页岩孔隙系统研究实验方法

基于页岩孔隙系统的特殊性,讨论了FESEM-QEMSCAN、FIB-FESEM、NANO-CT、氮气吸附法、小角中子散射等几种页岩孔隙系统研究方法的特点和适用范围。指出场发射扫描电镜以及与之结合的能谱和矿物定量评价系统(FESEM-QEMSCAN)是研究页岩纳米级孔隙类型、大小、形态以及矿物分布的基础手段;聚焦离子束扫描电镜、微纳米CT可刻画页岩孔隙系统在三维空间的展布特征,利用获得的三维数据体进行数值模拟,可进一步计算孔隙度、渗透率等物性参数;氮气吸附法可对小于100nm的极微孔隙的孔径、形态进行求算;小角中子散射则可利用孔隙中存在的气体分子,获得孔隙系统连通性等重要参数。最后从页岩岩石组构的角度,探讨了页岩孔隙控制因素,指出有机质含量与成熟度,黏土矿物类型、含量,碎屑颗粒的含量以及成岩强度是影响页岩孔隙系统的主要因素。     

海相页岩储层微观孔隙体系表征技术及分类方案

页岩储层作为一种非常规油气储集体,对其孔隙体系的研究备受重视。通过充分调研和系统总结国际上关于页岩储层微观孔隙体系的研究现状,综述了孔隙表征技术并指出了存在问题;以客观性和普适性为基础提出了两套分类方案;定性探讨了孔隙演化的一般规律。目前最常见定性观测页岩储层孔隙的方法为高分辨率电子显微镜结合氩离子抛光技术,聚焦离子束扫描电镜系统(FIB-SEM)和纳米CT技术可用于孔隙三维模型重构。高压压汞法结合气体吸附法用于定量分析页岩孔隙结构特征,此外核磁共振也是有效测试手段。分别根据孔隙发育位置与岩石基质关系以及孔隙发育成因与岩石基质关系,将页岩储层孔隙划分为粒间孔、粒内孔、有机质孔和微裂缝以及骨架矿物孔、黏土矿物孔、有机质孔和微裂缝。无机矿物成岩作用与有机质热成熟作用是控制页岩储层孔隙演化的重要因素。     

扬子北缘中二叠统孤峰组不同岩性孔隙特征及其地质意义

孔隙是页岩层系是否具有生烃能力、储气能力和开采价值的主要标志。采用场发射扫描电镜对鄂西建始扬子北缘中二叠统孤峰组硅质页岩、泥质灰岩和碳质页岩3类岩石采取二次电子模式扫描,发现并分析了5大类9小类孔隙,即①絮凝作用孔隙;②有机质化石孔;③有机质碎片沥青孔;④黄铁矿粒间孔;⑤矿物颗粒晶间孔;⑥微型通道;⑦微裂缝;⑧钙质化石孔;⑨碎屑与围岩之间孔。研究表明,硅质页岩中发育较多的黄铁矿微球粒以及絮凝结构,有机质孔隙从纳米级至微米级;泥质灰岩中以矿物质孔隙为主,微裂缝比较发育,脆性矿物多;碳质页岩中存在大量蜂窝状孔洞和广泛分布的微裂缝,孔隙类型主要为有机质纳米孔。碳质页岩与传统储层孔隙特征具有很大差异,是页岩气勘探最为有利的岩层。     

黔东南地区牛蹄塘组页岩孔隙结构多尺度表征及其对页岩气富集的影响

【研究目的 】研究黔东南地区牛蹄塘组页岩孔隙结构特征及其对页岩气富集的影响,抛开不利因素,为黔东南地区页岩气勘探提供建议。【研究方法 】通过聚焦离子束扫描电镜（FIB-SEM）、场发射扫描电镜（FE-SEM）和氮气吸附等手段,对页岩微纳米孔隙结构进行多尺度表征,并结合研究区牛蹄塘组页岩的生烃及埋藏史,研究构造运动与孔隙结构关系,进而分析对页岩气富集的影响。【研究结果 】牛蹄塘组页岩主要发育毫米级微裂缝、微米级黄铁矿晶间孔以及纳米级有机质孔隙,以墨水瓶状孔隙和平板结构的狭缝孔为主,孔隙结构复杂;结合FIB-SEM三维重构结果,有机质在页岩中占比较高,其孔隙度在0.04%～2.48%,对总孔隙的贡献率介于14%～96%,与有机质共生的黄铁矿晶间孔是沟通裂缝的主要孔隙类型;该地区页岩气赋存状态以欠饱和的吸附气为主,游离气含量偏低。【结论 】牛蹄塘组页岩大量构造裂缝,沟通了有机质孔及黄铁矿晶间孔,改变了原有孔隙结构,致使原位聚集的页岩气沿裂缝逸散,是牛蹄塘组页岩含气量低的关键因素。热演化程度适中、构造保存好的区域是古隆起周缘下一步页岩气勘探的有利方向。     

