High-temperature X-ray diffraction and Raman spectroscopy of diopside and pseudowollastonite

Diopside (CaMgSi₂O₆) and pseudowollastonite (CaSiO₃) have been studied by X-ray powder diffraction and Raman spectroscopy up to their respective melting points. In agreement with previous unit-cell parameters determinations below 1100 K, thermal expansion of diopside along the a and c axis is much smaller than along the b axis. For pseudowollastonite, the axis expansivity increases slightly in the order b>a>c. For both minerals, the change in unit-cell angles is very small and there are no anomalous variations of the other unit-cell parameters near the melting point. With increasing temperatures, the main changes observed in the Raman spectra are strong increases of the linewidths for those bands which mainly represent Si−O−Si bending (near 600 cm⁻¹) or involve Ca−O or Mg−O stretching, in the range 270–500 cm⁻¹ for diopside, and 240–450 cm⁻¹ for pseudowollastonite. At temperatures near the onset of calorimetric premelting effects, this extensive band widening results in a broad Raman feature that can no longer be deconvoluted into its individual components. No significant changes affect the Si−O streching modes. For both diopside and pseudowollastonite, premelting appears to be associated with enhanced dynamics of the alkaline-earth elements. This conclusion contrasts markedly with that drawn for sodium metasilicate in which weaker bonding of sodium allows the silicate framework to distort and deform in such a way as to prefigure the silicate entities present in the melt. Received 16 July 1997 / Revised, accepted: 6 March 1998     

场发射扫描电镜及PerGeos系统在安页1井龙马溪组页岩有机质孔隙研究中的联合应用

安页1井是中国地质调查局在我国南方盆地外围武陵山复杂构造区实施并取得页岩气突破的一口地质调查参数井。本文以安页1井龙马溪组富有机质页岩为研究对象,利用场发射扫描电镜,研究了上扬子地区盆地外围龙马溪组富有机质页岩储集空间类型,并将Per Geos数字岩石处理系统引入有机质孔隙定量分析,定量刻画了有机质微纳米孔隙结构及发育特征。研究认为:有机质孔隙是安页1井龙马溪组富有机质页岩最主要的储集空间,形态上表现为填隙于自生硅质中的有机质发育着均匀海绵状孔隙结构,或与黏土矿物交互生长的有机质发育着气泡状孔隙结构,这两类不同赋存形态的有机质的孔隙均极为发育。通过Per Geos数字岩石系统处理,揭示了两类有机质孔隙孔径发育呈现双众数分布,其中海绵状结构的有机质孔隙孔径众数为5~10 nm,气泡状结构的有机质孔隙孔径众数为51~100 nm,有机质孔隙主要介于中孔~宏孔范畴。安页1井龙马溪组有机质孔隙的大量发育,指示了盆地外围的龙马溪组页岩经历了较强烈的生烃过程并具有较好的储集能力,具备良好的开发潜力。     

TEM imaging of polytypism in pseudowollastonite

A study of polytypism in synthetic polycrystalline pseudowollastonite has been made using conventional and high resolution transmission electron microscopy (TEM and HRTEM). Three polytypes of 2, 4 and 6-layers coexist in the one sample in the form of lamellae parallel to (001). From the electron microscopy images the lamellae are interpreted as combinations of the stacking fault vectors: 1/3 [010], 1/6 [310] and 1/6 [3 $\bar 1$ 0], which are probably all equivalent at high temperatures. The polytype lamellae are stable even after prolonged annealing at high temperatures greater than 1700K. These observations suggest that the most frequently reported 4-layer polytype is not the only high-temperature stable polytype. No evidence of melt is detected in samples annealed in the regime where premelting behaviour of pseudowollastonite has previously been reported (above 1600 K).     

Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

非常规油气致密储集层微观结构研究进展*

致密储集层储集性能差, 孔喉以纳米级为主, 孔喉连通复杂。中国南方高过成熟海相页岩有机质纳米孔与粒内孔大小约为20～890 nm;陆相泥页岩孔喉类型为有机质孔与基质孔, 主体介于30～200 nm之间;致密砂岩微米级孔喉为粒间溶孔、颗粒溶蚀孔与微裂缝, 主体介于10～200μm之间, 纳米级孔隙大小介于70～400 nm之间, 以原生粒间孔与自生矿物晶间孔为主;致密灰岩孔喉类型有方解石粒内溶孔、粒间溶孔与微裂缝, 大小介于50～500 nm之间。页岩微孔喉总体随热演化程度增高呈先减少后增加趋势, 致密含油砂岩中油气赋存有4种状态, 粒间微孔为油气赋存最有利位置。针对非常规油气储集层独特特征, 仍需在仪器研发、技术方法与评价参数等方面加强研究探索。     

川西北中二叠统茅口组储层特征及成因

对四川盆地西北部钻井岩心、露头剖面样品的宏观及微观岩石学特征研究认为,川西北茅口组储层类型主要为生屑灰岩,储集空间主要为生物格架孔、粒间溶孔、粒内溶孔、溶蚀孔洞及裂缝。茅口组储层的发育主要受到沉积微相、古岩溶作用及构造作用等因素控制。其中沉积微相是储层形成的物质基础,古岩溶作用是储层形成的关键因素,而构造裂缝是储层改善及连通的重要因素。     

陆梁油田储层成岩作用与孔隙演化

对陆梁油田白垩系及侏罗系储层成岩作用过程的研究表明,储层的孔隙演化主要与压实作用、溶蚀作用和胶结作用等有密切关系。压实作用、石英次生加大和高岭石的后期充填作用是使孔隙遭受破坏的主要成岩作用类型,长石和碳酸盐矿物的溶蚀作用是形成次生孔隙的主要成岩作用类型。各种成岩作用的时空配置关系控制着孔隙的发育程度;储层孔隙发育具垂向分带性,在纵向上发育一个次生孔隙带,这对预测本区储层物性的空间分布具有重要意义。     

Premelting and calcium mobility in gehlenite (Ca2Al2SiO7) and pseudowollastonite (CaSiO3)

 Premelting effects in gehlenite (Ca₂Al₂SiO₇) have been studied by Raman spectroscopy and calorimetry, and in gehlenite and pseudowollastonite (CaSiO₃) by electrical conductivity. The enthalpy of premelting of gehlenite is 17.3 kJ mol⁻¹ and represents 9% of the reported enthalpy of fusion, which is in the range of the reported fraction of other minerals. The Raman and electrical conductivity experiments at high temperatures, for gehlenite and pseudowollastonite, show that the premelting effects of both compositions are associated with enhanced dynamics of calcium atoms near the melting point. This conclusion agrees with the results obtained for other minerals like diopside, but contrasts with those found for sodium metasilicate in which the weaker bonding of sodium allows the silicate framework to distort near the melting temperature and deform in such a way to prefigure the silicate entities present in the melt. Received: 30 April 2002 / Accepted: 7 August 2002 Acknowledgements We thank Y. Linard for help with DSC measurements and two anonymous reviewers for their constructive comments. This work has been partly supported by the EU Marie-Curie fellowship contract no. HPMF-CT-1999-00329, the CNRS-Carnegie Institution of Washington program PICS no.192, and the NSF grants EAR-9614432 and EAR-9901886 to B.O.M.     

