Orientational mapping of minerals in Pierre shale using X-ray diffraction tensor tomography.

Shales have a complex mineralogy with structural features spanning several length scales, making them notoriously difficult to fully understand. Conventional attenuation-based X-ray computed tomography (CT) measures density differences, which, owing to the heterogeneity and sub-resolution features in shales, makes reliable interpretation of shale images a challenging task. CT based on X-ray diffraction (XRD-CT), rather than intensity attenuation, is becoming a well established technique for non-destructive 3D imaging, and is especially suited for heterogeneous and hierarchical materials. XRD patterns contain information about the mineral crystal structure, and crucially also crystallite orientation. Here, we report on the use of orientational imaging using XRD-CT to study crystallite-orientation distributions in a sample of Pierre shale. Diffraction-contrast CT data for a shale sample measured with its bedding-plane normal aligned parallel to a single tomographic axis perpendicular to the incoming X-ray beam are discussed, and the spatial density and orientation distribution of clay minerals in the sample are described. Finally, the scattering properties of highly attenuating inclusions in the shale bulk are studied, which are identified to contain pyrite and clinochlore. A path forward is then outlined for systematically improving the structural description of shales.

Self-Sensing Well Cement.

Chemical reactions with reservoir fluids and geology related in-situ stress changes may cause damages to cement sealing material in plugged and abandoned oil, gas and CO2 wells. To avoid leakages, a legitimate monitoring technique is needed that could allow for early warning in case such damages occur. In this paper, we test the utility of oil and gas well cement with a conductive filler in sensing stress changes. To this end, we have measured the resistance response of Portland G-oil and gas well cement with carbon nanofibers (CNF) to axial load during uniaxial compressive strength test. Simultaneously, the microseismicity data were collected. The resistance of the nanocomposite was measured using two-point method in the direction of loading. The resistance changes were correlated with acoustic emission events. A total of four different material response regions were distinguished and the resistivity and acoustic emission changes in these regions were described. Our results suggest that the two complementary methods, i.e., acoustic emission and resistance measurements, can be used for sensing stress state in materials including well cement/CNF composites. The results suggest that the well cement/CNF composites can be a good candidate material to be used as a transducer sensing changes in stress state in, e.g., well plugs up to material failure.

Nanoscale imaging of shale fragments with coherent X-ray diffraction.

Despite the abundance of shales in the Earth's crust and their industrial and environmental importance, their microscale physical properties are poorly understood, owing to the presence of many structurally related mineral phases and a porous network structure spanning several length scales. Here, the use of coherent X-ray diffraction imaging (CXDI) to study the internal structure of microscopic shale fragments is demonstrated. Simultaneous wide-angle X-ray diffraction (WAXD) measurement facilitated the study of the mineralogy of the shale microparticles. It was possible to identify pyrite nanocrystals as inclusions in the quartz-clay matrix and the volume of closed unconnected pores was estimated. The combined CXDI-WAXD analysis enabled the establishment of a correlation between sample morphology and crystallite shape and size. The results highlight the potential of the combined CXDI-WAXD approach as an upcoming imaging modality for 3D nanoscale studies of shales and other geological formations via serial measurements of microscopic fragments.

Effects of Water Content and Temperature on Bulk Resistivity of Hybrid Cement/Carbon Nanofiber Composites.

Cement nanocomposites with carbon nanofibers (CNFs) are electrically conductive and sensitive to mechanical loads. These features make them useful for sensing applications. The conductive and load sensing properties are well known to be dependent on carbon nanofiber content; however, much less is known about how the conductivity of hybrid cement-CNF depend on other parameters (e.g., water to cement ratio (w/c), water saturation of pore spaces and temperatures above ambient temperature). In this paper we fill-in these knowledge gaps by: (1) determining a relationship between the cement-CNF bulk resistivity and w/c ratio; (2) determining the effect of water present in the pores on bulk resistivity; (3) describing the resistivity changes upon temperature changes up to 180 °C. Our results show that the increase in the water to cement ratio results in increased bulk resistivity. The decrease in nanocomposite resistivity upon a stepwise temperature increase up to 180 °C was found to be related to free water release from cement pores and the dry materials were relatively insensitive to temperature changes. The re-saturation of pores with water was not reversible with respect to electrical resistivity. The results also suggest that the change in the type of electrical connection can lead to two orders of magnitude different bulk resistivity results for the same material. It is expected that the findings from this paper will contribute to application of cement-CNF-based sensors at temperatures higher than ambient temperature.