渝东南—黔北地区牛蹄塘组页岩微-纳米级孔隙发育特征及主控因素分析

以渝东南-黔北地区牛蹄塘组页岩岩心及野外新鲜露头样品为研究对象,运用低温液氮吸附实验和氩离子抛光扫描电镜观察,划分页岩微纳米级孔隙类型,并对其发育程度和形态结构进行定量表征,结合页岩样品地球化学测试数据,明确页岩微观孔隙发育主控因素,试图建立微纳米级孔隙发育程度与主控因素定性或半定量关系。结果表明：研究区牛蹄塘组页岩微纳米级孔隙分为有机孔、无机孔和微裂缝3大类,包括7个亚类。有机质粒内孔结构特征为球状、细瓶颈状和墨水瓶状,无机孔主要为串珠状、球状和楔状,微裂缝呈四方开口的平行板状、夹板状。有机质粒内孔、矿物粒间孔和微裂缝为主要孔隙类型,且具有较好连通性,可作为页岩气赋存空间和渗流通道。页岩孔隙以中孔为主,其次为宏孔,孔隙直径分布范围主要在1~50 nm。比表面积主要由孔径≤5 nm孔隙所提供,页岩孔隙孔径越小,对比表面积贡献越大,越有利于页岩气吸附聚集,随着孔隙体积的增加,比表面积不断增加。有机碳含量是控制页岩微纳米级孔隙发育和比表面积的最重要内因,特别体现在对微孔和中孔发育的控制上;黏土矿物含量增加能增强页岩吸附能力,但对孔隙体积和比表面积主控作用不明显;脆性矿物含量主要控制宏孔发育,对页岩吸附的贡献可以忽略;热演化程度过低或过高均不利于有机质孔隙的发育,微纳米孔隙体积随着成熟度增加呈现出先增后减的趋势,对于高过成熟页岩,不同干酪根类型的有机质孔隙发育程度和比表面积大小次序为Ⅰ型＞Ⅱ型＞Ⅲ型。     

基于聚焦离子束-扫描电镜方法研究页岩有机孔三维结构

页岩中纳米级有机孔的大小直接影响页岩气含气量,其连通性亦对气体运移和开采至关重要。本文选择漆辽地区龙马溪组富有机质页岩,利用聚焦离子束-扫描电镜(FIB-SEM)在纳米尺度上(10 nm)进行有机孔结构的三维重构。研究结果表明:(1)FIB-SEM方法适用于微米级页岩的纳米(3 nm)孔隙结构特征研究。(2)蜂窝状有机孔发育均匀,孔径集中于10~200 nm,连通性较差;界面有机孔孔径集中于200~300 nm,局部连通性较好。(3)页岩总孔隙度与有机质含量成正比。研究认为,对于以有机孔为重要储集空间的页岩,有机质分布越集中,连续性越好,研究孔隙度的表征单元体尺度越小。     

