Mechanism of shale oil displacement by CO2 in nanopores: A molecular dynamics simulation study

Utilizing CO2 to enhance shale oil recovery has a huge potential and thus has gained widespread popularity in recent years. However, the microscopic mechanisms of CO2 enhancing shale oil recovery remain poorly understood. In this paper, the molecular dynamics simulation method is adopted to investigate the replacement behavior of CO2 in shale oil reservoirs from a micro perspective. Three kinds of n-alkanes are selected as the simulative crude oil in silica nanopores. Molecular dynamics models are established to study the occurrence patterns of different alkanes on the rock surface and the alkane[1]stripping characteristics of CO2. The fluid density, mean square displacement and centroid variation are evaluated to reveal the effect of CO2 on alkanes. The results indicate that different alkanes exhibit varying occurrence characteristics of oil film on the rock surface of the shale reservoir. Specifically, a higher carbon number leads to a thicker oil film. Through the alkane molecular gaps, CO2 penetrates the alkane molecular system and reaches the rock surface to effectively strip the oil film of different alkane molecules. CO2 will more readily mix with the stripped oil molecules and displace them from the rock surface when the carbon number is small. The process for CO2 replacing crude oil on the rock surface can be divided into four typical stages, namely, CO2 diffusion, competitive adsorption, emulsification and dissolution, and CO2-alkanes miscible phase (for light alkanes). This study contributes to the improvement of micro-scale enhanced oil recovery mechanisms for shale oil via CO2 injection and provides a guidance for enhancing shale oil recovery by using CO2.Document Type: Original articleCited as: Wu, Z., Sun, Z., Shu, K., Jiang, S., Gou, Q., Chen, Z. Mechanism of shale oil displacement by CO2 in nanopores: A molecular dynamics simulation study. Advances in Geo-Energy Research, 2024, 11(2): 141-151. https://doi.org/10.46690/ager.2024.02.0

Neutron Scattering Signature of Phonon Renormalization in Nickel (II) Oxide

The physics of mutual interaction of phonon quasiparticles with electronic spin degrees of freedom, leading to unusual transport phenomena of spin and heat, has been a subject of continuing interests for decades. Despite its pivotal role in transport processes, the effect of spin-phonon coupling on the phonon system, especially acoustic phonon properties, has so far been elusive. By means of inelastic neutron scattering and first-principles calculations, anomalous scattering spectral intensity from acoustic phonons was identified in the exemplary collinear antiferromagnetic nickel (II) oxide, unveiling strong spin-lattice correlations that renormalize the polarization of acoustic phonon. In particular, a clear magnetic scattering signature of the measured neutron scattering intensity from acoustic phonons is demonstrated by its momentum transfer and temperature dependences. The anomalous scattering intensity is successfully modeled with a modified magneto-vibrational scattering cross section, suggesting the presence of spin precession driven by phonon. The renormalization of phonon eigenvector is indicated by the observed "geometry-forbidden" neutron scattering intensity from transverse acoustic phonon. Importantly, the eigenvector renormalization cannot be explained by magnetostriction but instead, it could result from the coupling between phonon and local magnetization of ions.Comment: Research pape

Matryoshka Phonon Twinning in alpha-GaN

Understanding lattice dynamics is crucial for effective thermal management in high-power electronic devices because phonons dominate thermal transport in most semiconductors. This study utilizes complementary inelastic X-ray and neutron scattering techniques and reports the temperature-dependent phonon dynamics of alpha-GaN, one of the most important third-generation power semiconductors. A prominent Matryoshka phonon dispersion is discovered with the scattering tools and confirmed by the first-principles calculations. Such Matryoshka twinning throughout the three-dimension reciprocal space is demonstrated to amplify the anharmonicity of the related phonon modes through creating abundant three-phonon scattering channels and cutting the phonon lifetime of affected modes by more than 50%. Such phonon topology effectively contributes to the reduction of the in-plane thermal transport, thus the anisotropic thermal conductivity of alpha-GaN. The results not only have significant implications for engineering the thermal performance and other phonon-related properties of alpha-GaN, but also offer valuable insights on the role of anomalous phonon topology in thermal transport of other technically important semiconductors.Comment: 34 pages, 15 figure

Review about evaluation methods of recoverable reserves of deep water drive gas reservoirs in China

It has been widely accepted that China is one of the biggest natural gas consumers. Related to the imports of LNG, China stands in a very uncomfortable situation. Most domestic gas reservoirs fall within deep water drive gas reservoirs inordinately, which has entered the production depletion stage. Accurate estimation of SEC recoverable reserves of deep water drive gas reservoirs is of great significance for gas consumption planning and peak shaving. The existing calculation methods of recoverable reserves mainly consist of static methods and dynamic methods. In the early stage of exploration and development, the volumetric method has often been utilized to calculate the recoverable reserves. With the continuous development of gas reservoirs, the main methods for evaluation are dynamic methods, including the successive subtraction of production method, water drive curve method, prediction model method, attenuation curve method, improved virtual curve method, and material balance method for deep gas reservoirs