高岭-蒙脱混合黏土渗透各向异性模型研究

完善的渗透各向异性模型有助于指导地下建筑施工期和运营期的排水注浆方案的选定,为了建立完善的渗透各向异性模型,利用三轴渗透仪对高岭-蒙脱混合黏土开展一系列渗透试验,并从宏观和微观两个角度尝试建立渗透各向异性模型。研究结果表明：随着膨润土掺入量增加,混合黏土中小孔隙含量不变,中孔隙含量增多,而大孔隙含量减少;随着固结应力的增大,混合黏土中孔隙均减少,且孔隙最大孔径减小;宏观参数孔隙比和液限孔隙比与渗透各向异性比之间的规律性较弱,说明孔隙比和液限孔隙比不是决定渗透各向异性比的关键参数;用微观参数表述的渗透各向异性模型有较强的规律性,说明从微观角度探究渗透各向异性模型不仅可行,而且更能揭示混合黏土渗透各向异性的本质,且微观参数模型中,用能反映较大孔隙变化的孔径指数 ～ 表述的渗透各向异性模型相关性最好。     

Uvarovite: Stability of uvarovite-andradite solid solutions at low pressure

Uvarovite (Ca₃Cr₂Si₃O₁₂) forms a complete solid solution series with andradite (Ca₃Fe ₂ ⁺³ Si₃O₁₂) below 1,137±5 ° C at a total pressure of 1 atm. Pure uvarovite decomposes to pseudowollastonite (CaSiO₃)+eskolaite (Cr₂O₃) at 1,385 ± 10 ° C. The incorporation of Ca₃Fe ₂ ⁺³ Si₃O₁₂ component in the uvarovite structure lowers the thermal stability of the garnet. The breakdown assemblage is garnet_ss (Ca₃(Cr,Fe⁺³ ₂)Si₃O₁₂)+pseudowollastonite (CaSiO₃)+hemeskolaite_ss(Cr,Fe⁺³O₃). Pure andradite decomposes to pseudowollastonite (CaSiO₃)+hematite (Fe₂O₃) at 1,137±5 °C. Andradite thermal stability is increased by incorporation of Ca₃Cr₂Si₃O₁₂ component by 248 °C.At 1,264±5 °C pseudowollastonite+hematite react to liquid defining a thermal minimum of the CaSiO₃-Cr₂O₃-Fe₂O₃ ternary system. This minimum is located at about 64.5 wt.-% CaSiO₃, 0.5 wt.-% Cr₂O₃, and 35.0 wt.-% Fe₂O₃. Uvarovite and andradite bulk compositions start to melt at 1,420 °C and 1,265 ±5 °C, respectively.The unit-cell parameter for uvarovite is 11.999 (2) Å, the refractive index 1.866 (2). The substitution of Cr⁺³ by Fe⁺³ increases a and n almost linearly toward the andradite end member which displays a unit-cell parameter of 12.059 (3) Å and a refractive index of 1.887 (2).     

Bio-mediated calcium carbonate precipitation and its effect on the shear behaviour of calcareous sand

Calcareous sands have abundant intraparticle pores and are prone to particle breakage. This often leads to poor engineering properties, which poses a challenge to coastal infrastructure construction. A study using bio-cementation to improve the engineering properties of calcareous sand is presented in this paper. The macro- and microscopic properties of bio-cemented calcareous sand were characterized by drained triaxial tests and scanning electron microscopy observations. Experimental results show that the precipitated calcium carbonate can effectively fill the intra- and interparticle pores and bond adjacent particles, thus enhancing the shear strength of calcareous sand. The special structures (e.g. abundant intraparticle pores and rough surface) and mineral components (i.e. calcium carbonate) of calcareous sand are beneficial for improving bacterial retention in soil, which leads to a relatively uniform and dense calcium carbonate distribution on the sand particle surface, exhibiting a layer-by-layer growth pattern. This growth pattern and the abundant interparticle pores would result in less effective calcium carbonate. The strength enhancement of bio-cemented calcareous sand is significantly lower than that of bio-cemented silica sand at the same calcium carbonate content, which may be caused by the differences in the following: (a) soil skeleton strength; (b) the amount of effective calcium carbonate; and (c) interparticle pore-filling of calcium carbonate.