页岩纳米孔隙研究新进展

随着页岩油气勘探的兴起及近年来北美地区页岩油气开发取得的巨大成功,含气页岩储层的孔隙研究受到越来越多的重视。页岩储层不同于常规储层,其以纳米孔隙为主,无法用常规储层孔隙研究方法进行表征和评价。对目前国内外含气页岩孔隙分类及孔隙表征方法进行了综述,从定性及定量的角度对表征方法进行归类和总结,指出了各类方法的优缺点及应用范围。定性表征方法主要是利用聚焦离子束扫描电子显微镜、高分辨率的场发射扫描电子显微镜、透射电子显微镜、宽离子束扫描电子显微镜、原子力显微镜等电子显微成像分析技术及Nano-CT技术等直观描述页岩孔隙的几何形态、连通性和充填情况等;定量表征方法是利用气体吸附法、压汞实验、小角散射及核磁共振等技术定量分析页岩孔径大小及分布、比表面积等。进一步探讨了含气页岩纳米孔隙发育演化的控制因素以及纳米孔隙对页岩气聚集的影响。展望未来,在页岩纳米孔隙结构表征技术方面,应不断提高实验精度和效率,定性与定量表征相结合,改进三维成像技术;在页岩纳米孔隙储层评价研究方面,纳米孔隙发育演化的控制因素、纳米孔隙储层的储气及产气能力、陆相非均质页岩纳米孔隙的表征与评价是关注的重点领域。     

渝东北下寒武统牛蹄塘组页岩微纳米孔隙结构特征

中国南方下寒武统牛蹄塘组页岩是目前页岩气勘探的主要目的层位之一,然而在渝东北地区其勘探效果不尽如人意,原因在于其孔隙结构特征并未清楚.采用聚焦离子束扫描电子显微镜、纳米C和气体吸附实验等方法对渝东北地区下寒武统牛蹄塘组页岩微纳米孔隙结构进行了定量表征.结果表明,牛蹄塘组页岩的微纳米孔隙类型主要为无机质孔隙,包括粒间孔和粒内孔,而N₂吸附滞后环类型属于4型,对应孔隙类型为单边狭缝型孔隙;牛蹄塘组页岩的平均总孔体积为0.0317mL/g,平均总比表面积为34.7m2/g.牛蹄塘组页岩过高的演化程度导致有机质孔隙不发育,进而导致其微纳米孔隙具有较差的连通性;中孔贡献了绝大部分的孔体积,而微孔则贡献了相对较多的比表面积.      

吉木萨尔凹陷芦草沟组页岩储层微纳米孔隙成因及含油特征

为深化吉木萨尔凹陷芦草沟组页岩储层孔隙及含油性认识,通过氩离子抛光、场发射扫描电镜、核磁共振、微纳米CT及激光共聚焦实验技术,对芦草沟组微纳米孔隙类型、成因及含油特征进行研究.结果表明,微纳米级孔隙按照成因分为无机矿物晶间孔和有机质生烃孔两大类.微纳米孔隙中重质组分附着于颗粒表面或充填于纳米级小孔中,轻质组分主要赋存于...     

泥岩微观组构对有机质赋存形式和孔隙发育的影响研究：以白垩系Eagle Ford页岩为例

以美国Texas州白垩系Eagle Ford页岩为研究对象,采用氩离子抛光-场发射扫描电镜技术,并结合X射线能谱分析,对位于生油窗的原始岩心样品和位于生气窗的柱状模拟样品开展镜下有机质赋存形式和孔隙发育、演化特征研究。结果表明,Eagle Ford页岩样品在镜下的不同微区可以划分出硅质黏土质条带、钙质有孔虫化石和富颗石藻透镜体3种典型组构类型,并且不同类型组构中有机质赋存形式和孔隙发育、演化特征存在显著差异。其中,硅质黏土质条带中富集大量无定形干酪根和少量结构型干酪根,无定形干酪根在生油窗由于结构内部滞留了大量吸附油基本不发育孔隙,到了生气窗伴随吸附油裂解开始形成丰富的纳米级海绵状孔隙,而结构型干酪根由于异常低的生烃潜力,基本不发育孔隙;有孔虫化石腔室内部赋存的有机质代表早期充注的运移沥青,在生油窗发育大量气泡状孔隙和丰富的纳米级海绵状孔隙,但在生气窗纳米级孔隙发生相互融合,则开始以发育微米级孔隙为主;富颗石藻透镜体中赋存的有机质可能代表相对后期充注的运移沥青,在生油窗发育丰富的纳米级海绵状孔隙,并未见气泡状孔,且在生气窗由于异常高的有机质转化率,原矿物粒间孔重新暴露,有机质几乎被消耗...     

