d'un minimum local vers un autre et d'autre part de contrôler les recherches pour vite trouver le minimum global. En plus, ces travaux nous ont amené à comprendre la force de ces méthodes sur la cinétique de l'évolution structurale de ces matériaux complexes. Dans la deuxième partie, nous avons mis en place un outil de simulation (le potentiel ReaxFF couplé avec ART-cinétique) capable d'étudier les étapes et les processus d'oxydation du silicium pendant des temps long comparable expérimentalement. Pour valider le système mis en place, nous avons effectué des tests sur les premières étapes d'oxydation du silicium. Les résultats obtenus sont en accord avec la littérature. Cet outil va être utilisé pour comprendre les vrais processus de l'oxydation et les transitions possibles des atomes d'oxygène à la surface du silicium associée avec les énergies de barrière, des questions qui sont des défis pour l'industrie micro-électronique.