Pore Structure Evolution and Failure Mechanism of Limestone in the Taiyuan Formation of the Ordos Basin under High Temperature.

The study on the destruction of the limestone microstructure after high-temperature treatment has a significant value in the airtightness and safety of underground high-temperature geotechnical engineering. In order to truly simulate the influence of the underground high-temperature environment on limestone, taking seven groups of limestones of the Taiyuan Formation in the Ordos Basin as examples, we carried out a high-temperature (25-1200 °C) heating experiment of limestone in an argon atmosphere. The pore structure of limestone after the high temperature is studied based on scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), porosity, and permeability, and the change in the fractal dimension of the limestone pore structure was discussed based on the thermodynamic fractal theory, combined with X-ray diffraction (XRD) and thermogravimetry differential scanning calorimetry (TG-DSC), the variation of mineral composition with temperature is characterized, and the evolution mechanism of the limestone microstructure under high temperature is discussed. The results show that the evaporation of pore water does not destroy the lattice structure of limestone minerals; however, with the increase of temperature, the complete decomposition of dolomite and calcite occurs, along with the tensile fracture of calcite crystals under the effect of swelling stress. Moreover, the new minerals generated by the decomposition products under the effect of temperature severely damage the crystal structure, leading to the rapid increase of porosity and permeability. The comprehensive results show that the decomposition, expansion, and recrystallization of calcite and dolomite minerals after 800 °C led to the development of limestone macropores and fissures, increased the pore throat radius, enhanced the pore connectivity, simplified the pore structure, and sharply increased the permeability; thus, 800 °C can be used as the critical temperature to change the limestone pores and fractures. The research results can provide data support for subsurface high-temperature geotechnical engineering.

Dissociation mechanism of methane hydrate by CaCl2: an experimental and molecular dynamics study.

The formation of gas hydrate is a serious threat to the safe and effective completion of deepwater drilling and transportation operations, although it is considered as a potential energy resource. The inorganic salts are generally used as thermodynamic inhibitors; CaCl2 as a common additive in drilling fluids exhibits unique properties. In this study, we explored the dissociation mechanism of CH4 hydrate in CaCl2 solutions at the macroscopic and microscopic scale using experiment and molecular dynamics (MD) simulation. The experimental results showed that CaCl2 accelerated the dissociation rate of CH4 hydrate. The dissociation rate of CH4 hydrate increased with the increase of CaCl2 concentration at large depressurization pressure and was mainly affected by pressure when the depressurization pressure was lower. MD simulations were used to give an atomic scale interpretation of the macroscopic results obtained from the experiment. The results showed that the addition of CaCl2 destroyed the resistance liquid film formed during CH4 hydrate dissociation, thus accelerating the dissociation process, in good agreement with experimental results. HIGHLIGHTS: • The amount of CaCl2 affects CH4 hydrate dissociation at large depressurization pressure. • The dissociation of CH4 hydrate at low depressurization pressure is dependent on pressure. • Ca2+ destroys effectively the resistance liquid film produced during hydrate dissociation. • MD simulation results are in agreement with those of the experiment.

Iterative Cup Overlapping: An Efficient Identification Algorithm for Cage Structures of Amorphous Phase Hydrates.

Molecular dynamics studies have revealed that the nucleation pathway of clathrate hydrates involves the evolution from amorphous to crystalline hydrates. In this study, complete cages are further classified into the standard edge-saturated cages (SECs) and nonstandard edge-saturated cages (non-SECs). Centered on studying the structure and evolution of non-SECs and SECs, we propose a novel and efficient algorithm, iterative cup overlapping (ICO), to monitor hydrate nucleation and growth in molecular simulations by identifying SECs and discuss possible causes of the instability of non-SECs. Manipulation of topological information makes it possible for ICO to avoid the repeated searches for identified cages and deduce all SECs with low time costs, improving the efficiency of identification significantly. The accuracy and efficiency of ICO were verified by comparing the identification results with other well-proven algorithms. Furthermore, it was found that non-SECs have short lifetimes and eventually decompose or reorganize into more stable structures. Some evidence suggests that the instability of non-SECs is closely related to the hydrogen-bonding configuration of water-ring aggregations that they contain. The spontaneous evolution of the hydrogen-bonding network into the tetrahedral network may be the main factor that causes the conversion of QWRAs and the evolution of non-SECs.

Unraveling nucleation pathway in methane clathrate formation.

Methane clathrates are widespread on the ocean floor of the Earth. A better understanding of methane clathrate formation has important implications for natural-gas exploitation, storage, and transportation. A key step toward understanding clathrate formation is hydrate nucleation, which has been suggested to involve multiple evolution pathways. Herein, a unique nucleation/growth pathway for methane clathrate formation has been identified by analyzing the trajectories of large-scale molecular dynamics (MD) simulations. In particular, ternary water-ring aggregations (TWRAs) have been identified as fundamental structures for characterizing the nucleation pathway. Based on this nucleation pathway, the critical nucleus size and nucleation timescale can be quantitatively determined. Specifically, a methane hydration layer compression/shedding process is observed to be the critical step in (and driving) the nucleation/growth pathway, which is manifested through overlapping/compression of the surrounding hydration layers of the methane molecules, followed by detachment (shedding) of the hydration layer. As such, an effective way to control methane hydrate nucleation is to alter the hydration layer compression/shedding process during the course of nucleation.

