Critical Sensing Modalities for Hydrogen: Technical Needs and Status of the Field to Support a Changing Energy Landscape.

Decarbonization of the energy system is a key aspect of the energy transition. Energy storage in the form of chemical bonds has long been viewed as an optimal scheme for energy conversion. With advances in systems engineering, hydrogen has the potential to become a low cost, low emission, energy carrier. However, hydrogen is difficult to contain, it exhibits a low flammability limit (>40000 ppm or 4%), low ignition energy (0.02 mJ), and it is a short-lived climate forcer. Beyond commercially available sensors to ensure safety through spot checks in enclosed environments, new sensors are necessary to support the development of low emission infrastructure for production, transmission, storage, and end use. Efficient scalable broad area hydrogen monitoring motivates lowering the detection limit below that (10 ppm) of best in class commercial technologies. In this perspective, we evaluate recent advances in hydrogen gas sensing to highlight technologies that may find broad utility in the hydrogen sector. It is clear in the near term that a sensor technology suite is required to meet the variable constraints (e.g., power, size/weight, connectivity, cost) that characterize the breadth of the application space, ranging from industrial complexes to remote pipelines. This perspective is not intended to be another standard hydrogen sensor review, but rather provide a critical evaluation of technologies with detection limits preferably below 1 ppm and low power requirements. Given projections for rapid market growth, promising techniques will also be amenable to rapid development in technical readiness for commercial deployment. As such, methods that do not meet these requirements will not be considered in depth.

Fracture-matrix fluid exchange in oil-bearing unconventional mudstones.

The poromechanical properties of unconventional reservoir materials are in large part dictated by their mineralogy. Since these properties govern the response to stress experienced during hydraulic fracturing, fluid production, and fluid injection, they play a central role in the formation of microcracks or bedding delaminations which ultimately dominate mass transport. In this work we study access to the porosity of end member unconventional reservoir materials, where the end members are predominantly dictated by carbonate content. Access to the porosity is quantified using state of the art 3D x-ray computed tomography coupled with physics informed data analytics. Xenon gas, which attenuates x-rays, provides a spatiotemporal map of access to the porosity. The accessible porosity is quantified over a range of net confining stress relevant to the manmade disturbances listed above. These experiments demonstrate that heavily carbonated mudstones are nearly impermeable at the core (~ cm) scale, while carbonate free analogues afford better access to the microstructure. Consistent with previous qualitative 2D radiographs, access to the interior of the clastic mudstones is first observed along planar microcracks, followed by slow penetration into the surrounding matrix. Physics informed data analytics of the 3D tomography measurements presented here show that these microcracks do not permit uniform access to the adjacent rock matrix. In addition, variation of the effective pressure elucidates the mechanisms that govern fracture/matrix fluid exchange. Under conditions consistent with hydrocarbon production fluid accumulates in the immediate vicinity of the nearest microcrack. While there is clear evidence that, as intended, part of this accumulation is from the more distant matrix, fluid is also squeezed out of the microcrack. The fluid build-up at the microcrack indicates that migration out of the rock is hindered by the coupled poroelastic response of the microcrack and adjacent rock matrix. We show that these mechanisms ultimately account for the meager oil recovery factors realized in practice. These insights have implications for making reservoir scale predictions based on core scale observations, and provide a basis for devising new asset development techniques to access more porosity, and enhance fluid extraction. Finally, these findings shed light on key features and mechanisms that govern shale storage capacity, with relevance to other important industrial processes, such as geologic CO2 storage.

Ultrasonic study of water adsorbed in nanoporous glasses.

Thermodynamic properties of fluids confined in nanopores differ from those observed in the bulk. To investigate the effect of nanoconfinement on water compressibility, we perform water sorption experiments on two nanoporous glass samples while concomitantly measuring the speed of longitudinal and shear ultrasonic waves in these samples. These measurements yield the longitudinal and shear moduli of the water-laden nanoporous glass as a function of relative humidity that we utilize in the Gassmann theory to infer the bulk modulus of the confined water. This analysis shows that the bulk modulus (inverse of compressibility) of confined water is noticeably higher than that of the bulk water at the same temperature. Moreover, the modulus exhibits a linear dependence on the Laplace pressure. The results for water, which is a polar fluid, agree with previous experimental and numerical data reported for nonpolar fluids. This similarity suggests that irrespective of intermolecular forces, confined fluids are stiffer than bulk fluids. Accounting for fluid stiffening in nanopores may be important for accurate interpretation of wave propagation measurements in fluid-filled nanoporous media, including in petrophysics, catalysis, and other applications, such as in porous materials characterization.

Origins of pressure dependent permeability in unconventional hydrocarbon reservoirs.

Unconventional hydrocarbon assets represent a rapidly expanding proportion of North American oil and gas production. Similar to the incipient phase of conventional oil production at the turn of the twentieth century, there are ample opportunities to improve production efficiency. In this work we demonstrate that pressure dependent permeability degradation exhibited by unconventional reservoir materials is due to the mechanical response of a few commonly encountered microstructural constituents. In particular, the mechanical response of unconventional reservoir materials may be conceptualized as the superposed deformation of matrix (or ~ cylindrical/spherical), and compliant (or slit) pores. The former are representative of pores in a granular medium or a cemented sandstone, while the latter represent pores in an aligned clay compact or a microcrack. As a result of this simplicity, we demonstrate that permeability degradation is accounted for through a weighted superposition of conventional permeability models for these pore architectures. This approach permits us to conclude that the most severe pressure dependence is due to imperceptible bedding parallel delamination cracks in the oil bearing argillaceous (clay-rich) mudstones. Finally, we demonstrate that these delaminations tend to populate layers that are enriched with organic carbon. These findings are a basis for improving recovery factors through the development of new completion techniques to exploit, then mitigate pressure dependent permeability in practice.