Rapid screening of Zr-containing particles from Chang’e-5 lunar soil samples for isotope geochronology: Technical roadmap for future study

New samples returned by China Chang’e-5 (CE-5) mission offer an opportunity for studying the lunar geologic longevity, space weathering, and regolith evolution. The age determination of the CE-5 samples was among the first scientific questions to be answered. However, the precious samples, most in the micrometer size range, challenge many traditional analyses on large single crystals of zircon developed for massive bulk samples. Here, we developed a non-destructive rapid screening of individual zirconium-containing particle for isotope geochronology based on a Micro X-ray fluorescence analysis (µXRF). The selected particles were verified via scanning electron microscopy (SEM), 3D X-ray microscopy (XRM), and focused ion beam scanning electron microscopy (FIB-SEM) techniques, which showed that zirconium-bearing minerals with several microns were precisely positioned and readily suitable for site-specific isotopic dating by second ion mass spectrometry (SIMS). Such protocol could be also applicable in non-destructively screening other types of particles for different scientific purposes. We therefore proposed a correlative workflow for comprehensively studying the CE-5 lunar samples from single particles on nanometer to atomic scales. Linking various microscopic and spectromicroscopic instruments together, this workflow consists of six steps: (1) single-particle selection with non-destructive µXRF technique, (2) 2D/3D morphological and structural characterization with a correlative submicron 3D XRM and nanoscale resolution FIB-SEM imaging methods, (3) SEM analysis of the surface morphology and chemistry of the selected particle, (4) a series of microscopic and microbeam analyses (e.g., SEM, electron probe microanalysis, and SIMS) on the cross-section of the selected particle to obtain structural, mineralogical, chemical, and isotopic features from the micron to nanometer scale, (5) advanced 2D/3D characterization and site-specific sample preparation of thin foil/tip specimens on a microregion of interest in the selected particle with FIB-SEM technique, and (6) comprehensive analyses on the FIB-milled specimens at nanometer to atomic scale with synchrotron-based scanning transmission X-ray microscopy, analytic transmission electron microscopy, and atom probe tomography. Following this technical roadmap, one can integrate multiple modalities into a uniform frame of multimodal and multiscale correlated datasets to acquire high-throughput information on the limited or precious terrestrial and extraterrestrial samples.     

Characteristics and Controlling Factors of Shale Oil Reservoir Spaces in the Bohai Bay Basin

The Cenozoic continental strata of the Bohai Bay Basin are rich in shale oil resources, and they contain various types of reservoir spaces that are controlled by complex factors. Using field emission scanning electron microscopy(FESEM), automatic mineral identification and characterization system(AMICS), CO2 and N2 gas adsorption, and focused ion beam scanning electron microscopy(FIB-SEM), the types of shale reservoir spaces in the Bohai Bay Basin are summarized, the spatial distribution and connectivity of the various types of pores are described in detail, the microscopic pore structures are characterized, and the key geological mechanisms affecting the formation and evolution of the reservoir spaces are determined. Three conclusions can be drawn in the present study. First, the shale reservoir spaces in the Bohai Bay Basin can be divided into three broad categories, including mineral matrix pores, organic matter pores, and micro fractures. Those spaces can be subdivided into seven categories and fourteen sub-categories based on the distribution and formation mechanisms of the pores. Second, the complex pore-throat structures of the shale reservoir can be divided into two types based on the shape of the adsorption hysteresis loop. The pore structures mainly include wedge-shaped, flat slit-shaped, and ink bottle-shaped pores. The mesopores and micropores are the main contributors to pore volume and specific surface area, respectively. The macropores provide a portion of the pore volume, but they do not significantly contribute to the specific surface area. Third, the factors controlling the development of microscopic pores in the shale are complex. The sedimentary environment determines the composition and structure of the shale and provides the material basis for pore development. Diagenesis controls the types and characteristics of the pores. In addition, the thermal evolution of the organic matter is closely related to inorganic diagenesis and drives the formation and evolution of the pores.     

Characterization of shale matrix pore structure via experiment and model

Shale gas reservoirs develop multi-scale pores ranging in size from nanometer to micrometer, the characteristics of gas transport involve the multi-scale pore space which divided into organic and inorganic matrix pores. This paper reveals the shale pore structure with large amounts of organic mesoporous based on the techniques of focused ion beam scanning electron microscopes (FIB-SEM), high-pressure mercury intrusion (MICP), and low-pressure adsorption (LPA), which also shows the size and distribution of these pores. Then the research characterizes effective pore scale via circular tube bundle model with due regard for gas adsorption layer thickness on the walls of organic pores and water film thickness on the walls of inorganic pores, and the investigation of shale pore geometry is significant for designing and developing shale gas reservoirs. This work shows that the widely existing shale mesoporous volume with diameter of 2~50 nm accounts for 81% based on experimental testing, then it reduces to about 76% via effective diameter model calculation.     