Lipocalin-2 promotes adipose-macrophage interactions to shape peripheral and central inflammatory responses in experimental autoimmune encephalomyelitis

Objective: Accumulating evidence suggests that dysfunctional adipose tissue (AT) plays a major role in the risk of developing multiple sclerosis (MS), the most common immune-mediated and demyelinating disease of the central nervous system. However, the contribution of adipose tissue to the etiology and progression of MS is still obscure. This study aimed at deciphering the responses of AT in experimental autoimmune encephalomyelitis (EAE), the best characterized animal model of MS. Results and methods: We observed a significant AT loss in EAE mice at the onset of disease, with a significant infiltration of M1-like macrophages and fibrosis in the AT, resembling a cachectic phenotype. Through an integrative and multilayered approach, we identified lipocalin2 (LCN2) as the key molecule released by dysfunctional adipocytes through redox-dependent mechanism. Adipose-derived LCN2 shapes the pro-inflammatory macrophage phenotype, and the genetic deficiency of LCN2 specifically in AT reduced weight loss as well as inflammatory macrophage infiltration in spinal cord in EAE mice. Mature adipocytes downregulating LCN2 reduced lipolytic response to inflammatory stimuli (e.g. TNFα) through an ATGL-mediated mechanism. Conclusions: Overall data highlighted a role LCN2 in exacerbating inflammatory phenotype in EAE model, suggesting a pathogenic role of dysfunctional AT in MS

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss

Spin and Lattice Dynamics, and Spin-phonon Interactions in Transition Metal Oxides

The physics of mutual interaction of phonon quasiparticles with electronic spin degrees of freedom, leading to unusual transport phenomena of spin and heat, has been a subject of continuing interest for decades. Understanding the underlying mechanisms of spin-phonon interactions is pivotal for engineering spin and phonon transport and developing novel spintronic applications. By means of inelastic neutron scattering and first-principles calculations, spin-phonon dynamics in transition metal oxides are investigated.In the first part of the thesis, spin-phonon interactions and their effects on thermal transport were investigated in the exemplary collinear antiferromagnetic NiO. Anomalous scattering spectral intensity from acoustic phonons was identified, unveiling spin precession driven by phonon and strong spin-lattice correlations that renormalize the polarization of acoustic phonons. Time-domain thermoreflectance measurements of the thermal conductivity vs. temperature follow T$^{-1.5}$ in the antiferromagnetic phase. This temperature dependence cannot be explained by phonon-isotope and phonon-defect scattering or phonon softening. Instead, we attribute this to magnon-phonon scattering and spin-induced dynamic symmetry breaking. Our results provide approaches to identify and quantify strong spin-phonon interactions, shedding light on engineering functional spintronic and spin-caloritronic materials through these interactions. In the second part of the thesis, temperature-dependent spin and phonon dynamics in Cr$_2$O$_3$ were characterized and analyzed. We unveiled the emergence of paramagnons above the T$_N$ and at 280 K, closely below T$_N$. We demonstrated a significant softening of linear magnons upon heating in the antiferromagnetic state. Further analysis revealed that this softening primarily originated from four-magnon interactions, while thermal expansion played a subsidiary role. For phonon dynamics, while most phonon modes exhibit expected softening from 50 to 450 K, we observe significant stiffening in the longitudinal optical modes, which involve changing the distances between the nearest Cr$^{3+}$ pairs. Instead of effects from thermal expansion, phonon anharmonicity, magnetostriction, or electron-phonon interactions, the anomalous stiffening can be attributed to the renormalization of electron states due to the change of spin order. Our results point to a purely static magnetoelectric-coupling origin for the observed phonon stiffening, suggest the high-tunability of phonon energies in Cr$_2$O$_3$, and provide insights into controlling lattice dynamics in novel magnetoelectric spintronics

Colossal oxygen vacancy formation at a fluorite-bixbyite interface

Oxygen vacancies in complex oxides are indispensable for information and energy technologies. There are several means to create oxygen vacancies in bulk materials. However, the use of ionic interfaces to create oxygen vacancies has not been fully explored. Herein, we report an oxide nanobrush architecture designed to create high-density interfacial oxygen vacancies. An atomically well-defined (111) heterointerface between the fluorite CeO2 and the bixbyite Y2O3 is found to induce a charge modulation between Y3+ and Ce4+ ions enabled by the chemical valence mismatch between the two elements. Local structure and chemical analyses, along with theoretical calculations, suggest that more than 10% of oxygen atoms are spontaneously removed without deteriorating the lattice structure. Our fluorite–bixbyite nanobrush provides an excellent platform for the rational design of interfacial oxide architectures to precisely create, control, and transport oxygen vacancies critical for developing ionotronic and memristive devices for advanced energy and neuromorphic computing technologies.United States. Department of Energy. Office of Science User Facility (Contract DE-AC02-05CH11231)United States. Department of Energy. Office of Science (Contract DE-AC02-06CH11357