     

Effects of internal pores on the mechanical properties of marine calcareous sand particles

Calcareous sand is a typical problematic marine sediment because of its angular and porous particles. The effects of internal pores on the mechanical properties of calcareous sand particles have rarely been investigated. In this paper, the apparent morphology and internal structure of calcareous sand particles are determined by scanning electron microscopy and computed tomography tests, finding that the superficial pores connect inside and outside of the particles, forming a well-developed network of cavities and an internal porosity of up to 40%. The effects of particle morphology and internal porosity on the mechanical responses of particle were investigated by conducting photo-related compression test and 3D numerical simulations. Two failure modes are observed for the porous calcareous sand, i.e., compressive failure indicates that the particle skeleton is continually compressed and fragmented into small detritus without obvious splitting, and tensile failure indicates that the particles are broken into several fragments when the axial force clearly peaks. Calcareous sand particles with a high internal porosity or with small and dense pores often exhibit compressive failure, and vice versa. The particle strength is considerably reduced by increasing the internal porosity, but affected by pore size in nonlinear correlation. The crushing stress–strain points can be well fitted by an exponential curve, which is supplied for discussion.

     

安徽铜陵早二叠世茅口期Tubiphytes—叶状藻丘储集条件研究

茅口期 Tubiphytes—叶状藻丘及其碳酸盐岩组合的储集空间类型包括孔隙、洞穴、缝隙和喉道,形成了孔隙—喉道型、裂隙—喉道型、孔洞—裂隙型等三种类型的储集空间结构。据孔隙度、渗透率、压汞等分析测试认为,叶状藻障积岩可以成为差的储集岩,而亮晶藻屑灰岩、生屑灰泥岩、Tubiphytes 粘结岩等均为非储集岩。研究区藻丘中含有大量的碳沥青(尤其是深埋溶孔中)也说明了在潜伏礁(丘)体中寻找良好油气储层的潜力是很大的。     

塔中Ⅰ号断裂坡折带上奥陶统碳酸盐岩储层微观孔隙成因

塔中Ⅰ号断裂坡折带上奥陶统良里塔格组碳酸盐岩储集空间类型主要有孔、洞、缝三大类,微观储集空间主要有粒内溶孔、铸模孔、粒间溶孔、晶间溶孔和微裂缝。通过对台地边缘16口井的良里塔格组灰岩进行岩石薄片鉴定、胶结物地球化学分析以及成岩演化序列研究,指出微观孔隙主要形成于埋藏成岩环境中,并列出4项具有指示意义的证据,包括：方解石胶结物中高温包裹体普遍存在;方解石胶结物稳定氧碳同位素丰度分异特征;灰岩中丰富与优质储层伴生的指示埋藏成岩作用的白云石;广泛分布的H₂S气体。此外,分析了溶蚀性流体的主要组分和不同区域埋藏溶蚀作用强度的差异性。     

Elastic-wave velocities for porous media with power-law distribution of pore sizes

 A system consisting of an elastic matrix with randomly distributed pores of uniform shapes but with sizes governed by a power-law distribution is investigated in a theoretical way. The velocities of elastic waves propagating through such a system are calculated. The obtained results are that the velocities decrease with increasing total porosity and for a given porosity velocities moderately decrease with increasing absolute value of the exponent D in a power-law distribution of pore sizes. Received: 3 July 1995 / Accepted: 2 August 1996     

富有机质页岩有机质孔隙度研究——以黔西北下志留统五峰—龙马溪组为例

黔西北下志留统五峰—龙马溪组是我国南方海相页岩气勘探的重要目的层,其孔隙类型除了与常规储层相似的粒间孔、粒内孔、溶蚀孔等孔隙外,还发育了大量的有机质孔。近年来,越来越多的研究发现,页岩气储层中有机质孔占有十分重要的地位。本次研究中发现页岩岩石样品中占主要体积的孔隙类型是中孔(2 nm～50 nm)占比44.16%～82.39%,其次是微孔(<2 nm)占比8.57%～41.23%,宏孔(>50 nm)最少,占比4.02%～16.41%;从场发射扫描电子显微镜照片中可以看出,许多宏孔、中孔有明显的挤压变形现象,说明岩石经历了较长时间的压实作用,并可能伴随着部分孔隙被其他矿物充填的过程。由回归分析可以看出:总有机碳(TOC)含量强烈影响微孔和中孔的发育和演化,尤其是对中孔的影响明显,TOC与这两种孔隙体积之间都存在着明显的正相关关系;石英对中孔发育有一定影响,但不如前者明显,同时石英与微孔之间存在一定的负相关关系;黏土矿物与中孔发育之间存在负相关关系;Ro与微孔、中孔占总孔隙体积的百分比有着良好的正相关关系,而与宏孔占总孔隙百分比有着良好的负相关关系。     

