A comparative study of X-ray tomographic microscopy on shales at different synchrotron facilities: ALS, APS and SLS.

Synchrotron radiation X-ray tomographic microscopy (SRXTM) was used to characterize the three-dimensional microstructure, geometry and distribution of different phases in two shale samples obtained from the North Sea (sample N1) and the Upper Barnett Formation in Texas (sample B1). Shale is a challenging material because of its multiphase composition, small grain size, low but significant amount of porosity, as well as strong shape- and lattice-preferred orientation. The goals of this round-robin project were to (i) characterize microstructures and porosity on the micrometer scale, (ii) compare results measured at three synchrotron facilities, and (iii) identify optimal experimental conditions of high-resolution SRXTM for fine-grained materials. SRXTM data of these shales were acquired under similar conditions at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory, USA, the Advanced Photon Source (APS) of Argonne National Laboratory, USA, and the Swiss Light Source (SLS) of the Paul Scherrer Institut, Switzerland. The data reconstruction of all datasets was handled under the same procedures in order to compare the data quality and determine phase proportions and microstructures. With a 10× objective lens the spatial resolution is approximately 2 µm. The sharpness of phase boundaries in the reconstructed data collected from the APS and SLS was comparable and slightly more refined than in the data obtained from the ALS. Important internal features, such as pyrite (high-absorbing), and low-density features, including pores, fractures and organic matter or kerogen (low-absorbing), were adequately segmented on the same basis. The average volume fractions of low-density features for sample N1 and B1 were estimated at 6.3 (6)% and 4.5 (4)%, while those of pyrite were calculated to be 5.6 (6)% and 2.0 (3)%, respectively. The discrepancy of data quality and volume fractions were mainly due to different types of optical instruments and varying technical set-ups at the ALS, APS and SLS

Rietveld texture analysis from synchrotron diffraction images. II. Complex multiphase materials and diamond anvil cell experiments

Synchrotron X-ray diffraction images are increasingly used to characterize crystallographic preferred orientation distributions (texture) of fine-grained polyphase materials. Diffraction images can be analyzed quantitatively with the Rietveld method as implemented in the software package Materials Analysis Using Diffraction. Here we describe the analysis procedure for diffraction images collected with high energy X-rays for a complex, multiphase shale, and for those collected in situ in diamond anvil cells at high pressure and anisotropic stress