Research Progress in Shale Nanopores

With the rise of shale oil and gas exploration and great success of North American shale oil and gas development in recent years, the study of gas shale reservoir pores gets more and more attention. The pore diameters of shale reservoirs are mainly in nano-scale which are different from conventional reservoirs, and they can not be evaluated by conventional methods. On the basis of the research on the classification of shale pore types and nanopore characterization techniques, qualitative and quantitative nanopore characterization methods were classified and summarized. In addition, the advantages and disadvantages of various methods as well as application scopes were summarized. Qualitative characterization methods can obtain the morphologic information, connectivity and filling conditions of shale pores directly by focused ion beam milling scanning electron microscopy, field emission scanning electron microscopy, transmission electron microscopy, broad ion beam scanning electron microscope, atomic force microscope and Nano-CT. Quantitative characterization methods can measure pore diameters, pore distribution and specific surface area by nitrogen adsorption experiments, carbon dioxide adsorption experiments, mercury injection experiments, small-angle neutron scattering, and nuclear magnetic resonance. The factors that control nanopore developments and the effects of nanopore on shale gas accumulation were discussed. The nanopore developments are related to total organic carbon content, clay minerals content, carbonate content and thermal maturity. Nanopores have influences on shale gas storage capacity, occurrences of shale gas and seepage mechanisms. Frontier research and development directions were proposed. In the aspect of nanopore characterization techniques of shales, the accuracy and efficiency of the experiments and three dimensional imaging technology should be improved constantly. Qualitative and quantitative characterization techniques should be combined. As to the evaluation of shale nanopore reservoirs, the factors that control nanopore developments, shale gas storing and producing and nanopores characterization and evaluation of continental heterogeneous shale are the key issues for further research.     

Sub-Micrometre Resolution FIB-SEM-based ToF-SIMS Used to Map Geochemical Zoning in Four Zircon Reference Materials

Zircon geochemistry can vary over micrometre scales; therefore, natural reference materials need to be well characterised before being used to calculate trace element mass fractions in unmeasured samples. Moreover, reference material homogeneity needs to be ensured with the accelerating rate of geoanalytical developments to map mineral chemistry at increasingly finer scales. Here, we investigate trace element zoning in four widely used zircon reference materials: 91500, Mud Tank, Temora and Plešovice, as well as zircon crystals from the Mount Dromedary/Gulaga Igneous Complex, Australia. Sub-micrometre resolution focused ion beam scanning electron microscope (FIB-SEM) based time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 5 μm resolution LA-ICP-MS mapping show that trace elements are zoned in all reference materials, though 91500 exhibited the least zonation. We demonstrate that FIB-SEM-based ToF-SIMS can rapidly resolve variations in trace elements (e.g., U, Th, Sc, Y, Gd, Dy, Yb and Li) at sensitivities down to the μg g^-1 level with a spatial resolution of 195 nm for areas 100 × 85 μm to 959 × 828 μm. Zircon 91500 is recommended for future quantitative analyses provided that (1) the spatial distribution of elements is imaged before analysis of unknown samples and (2) it is used in conjunction with a doped glass as the primary reference material.     

