Elucidating the Structure and Composition of Individual Bimetallic Nanoparticles in Supported Catalysts by Atom Probe Tomography.

Understanding and controlling the structure and composition of nanoparticles in supported metal catalysts are crucial to improve chemical processes. For this, atom probe tomography (APT) is a unique tool, as it allows for spatially resolved three-dimensional chemical imaging of materials with sub-nanometer resolution. However, thus far APT has not been applied for mesoporous oxide-supported metal catalyst materials, due to the size and number of pores resulting in sample fracture during experiments. To overcome these issues, we developed a high-pressure resin impregnation strategy and showcased the applicability to high-porous supported Pd-Ni-based catalyst materials, which are active in CO2 hydrogenation. Within the reconstructed volume of 3 × 105 nm3, we identified over 400 Pd-Ni clusters, with compositions ranging from 0 to 16 atom % Pd and a size distribution of 2.6 ± 1.6 nm. These results illustrate that APT is capable of quantitatively assessing the size, composition, and metal distribution for a large number of nanoparticles at the sub-nm scale in industrial catalysts. Furthermore, we showcase that metal segregation occurred predominately between nanoparticles, shedding light on the mechanism of metal segregation. We envision that the presented methodology expands the capabilities of APT to investigate porous functional nanomaterials, including but not limited to solid catalysts.

Geomechanical simulation of energy storage in salt formations.

A promising option for storing large-scale quantities of green gases (e.g., hydrogen) is in subsurface rock salt caverns. The mechanical performance of salt caverns utilized for long-term subsurface energy storage plays a significant role in long-term stability and serviceability. However, rock salt undergoes non-linear creep deformation due to long-term loading caused by subsurface storage. Salt caverns have complex geometries and the geological domain surrounding salt caverns has a vast amount of material heterogeneity. To safely store gases in caverns, a thorough analysis of the geological domain becomes crucial. To date, few studies have attempted to analyze the influence of geometrical and material heterogeneity on the state of stress in salt caverns subjected to long-term loading. In this work, we present a rigorous and systematic modeling study to quantify the impact of heterogeneity on the deformation of salt caverns and quantify the state of stress around the caverns. A 2D finite element simulator was developed to consistently account for the non-linear creep deformation and also to model tertiary creep. The computational scheme was benchmarked with the already existing experimental study. The impact of cyclic loading on the cavern was studied considering maximum and minimum pressure that depends on lithostatic pressure. The influence of geometric heterogeneity such as irregularly-shaped caverns and material heterogeneity, which involves different elastic and creep properties of the different materials in the geological domain, is rigorously studied and quantified. Moreover, multi-cavern simulations are conducted to investigate the influence of a cavern on the adjacent caverns. An elaborate sensitivity analysis of parameters involved with creep and damage constitutive laws is performed to understand the influence of creep and damage on deformation and stress evolution around the salt cavern configurations. The simulator developed in this work is publicly available at https://gitlab.tudelft.nl/ADMIRE_Public/Salt_Cavern .

Seismic Slip-Pulse Experiments Simulate Induced Earthquake Rupture in the Groningen Gas Field.

Rock materials show dramatic dynamic weakening in large-displacement (m), high-velocity (∼1 m/s) friction experiments, providing a mechanism for the generation of large, natural earthquakes. However, whether such weakening occurs during induced M3-4 earthquakes (dm displacements) is unknown. We performed rotary-shear experiments on simulated fault gouges prepared from the source-, reservoir- and caprock formations present in the seismogenic Groningen gas field (Netherlands). Water-saturated gouges were subjected to a slip pulse reaching a peak circumferential velocity of 1.2-1.7 m/s and total displacements of 13-20 cm, at 2.5-20 MPa normal stress. The results show 22%-81% dynamic weakening within 5-12 cm of slip, depending on normal stress and gouge composition. At 20 MPa normal stress, dynamic weakening from peak friction coefficients of 0.4-0.9 to 0.19-0.27 was observed, probably through thermal pressurization. We infer that similar effects play a key role during induced seismic slip on faults in the Groningen and other reservoir systems.