Synchrotron X-ray Applications Toward an Understanding of Elastic Anisotropy

The contribution of this dissertation is to expand the current knowledge of factors and mechanisms that influence the development of preferred orientation of minerlas and pores in different materials, ranging from rocks in Earth's crust to minerals in the deep Earth. Preferred orientation-a main contributing component to elastic anisotropy-is however very challenging to quantify. The overall focus of this thesis thus aims to (1) apply the capabilities of synchrotron X-ray techniques to determine preferred orientations of hexagonal metals and shales under different conditions and (2) enhance our understanding of their relationships to the elastic properties. Lattice preferred orientation (LPO) or `texture' of hexagonal close-packed iron (hcp- Fe) crystals during deformation has been suggested as the cause of the elastic anisotropy observed in Earth's inner core. However, relatively little is known about LPO of other hcp metals. An investigation of a wide range of hcp metals (Cd, Zn, Os, and Hf) as analogs to hcp-Fe was thus undertaken to better understand deformation mechanisms at high pressure and temperature in Chapter 2. The diamond anvil cell in a radial geometry (rDAC) and the D-DIA multi-anvil apparatus, equipped with a heating system, were used to impose both pressure and stress on the samples. These state-of-the-art tools enable us to create extreme conditions similar to the Earth's interior. A synchrotron X-ray beam is then employed to record diffraction patterns of the deformed materials. Results show that all hcp metals preferentially align their c-axes near the compression axis during deformation but with considerable differences. The gradual texture evolution in Cd and Zn is mainly controlled by basal slip systems while a rapid texture development in Os and Hf at ambient temperature is due to a dominant role of tensile twinning, with some degree of basal slip. At elevated temperature, tensile twinning is suppressed and texturing is governed by combined basal and prismatic slip. Under all conditions, basal slip appears to be the main deformation mechanism in hcp metals at high pressure and temperature. These findings are similar to those of hcp-Fe and useful to better understand the deformation mechanisms of hcp metals and their implications for elastic anisotropy. Besides the investigation of deep Earth materials, this dissertation also considers crustal rocks: particularly shales, which are among the most anisotropic rocks. Shale has increasingly received attention because of its significance in prospecting for petroleum deposits, as well as seals in the context of CO2 sequestration. Elastic anisotropy in shales is caused by the LPO of clay minerals as well as by shape preferred orientation (SPO) of pore, fractures, and the organic material (kerogen) network. However, due to the small grain size and poor crystallinity of swelling clays, the LPO of clays is difficult to quantify. In Chapter 3, a high-energy synchrotron X-ray diffraction technique was applied to characterize LPO and phase proportions of Posidonia Shale collected in the Hils Syncline from Germany, in order to examine the influence of clay content, burial depth, and thermal history. The samples used in this study had experienced different local temperatures during burial and uplifting, as established by the maturity of kerogen (0.68-1.45% vitrinite reflectance, Ro), but their constituent clay minerals, including kaolinite, illite-mica, and illite-smectite, show similar degrees of LPO in all samples, ranging between 3.7 and 6.3 multiple of random distribution (m.r.d.). These observations imply that the difference in local thermal history, which significantly affects the maturity of kerogen, at most marginally influences LPO of clays, as the alignment of clays was established early in the history. In Chapter 4, the SPO of constituents phases in Kimmeridge Shale (North Sea, UK) and Barnett Shale (Gulf of Mexico, USA) was quantified to a resolution of ~1 μm by using synchrotron X-ray microtomography (SXMT) technique. Measurements were done at different facilities (ALS, APS, and SLS) to characterize 3D microstructures, explore resolution limitations, and develop satisfactory procedures for data quantification. Segmentation images show that the SPO of low density features, including pores, fractures, and kerogen, is mostly anisotropic and oriented parallel to the bedding plane. Small pores are generally dispersed, whereas some large fractures and kerogen have irregular shapes and remain aligned horizontally. In contrast, pyrite exhibits no SPO. The volume fractions and aspect ratios of low density features extracted from three synchrotron sources show excellent agreement with 6.3(6)% for Kimmeridge Shale and 4.5(4)% for Barnett Shale. A small variation is mainly due to differences of optical instruments and technical setups. The SXMT is proven to be a crucial technique to investigate 3D internal structures of fine-grained materials at high-resolution. A relationship between LPO, SPO, and elastic anisotropy of the Qusaiba Shale from the Rub'al-Khali basin in Saudi Arabia is established in Chapter 5. The Qusaiba samples exhibit strong LPO of clay minerals (2.4-6.8 m.r.d.) due to their high total clay content and high degree of compaction. The SPO of pores, fractures, and kerogen here are also anisotropic and organized mainly parallel to bedding, with little connectivity of the flat pores normal to the bedding. The microscopic information (LPO) extracted from different synchrotron X-ray techniques is then applied in different averaging approaches (Voigt, Reuss, Hill, and Geometric mean) to calculate macroscopic properties of shales. A comparison of calculated elastic properties (Vp(max)=6.2 km/s, Vp(max)=5.5 km/s, and Vp ani.% =12%) with ultrasonic measurements (Vp(max)=5.3 km/s, Vp(max)=4.1 km/s, and Vp ani.% =27%) suggests some discrepancy as the distribution of kerogen and the orientation of the microfracture and porosity network are not included in the averaging model. These features reduce the strength of the matrix, enhancing the elastic anisotropy. Through linking the matrix and porosity components, a more comprehensive model of shale elastic properties is thus necessary for a further study