丁二酸桥联双核铜Cu(C_3N_2H_4)_2(C_4H_5O_4)_2晶体的超分子结构及形貌特征

用XRD,SEM和TEM研究新型配合物Cu(C3N2H4)2(C4H5O4)2的超分子结构和微观形貌,并对新型晶体的平衡外形进行模拟计算,结果表明:该配合物分子具有丁二酸桥联的双核铜结构,中心铜离子处在2个咪唑和4个丁二酸以单齿配位组成的八面体中心,在ab平面,分子中有十四元大环,环内Cu(1)-Cu(2)原子间距为0.8031nm,C(2)-C(2′)为0.4183nm;在ac平面,沿着[010]方向分子内呈现凹的六边形纳米级孔洞;沿[100]方向分子依靠弱的氢键作用,层状堆积成三维超分子结构。此外,随着丁二酸的碳链沿[001]方向无限延伸,形成以铜离子为交叉中心的带状拓扑构型。SEM观察到晶体表面形成有明显的凹坑,区域呈现层状阶梯,说明晶体在(100)面遵照台阶-扭折模型呈层状生长结晶。TEM微区形貌像显示晶体存在条纹和缺陷结构,整体保持柱状构型,这与模拟的晶体平衡外形呈柱状一致。模拟结果表明晶体最易外显晶面为(100)面,外显比例达41.247%,这与晶体超分子层沿[100]方向通过氢键作用堆积,键作用力较弱密切相关。     

叶腊石微结构及其晶体结构缺陷的高分辨透射电镜分析

采用场发射扫描电镜（FE-SEM）、高分辨透射电镜（HRTEM）结合选区电子衍射（SAED）、X射线粉晶衍射（XRD）及X射线荧光光谱（XRF）等对浙江青田叶腊石的微结构特征进行较系统的研究。结果表明：①粉晶X射线衍射证实青田叶腊石具有典型的单斜晶系特征,该结论与叶腊石粉体选区电子衍射结果吻合,且其伴生矿为石英。②叶腊石微晶体呈＂复式板片＂构型,且＂复式＂板片中薄片厚度约为8±2 nm。③在高能电子束辐照下,叶腊石矿物颗粒形貌及晶格结构发生明显的改变,且由此产生晶格膨胀,并最终形成非晶态。     

Anatomy of a low temperature zircon outgrowth

Outgrowths of zircon and xenotime are abundant on detrital zircon in a greenschist facies regional metamorphic slate from the Scottish Highlands. Back-scattered electron images reveal that ca. 3-μm wide zircon outgrowths are porous, inclusion-rich and contain fine-grained intergrowths with xenotime. Focused ion beam milling, transmission electron microscopy and low-voltage scanning transmission electron microscopy show that the outgrowth microstructure is complex, composed of mis-orientated nano-crystalline zircon and a poorly crystalline zircon–xenotime complex. Well-defined micron-sized xenotime is also present within the outgrowth. Micro-textures show that the outgrowth developed in a polyphase history during cooling and exhumation. Accommodation space for the outgrowth is probably generated by a combination of thermal decompaction and the migration of defects in adjacent quartz driven by the force of crystallisation. Zircon may be unique in its ability to record textural evidence of events during uplift and exhumation that are not recorded in major silicate phases.     

Focussed ion beam–transmission electron microscopy applications in ore mineralogy: Bridging micro- and nanoscale observations

Focussed ion beam–scanning electron microscopy (FIB–SEM) is a relatively new analytical tool that has been little applied to problems of ore genesis. The technique enables high-resolution (cross-section) imaging and can be used to prepare thinned foils for study by transmission electron microscopy (TEM). FIB–SEM methods applied to sulphides and related compounds represent an in-situ approach for sample characterisation and thus provides for crystal–chemical data that can be placed into the geological context of a given ore deposit.We present four study cases: these deal with minor element incorporation and release in ZnS; intergrowths and replacement among Cu–(Fe)-sulphides; fabrics in Au-bearing, As-free pyrite; and symplectites of Bi-sulphosalts within galena. The data is discussed in the context of polytypism and planar defects for minor element incorporation and release, superstructure ordering and formation of fine particles (100–2500 nm) or nanoparticles (< 100 nm) during replacement processes. Several analytical difficulties encountered when preparing FIB–TEM samples from sulphides are discussed, in particular mechanical and chemical damage to the surface. The FIB–TEM foils are difficult to thin for direct high-resolution TEM imaging but are usable for Scanning Transmission Electron Microscopy (STEM) and High-Angle Annular Dark Field (HAADF)-STEM imaging.     

微束分析技术在有机岩石学研究中的应用现状

介绍了扫描电镜能谱、透射电镜、二次离子质谱、激光微探针质谱、显微傅立叶红外光谱等几种微束分析技术的性能特点，系统地论述了其在有机岩石学在应用现状与进展，并较详细地阐述了利用上述技术研究塔里木盆地烃源岩显微组分的结果。