Controllable syngas production on gold nanowires/nickel foam electrode in non-aqueous system.

A hierarchical electrode is prepared with Au nanowires grown on nickel foam. With large specific active surface area, it is used for producing syngas (H2/CO) with controllable ratio, through electrochemical process in DMF. The synthetic innovation lies in the use of 3-cyanopropyltriethoxysilane, to achieve the adsorption of appropriate amount of Au seeds for the one-dimensional growth of ultrathin Au nanowires (d ≈ 5 nm). With the nanowires forest on the three-dimensional porous nickel foam substrate, syngas is produced by electro-catalysis with high overall Faradic efficiency and tunable H2/CO ratios. This synthetic strategy opens a facile way to synthesize the hierarchical nanostructured materials, and broaden the choice of the catalysts for electrochemical applications.

Dissipative Particle Dynamics Simulation on Vesicles Self-Assembly Controlled by Terminal Groups.

Block copolymer vesicles have been widely used in the field of drug delivery, microreactors, and cell membrane mimetics. Introducing terminal groups to the block copolymer can control the structures of vesicles, which is important for improving the application of vesicles. In this paper, the effects of terminal groups on the structure of vesicles were studied by dissipative particle dynamics simulation. We considered different locations, hydrophobicity, and numbers of terminal groups. When the terminal group located at the end of a hydrophobic block, the increase of wall thickness and the decrease of cavity size of vesicles were observed with the hydrophobicity of the terminal group increasing. In contrast, when the terminal group located at the end of the hydrophilic block, with the hydrophobicity of terminal groups increasing, the vesicular cavity size increased but the wall thickness of vesicles remained nearly unchanged. Finally, increasing the number of terminal groups lead to a decrease of cavity size and an increase of wall thickness of vesicles. The hydrophobic changes of polymer molecules are regarded as the origin of the structural changes of vesicles. This simulation study supplies a potential approach that controls the structures of vesicles and is expected to facilitate its further applications.

The molecular mechanism of the inhibition effects of PVCaps on the growth of sI hydrate: an unstable adsorption mechanism.

The inhibition properties of kinetic hydrate inhibitor (KHI) molecules on the dynamic growth of a hydrate/water interface are investigated by using molecular dynamics simulations. The shape of the hydrate interface is transformed from laminar to funnel by PVCaps. Results indicate that the inhibition effects not only depend on the adsorption capacity which was believed to determine inhibition, but also on the fact that PVCaps must have some non-binding-hydrate sites that don't tend to combine with hydrate. By observing the time evolution of the distance between each component of PVCaps and hydrate, the heterocyclic ring of PVCaps mainly contributes to adsorption and can preferentially adjust itself to come into contact with a hydrate semi-large-cage. The distance between the amide of PVCaps and hydrate is about 4 Å and exceeds the range of a general hydrogen bond (3.5 Å), which proves that the non-binding-hydrate sites of PVCaps exist. On the other hand, the amide of PVCaps is at the intersection of the solid-liquid interface but has no adsorption affinity for hydrate, so this adsorption pattern indicates that the PVCaps at the hydrate interface are not stable. Due to this unstable adsorption, a repeated hydrate destruction phenomenon was revealed by the identification algorithm of hydrate and the calculation of the local number density of methane. The statistical evolution of water rings further proved the existence of non-binding-hydrate sites in PVCaps and the inhibition mechanism to destroy the hydrate cages by PVCaps. This unstable adsorption mechanism may shed light on the development of novel efficient KHIs.

A molecular dynamic study on the dissociation mechanism of SI methane hydrate in inorganic salt aqueous solutions.

Gas hydrate is not only a potential energy resource, but also almost the biggest challenge in oil/gas flow assurance. Inorganic salts such as NaCl, KCl and CaCl2 are widely used as the thermodynamic inhibitor to reduce the risk caused by hydrate formation. However, the inhibition mechanism is still unclear. Therefore, molecular dynamic (MD) simulation was performed to study the dissociation of structure I (SI) methane hydrate in existence of inorganic salt aqueous solution on a micro-scale. The simulation results showed that, the dissociation became stagnant due to the presence of liquid film formed by the decomposed water molecules, and more inorganic ions could shorten the stagnation-time. The diffusion coefficients of ions and water molecules were the largest in KCl system. The structures of ion/H2O and H2O/H2O were the most compact in hydrate/NaCl system. The ionic ability to decompose hydrate cells followed the sequence of: Ca2+>2K+>2Cl->2Na+.