Seismic characteristics of polygonal fault systems in the Great South Basin, New Zealand

A well-developed multi-tier polygonal fault system is located in the Great South Basin offshore New Zealand’s South Island. The system has been characterised using a high-quality three-dimensional seismic survey tied to available exploration boreholes using regional two-dimensional seismic data. In this study area, two polygonal fault intervals are identified and analysed, Tier 1 and Tier 2. Tier 1 coincides with the Tucker Cove Formation (Late Eocene) with small polygonal faults. Tier 2 is restricted to the Paleocene-to-Late Eocene interval with a great number of large faults. In map view, polygonal fault cells are outlined by a series of conjugate pairs of normal faults. The polygonal faults are demonstrated to be controlled by depositional facies, specifically offshore bathyal deposits characterised by fine-grained clays, marls and muds. Fault throw analysis is used to understand the propagation history of the polygonal faults in this area. Tier 1 and Tier 2 initiate at about Late Eocene and Early Eocene, respectively, based on their maximum fault throws. A set of three-dimensional fault throw images within Tier 2 shows that maximum fault throws of the inner polygonal fault cell occurs at the same age, while the outer polygonal fault cell exhibits maximum fault throws at shallower levels of different ages. The polygonal fault systems are believed to be related to the dewatering of sedimentary formation during the diagenesis process. Interpretation of the polygonal fault in this area is useful in assessing the migration pathway and seal ability of the Eocene mudstone sequence in the Great South Basin

Mineral preferred orientation and microstructure in the Posidonia Shale in relation to different degrees of thermal maturity

The thermal maturity of samples of the Posidonia Shale collected from the Hils Syncline, northern Germany, varies significantly as a function of location indicating variations in local history. Synchrotron X-ray diffraction was used to document the composition and the preferred orientation of four samples of the Posidonia Shale with different degrees of maturity (0.68-1.45%, R) to determine possible effects on diagenesis and preferred orientation. Overall, the degree of preferred orientation of all clay minerals (illite-smectite, illite-mica, and kaolinite) and in all samples is similar, with (001) pole figure maxima ranging from 3.7 to 6.3 multiples of a random distribution (m.r.d.). Calcite displays weak preferred orientation, with c axes perpendicular to the bedding plane (1.1-1.3 m.r.d.). Other constituent phases such as quartz, feldspars, and pyrite have a random orientation distribution. The difference in thermal history, which causes significant changes in the maturity of organic matter, influenced the preferred orientation of clay minerals only marginally as most of the alignment seems to have evolved early in their history. Synchrotron X-ray microtomography was used to characterize the three-dimensional microstructure of a high-maturity sample. Low-density features, including porosity, fractures, and kerogen, were observed to be elongated and aligned roughly parallel to the bedding plane. The volume of low-density features was estimated to be ~7 vol.%, consistent with previous petrophysical measurements of porosity of 8-10 vol.%. Transmission electron microscopy analysis of samples with different degrees of maturity (0.74%R and 1.45%R) was used to document microstructures at the nanoscale as well as the presence of kerogen. In the high-maturity sample, pores were less abundant while minerals were more deformed as shown by fractured calcite and by kinked and folded illite. Some of the porosity was aligned with clay platelets

Incorporating carbon sequestration materials in civil infrastructure: A micro and nano-structural analysis