Surface microstructures developed on polished quartz crystals embedded in wet quartz sand compacted under hydrothermal conditions.

Intergranular pressure solution plays a key role as a deformation mechanism during diagenesis and in fault sealing and healing. Here, we present microstructural observations following experiments conducted on quartz aggregates under conditions known to favor pressure solution. We conducted two long term experiments in which a quartz crystal with polished faces of known crystallographic orientation was embedded in a matrix of randomly oriented quartz sand grains. For about two months an effective axial stress of 15 MPa was applied in one experiment, and an effective confining pressure of 28 MPa in the second. Loading occurred at 350 °C in the presence of a silica-saturated aqueous solution. In the first experiment, quartz sand grains in contact with polished quartz prism ([Formula: see text]) faces became ubiquitously truncated against these faces, without indenting or pitting them. By contrast, numerous sand-grain-shaped pits formed in polished pyramidal ([Formula: see text]) and ([Formula: see text]) crystal faces in the second experiment. In addition, four-leaved and (in some cases) three-leafed clover-shaped zones of precipitation formed on these prism faces, in a consistent orientation and pattern around individual pits. The microstructures observed in both experiments were interpreted as evidence for the operation of intergranular pressure solution. The dependence of the observed indentation/truncation microstructures on crystal face orientation can be explained by crystallographic control of stress-induced quartz dissolution kinetics, in line with previously published experimental and petrographic data, or possibly by an effect of contact orientation on the stress-induced driving force for pressure solution. This should be investigated in future experiments, providing data and microstructures which enable further mechanism-based analysis of deformation by pressure solution and the effect of crystallographic control on its kinetics in quartz-rich sands and sandstones.

Microphysical Modeling of Carbonate Fault Friction at Slip Rates Spanning the Full Seismic Cycle.

Laboratory studies suggest that seismogenic rupture on faults in carbonate terrains can be explained by a transition from high friction, at low sliding velocities (V), to low friction due to rapid dynamic weakening as seismic slip velocities are approached. However, consensus on the controlling physical processes is lacking. We previously proposed a microphysically based model (the "Chen-Niemeijer-Spiers" [CNS] model) that accounts for the (rate-and-state) frictional behavior of carbonate fault gouges seen at low velocities characteristic of rupture nucleation. In the present study, we extend the CNS model to high velocities (1 mm/s ≤ V ≤ 10 m/s) by introducing multiple grain-scale deformation mechanisms activated by frictional heating. As velocity and hence temperature increase, the model predicts a continuous transition in dominant deformation mechanisms, from frictional granular flow with partial accommodation by plasticity at low velocities and temperatures, to grain boundary sliding with increasing accommodation by solid-state diffusion at high velocities and temperatures. Assuming that slip occurs in a localized shear band, within which grain size decreases with increasing velocity, the model results capture the main mechanical trends seen in high-velocity friction experiments on room-dry calcite-rich rocks, including steady-state and transient aspects, with reasonable quantitative agreement and without the need to invoke thermal decomposition or fluid pressurization effects. The extended CNS model covers the full spectrum of slip velocities from earthquake nucleation to seismic slip rates. Since it is based on realistic fault structure, measurable microstructural state variables, and established deformation mechanisms, it may offer an improved basis for extrapolating lab-derived friction data to natural fault conditions.

Healing Behavior of Simulated Fault Gouges From the Groningen Gas Field and Implications for Induced Fault Reactivation.