Multiphase flow detection with photonic crystals and deep learning.

Multiphase flows are ubiquitous in industrial settings. It is often necessary to characterize these fluid mixtures in support of process optimization. Unfortunately, existing commercial technologies often fail to provide frequent, accurate, and cost-efficient data necessary to enable process optimization. Here we show a new physics-based concept and testing with lab and field prototypes leveraging photonic crystals for real-time characterization of multiphase flows. In particular, low power (~1 mW) microwave transmission through photonic crystals filled with fluid mixtures may be interrogated by deep learning analysis techniques to provide a fast and accurate characterization of phase fraction and flow morphology. Moreover when these flow characteristics are known, the flow rate is accurately inferred from the differential pressure necessary for the flow to pass through the photonic crystal. This insight provides a basis to develop a unique class of inexpensive, accurate, and convenient techniques to characterize multiphase flows.

Sensitivity of coda wave interferometry to fluid migration through rock.

The sound speed of a porous medium changes with fluid substitution when the fluids have different acoustic properties. The authors demonstrate that coda wave interferometry is capable of sensing subtle local sound speed changes associated with minute fluid displacements, Δh. In fact the resolution on fluid motion is given by a simple scaling relationship, Δhmin/λ∼t-γe2αt, where t is the waveform time, λ is the wavelength, γ is a constant that varies based on the nature of the acoustic propagation, and α is a system specific acoustic attenuation coefficient. In contrast to the conventional notion that later arrivals (further into the coda) give greater sensitivity to fluid movement, this scaling relationship suggests that there is a temporal optimum in sensitivity to Δh. This is the case even though later arrivals exhibit signal intensities well above the noise floor. The authors elucidate the physical basis for determining the waveform time at which the sensitivity is optimal.

Stress-dependent normal-mode frequencies from the effective mass of granular matter.

A zero-temperature critical point has been invoked to control the anomalous behavior of granular matter as it approaches jamming or mechanical arrest. Criticality manifests itself in an anomalous spectrum of low-frequency normal modes and scaling behavior near the jamming transition. The critical point may explain the peculiar mechanical properties of dissimilar systems such as glasses and granular materials. Here we study the critical scenario via an experimental measurement of the normal modes frequencies of granular matter under stress from a pole decomposition analysis of the effective mass. We extract a complex-valued characteristic frequency which displays scaling |ω (σ)| ∼ σΩ' with vanishing stress σ for a variety of granular systems. The critical exponent is smaller than that predicted by mean-field theory opening new challenges to explain the exponent for frictional and dissipative granular matter. Our results shed light on the anomalous behavior of stress-dependent acoustics and attenuation in granular materials near the jamming transition.

Small-amplitude acoustics in bulk granular media.

We propose and validate a three-dimensional continuum modeling approach that predicts small-amplitude acoustic behavior of dense-packed granular media. The model is obtained through a joint experimental and finite-element study focused on the benchmark example of a vibrated container of grains. Using a three-parameter linear viscoelastic constitutive relation, our continuum model is shown to quantitatively predict the effective mass spectra in this geometry, even as geometric parameters for the environment are varied. Further, the model's predictions for the surface displacement field are validated mode-by-mode against experiment. A primary observation is the importance of the boundary condition between grains and the quasirigid walls.

Effect of granular media on the vibrational response of a resonant structure: theory and experiment.

The acoustic response of a structure that contains a cavity filled with a loose granular material is analyzed. The inputs to the theory are the effective masses of each subsystem: that of the empty-cavity resonating structure and that of the granular medium within the cavity. This theory accurately predicts the frequencies, widths, and relative amplitudes of the various flexural mode resonances observed with rectangular bars, each having a cavity filled with loose tungsten granules. Inasmuch as the dominant mechanism for damping is due to adsorbed water at the grain-grain contacts, the significant effects of humidity on both the effective mass of the granular medium as well as on the response of the grain-loaded bars are monitored. Here, depending upon the humidity and the preparation protocol, it is possible to observe one, two, or three distinct resonances in a wide frequency range (1-5 kHz) over which the empty bar has but one resonance. These effects are understood in terms of the theoretical framework, which may simplify in terms of perturbation theories.

Dynamic effective mass of granular media.

We develop the concept of frequency dependent effective mass, M[over ](omega), of jammed granular materials which occupy a rigid cavity to a filling fraction of 48%, the remaining volume being air of normal room condition or controlled humidity. The dominant features of M[over ](omega) provide signatures of the dissipation of acoustic modes, elasticity, and aging effects in the granular medium. We perform humidity controlled experiments and interpret the data in terms of a continuum model and a "trap" model of thermally activated capillary bridges at the contact points. The results suggest that attenuation of acoustic waves in granular materials can be influenced significantly by the kinetics of capillary condensation between the asperities at the contacts.