The Calera method for carbon sequestration promotes carbon mineralization through aqueous precipitation. This work reports a comprehensive analysis on a carbonate obtained by the Calera process to evaluate its suitability as a cement replacement for concrete applications. This work focuses on the analysis of two hydrated cement pastes made with a blend of Portland cement and Calera carbonates by various advanced analytical techniques. Scanning Electron Microscopy (SEM) equipped with Energy Dispersive Spectroscopy (EDS) was used to observe microstructures and determine elemental compositions. The synchrotron X-ray diffraction technique combined with Rietveld analysis were applied to identify constituent phases and refine crystal structures, crystallite sizes as well as relative phase abundances. Calcite and vaterite are observed in all samples while CSH II and portlandite are dominant in the cement pastes. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectrometry and Scanning Transmission X-ray Microscopy (STXM) experiments were conducted to investigate chemical speciation and morphological information of carbonate minerals with different absorption energies. STXM results confirmed heterogeneity of the samples, and also provided a nano-scale phase map across multiple particles. Differential Thermogravimetric (DTG) was used to observe heat transfer through structures and changes in mass upon heating. A compressive strength tests were performed on materials and shown comparable strength to Portland cement. © 2013 Elsevier Ltd. All rights reserved

A comparative study of X-ray tomographic microscopy on shales at different synchrotron facilities: ALS, APS and SLS.

Synchrotron radiation X-ray tomographic microscopy (SRXTM) was used to characterize the three-dimensional microstructure, geometry and distribution of different phases in two shale samples obtained from the North Sea (sample N1) and the Upper Barnett Formation in Texas (sample B1). Shale is a challenging material because of its multiphase composition, small grain size, low but significant amount of porosity, as well as strong shape- and lattice-preferred orientation. The goals of this round-robin project were to (i) characterize microstructures and porosity on the micrometer scale, (ii) compare results measured at three synchrotron facilities, and (iii) identify optimal experimental conditions of high-resolution SRXTM for fine-grained materials. SRXTM data of these shales were acquired under similar conditions at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory, USA, the Advanced Photon Source (APS) of Argonne National Laboratory, USA, and the Swiss Light Source (SLS) of the Paul Scherrer Institut, Switzerland. The data reconstruction of all datasets was handled under the same procedures in order to compare the data quality and determine phase proportions and microstructures. With a 10× objective lens the spatial resolution is approximately 2 µm. The sharpness of phase boundaries in the reconstructed data collected from the APS and SLS was comparable and slightly more refined than in the data obtained from the ALS. Important internal features, such as pyrite (high-absorbing), and low-density features, including pores, fractures and organic matter or kerogen (low-absorbing), were adequately segmented on the same basis. The average volume fractions of low-density features for sample N1 and B1 were estimated at 6.3 (6)% and 4.5 (4)%, while those of pyrite were calculated to be 5.6 (6)% and 2.0 (3)%, respectively. The discrepancy of data quality and volume fractions were mainly due to different types of optical instruments and varying technical set-ups at the ALS, APS and SLS

Incorporating carbon sequestration materials in civil infrastructure: A micro and nano-structural analysis

The Calera method for carbon sequestration promotes carbon mineralization through aqueous precipitation. This work reports a comprehensive analysis on a carbonate obtained by the Calera process to evaluate its suitability as a cement replacement for concrete applications. This work focuses on the analysis of two hydrated cement pastes made with a blend of Portland cement and Calera carbonates by various advanced analytical techniques. Scanning Electron Microscopy (SEM) equipped with Energy Dispersive Spectroscopy (EDS) was used to observe microstructures and determine elemental compositions. The synchrotron X-ray diffraction technique combined with Rietveld analysis were applied to identify constituent phases and refine crystal structures, crystallite sizes as well as relative phase abundances. Calcite and vaterite are observed in all samples while CSH II and portlandite are dominant in the cement pastes. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectrometry and Scanning Transmission X-ray Microscopy (STXM) experiments were conducted to investigate chemical speciation and morphological information of carbonate minerals with different absorption energies. STXM results confirmed heterogeneity of the samples, and also provided a nano-scale phase map across multiple particles. Differential Thermogravimetric (DTG) was used to observe heat transfer through structures and changes in mass upon heating. A compressive strength tests were performed on materials and shown comparable strength to Portland cement. © 2013 Elsevier Ltd. All rights reserved