We investigated the frictional strength recovery (healing) and subsequent reactivation and slip-weakening behavior of simulated fault gouges derived from key stratigraphic units in the seismogenic Groningen gas field (N. E. Netherlands). Direct-shear, slide-hold-slide (SHS) experiments were performed at in situ conditions of 100 °C, 40 MPa effective normal stress and 10-15 MPa pore fluid pressure (synthetic formation brine). Sheared gouges were allowed to heal for periods up to 100 days before subsequent reshearing. The initial coefficient of (steady) sliding friction µ was highest in the Basal Zechstein caprock (µ = 0.65 ± 0.02) and Slochteren sandstone reservoir (µ = 0.61 ± 0.02) gouges, and the lowest in the Ten Boer claystone at the reservoir top (µ = 0.38 ± 0.01) and in the Carboniferous shale substrate (µ ≈ 0.45). Healing and subsequent reactivation led to a marked increase (∆µ) in (static) friction coefficient of up to ~0.16 in Basal Zechstein and ~0.07 in Slochteren sandstone gouges for the longest hold periods investigated, followed by a sharp strength drop (up to ~25%) and slip-weakening trajectory. By contrast, the Ten Boer and Carboniferous gouges showed virtually no healing or strength drop. Healing rates in the Basal Zechstein and Slochteren sandstone gouges were significantly affected by the stiffness of different machines used, in line with the Ruina slip law, and with a microphysical model for gouge healing. Our results point to marked stratigraphic variation in healed frictional strength and healing rate of faults in the Groningen system, and high seismogenic potential of healed faults cutting the reservoir and Basal Zechstein caprock units, upon reactivation.

Microscale cavitation as a mechanism for nucleating earthquakes at the base of the seismogenic zone.

Major earthquakes frequently nucleate near the base of the seismogenic zone, close to the brittle-ductile transition. Fault zone rupture at greater depths is inhibited by ductile flow of rock. However, the microphysical mechanisms responsible for the transition from ductile flow to seismogenic brittle/frictional behaviour at shallower depths remain unclear. Here we show that the flow-to-friction transition in experimentally simulated calcite faults is characterized by a transition from dislocation and diffusion creep to dilatant deformation, involving incompletely accommodated grain boundary sliding. With increasing shear rate or decreasing temperature, dislocation and diffusion creep become too slow to accommodate the imposed shear strain rate, leading to intergranular cavitation, weakening, strain localization, and a switch from stable flow to runaway fault rupture. The observed shear instability, triggered by the onset of microscale cavitation, provides a key mechanism for bringing about the brittle-ductile transition and for nucleating earthquakes at the base of the seismogenic zone.

Rock mechanics. Superplastic nanofibrous slip zones control seismogenic fault friction.

Understanding the internal mechanisms controlling fault friction is crucial for understanding seismogenic slip on active faults. Displacement in such fault zones is frequently localized on highly reflective (mirrorlike) slip surfaces, coated with thin films of nanogranular fault rock. We show that mirror-slip surfaces developed in experimentally simulated calcite faults consist of aligned nanogranular chains or fibers that are ductile at room conditions. These microstructures and associated frictional data suggest a fault-slip mechanism resembling classical Ashby-Verrall superplasticity, capable of producing unstable fault slip. Diffusive mass transfer in nanocrystalline calcite gouge is shown to be fast enough for this mechanism to control seismogenesis in limestone terrains. With nanogranular fault surfaces becoming increasingly recognized in crustal faults, the proposed mechanism may be generally relevant to crustal seismogenesis.

Weakening of rock salt by water during long-term creep.

The rheological properties of rock salt are of fundamental importance in predicting the long-term evolution of salt-based radioactive waste repositories and strategic storage caverns, and in modelling the formation of salt diapirs and associated oil traps1,2. The short-term, high-stress rheology of rock salt is well known from laboratory experiments; however, extrapolation to appropriately low stresses fails to predict the rapid flow seen in certain natural structures. Furthermore, experiments have failed to reproduce the recrystallized microstructure of naturally deformed salt. Here we report experiments indicating that the above discrepancies can be explained by taking into account the influence of trace amounts of brine. Trace brine is always present in natural salt but sometimes escapes during experiments. Our tests on dry dilated salt show more or less conventional dislocation creep behaviour, but brine-bearing samples show marked weakening at low strain rates. This is associated with dynamic recrystallization and a change of deformation mechanism to solution transfer creep. Because natural rock salt always contains some brine, these results cast substantial doubt on the validity of presently accepted dislocation creep laws for predicting the long-term rheological behaviour of salt in nature.