基于统计学方法的页岩孔容预测

页岩气储集空间与储层矿物特征关系密切,以四川盆地东缘龙马溪组页岩为研究对象,利用矿物组成、微量元素、地球化学等测试结果,结合低温氮气吸附法和高分辨率成像技术,采用多元统计分析方法,建立了页岩孔容预测方程,并分析孔隙分布特征和影响因素。结果表明,龙马溪组中部和底部页岩组分含量差异较大,生物成因的自生石英发育是龙马溪组底部石英含量高的主要原因;页岩纳米级孔隙以2~5 nm为主,对孔容贡献率介于64.2%~70.1%;建立的页岩组分含量与孔容的预测模型高度显著。脆性矿物孔、黏土矿物片间孔及其粒内孔是富黏土矿物页岩的主要孔隙类型,孔隙呈微缝状,小于2 nm孔隙不发育;有机质含量是富有机质页岩孔容大小的主控因素,有机质孔的面孔率介于8.8%~12.5%;有机质含量及成熟度是小于2 nm微孔发育的主控因素,大于50 nm孔隙的发育则受控于黏土矿物、石英及长石含量。      

真空预压法淤堵泥层形成机理及预测模型研究

针对真空预压加固处理过程中容易形成的淤堵现象,结合室内真空预压模型试验,进行了不同颗粒组成和不同真空度条件下的室内试验,揭示了淤堵泥层的形成特性和机理,建立了排水量及平均含水率随时间变化的预测模型。试验表明,在低真空度作用下,由于其渗透路径宽而长,淤堵泥层厚度较大,但含水率和密实度低,形成的孔隙直径分布广且分布较均匀;而在高真空度作用下渗透路径窄而短,淤堵泥层厚度小但含水率和密实度高,形成的孔隙直径较小且分布集中;黏粒含量越高形成的孔隙直径越小,集中程度较高,滤层结构越稳定。     

Pore structure and adsorption behavior of shale gas reservoir with influence of maturity: a case study of Lower Silurian Longmaxi formation in China

Knowledge of pore structure and adsorption capacity provides guidance for better studying the origin, hydrocarbon distribution, and productivity of shale gas reservoir. In this study, pore structure characteristics of six shale core plugs with different maturity from the Lower Silurian Longmaxi formation in south China were investigated using the Rock-eval analysis, X-ray diffraction, total organic carbon (TOC) content test, and scanning electron microscope (SEM) observation. To further investigate the influence of maturity, the adsorption behavior of gas shale was experimentally measured, with the maximal pressure being 20 MPa. Rock-eval analysis indicates that Ro is 0.67~1.34%. SEM results show that organic matter (OM) pores are abundant in high-maturity shale sample. The OM pores are mainly irregular to elliptical in shape, the size is 8~100 nm. The TOC content is 0.16~4.21% and shows a positive correlation with the BET surface area. A negative relationship exists between TOC content and average pore diameter, which indicates that abundant nanometer pores are related to the OM. A noticeable characteristic in the pore size distribution curve is that the content of micropores (pore width <?2 nm) increases with the increasing TOC content. Additionally, the thermal maturity results in significant difference in methane adsorption capacity. Maximal adsorption capacity of shale samples is also lineally correlated with TOC content, which increases with maturity. This study provides a quantitative understanding of how maturity affects pore structure and adsorption behavior of shale gas reservoir.