Search Results (11)

The aim of this study is to generate density and viscosity data for carbon capture utilization and storage (CCUS) mixtures using equilibrium molecular dynamics (EMD) simulations. Binary CO₂ mixtures with SO₂ and H₂S impurities at mole fractions of 0.05, 0.10, and 0.20 were constructed. Simulations were performed across a temperature range of 223–323.15 K and at pressures up to 27.5 MPa using ms2 software. The simulation results were compared with predictions from established models. These included the Multi-Fluid Helmholtz Energy Approximation (MFHEA) for density, and the Lennard-Jones (LJ), Residual Entropy Scaling (ES-NIST), and Extended Corresponding States (SUPERTRAPP) models for viscosity. Available experimental data from the literature were also used for validation. Density predictions showed excellent agreement with MFHEA, especially for CO₂ + SO₂ mixtures, with %AARD values below 1% for 0.05 and 0.10, and 1.60% for 0.20 mole fraction SO₂. For CO₂ + H₂S mixtures, deviations also increased with impurity concentration, reaching a maximum %AARD of 4.72% at 0.20 mole fraction. Viscosity data were validated against experimental values from the literature for a CO₂ + CH₄ (xCH₄ = 0.25) mixture, showing strong agreement with both models and experiments. This confirms the reliability of the MD approach and the thermodynamic models, even for systems lacking experimental data. However, viscosity estimates showed higher uncertainty at lower temperatures and higher densities, a known limitation of the Green–Kubo method. This highlights the importance of selecting an appropriate correlation time to ensure the pressure correlation functions reach a plateau, avoiding inaccurate or uncertain viscosity values. Full article

Cis-1,4-polyisoprene is a widely used elastomer that demonstrates particular thermal and mechanical characteristics, in which the latter is influenced by temperature and strain rate. Molecular dynamic simulations were used to obtain thermal conductivities, glass transition temperatures (T_g), and tensile deformation. Thermal conductivities were calculated by applying the Green–Kubo method, and a decrease in thermal conductivity was observed with increasing temperature. Density–temperature relations were used to calculate T_g, which indicates the transition from the glassy to the rubbery state of the material, and this temperature influences mechanical properties. Investigation of the mechanical properties under uniaxial tensile deformation for constant strain rates indicates an increase in the stiffness and strength of the material at lower temperatures, while increasing molecular mobility at higher temperatures results in reducing these properties. The influence of strain rates at constant temperature highlighted the viscoelastic nature of the structure; increasing strain rates resulted in increases in stiffness, strength, elongation at maximum strength, and elongation at break because of restricted molecular relaxation time. The united-atom force field contributes to higher computational efficiency, which is suitable for large-scale simulations. These results provide important information on the thermo-mechanical properties and tunability of cis-1,4-polyisoprene, which supports applications in the production of interactive fiber rubber composites. Full article

The thermal conductivities and glass transition temperatures of polybutadiene crosslinked with randomly distributed sulfur chains having different lengths from mono-sulfur (S1) to octa-sulfur (S8) were investigated. The thermal conductivities of the related models as a function of the heat flux autocorrelation function, applying an equilibrium molecular dynamic (EMD) simulation and the Green–Kubo method, were studied for a wide range of temperatures. The influence of the length of sulfur chains, degree of crosslinking, and molar mass of the crosslinker on the glass transition temperature and final values of thermal conductivities were studied. First, the degree of crosslinking is considered constant for the eight simulation models, from mono-sulfur (S1) to octa-sulfur (S8), while the molar mass of the sulfur is increases. The results show that the thermal conductivities of the crosslinked structure decrease with increasing temperature for each model. Moreover, by increasing the lengths of the sulfur chains and the molar weight of the crosslinker, thermal conductivity increases at a constant temperature. The MD simulation demonstrates that the glass transition temperature and density of the crosslinked structure enhance as the length of the sulfur chains and molar mass of the sulfur increase. Second, the molar weight of sulfur is considered constant in these eight models; therefore, the degree of crosslinking decreases with the increase in the lengths of the sulfur chains. The results show that the thermal conductivities of the crosslinked structure decrease with the increase in the temperature for each model. Moreover, by increasing the lengths of sulfur chains and thus decreasing the degree of crosslinking, the trend in changes in thermal conductivities are almost the same for all of these models, so thermal conductivity is constant for a specific temperature. In addition, the glass transition temperature and density of the crosslinked structure decrease. Full article

Thermal conductivities of polybutadiene crosslinked with sulfur as a function of the heat flux autocorrelation function by using an equilibrium molecular dynamic (EMD) simulation were investigated. The Green–Kubo method was used to calculate thermal conductivities. All simulations were performed by applying the LAMMPS software (version 3 Mar 2020) package. The united-atom force field (OPLS-UA) from the Moltemplate software (version 2.20.3) was applied in the simulations. The influence of uniform and random distributions of sulfur in polybutadiene on the final value of thermal conductivities was studied by polymeric model structures with similar and variable degrees of crosslinking. The results showed that for identical degrees of crosslinking, the distribution of crosslinkers in the polymeric model structures significantly influenced the final value of thermal conductivity. Moreover, the influence of the crosslinking degree on the final value of thermal conductivity was studied by considering polymeric model structures with different degrees of crosslinking. The results demonstrate that by having a random distribution of sulfur, the thermal conductivity will be enhanced. However, by increasing the degree of crosslinking to the higher percentage in random crosslinked model structures, the value of thermal conductivity drops significantly due to possible higher crystallization of the model structures, which decrease the degree of freedom for phonon contributions. Full article

As the critical component of automotive engine coolant, ethylene glycol (E.G.) significantly matters in heat dissipation. In this study, the key aim is to investigate the heat transfer behaviour of E.G. as nano-additives base fluid. The heat transfer capability of E.G./SiC nanofluid (N.F.) was experimentally and theoretically evaluated via transient hot wire methods and equilibrium molecular dynamics (EMD) simulation, respectively. M.D. simulation exhibited a great ability to accurately forecast the thermal conductivity of N.F. compared with the experiment results. The results confirmed that the thermal stability of N.F. is relatively greater than that of E.G. base fluids. An improvement mechanism of thermal conductivity and thermal stability under an atomic scale via the analysis of mean square displacement (MSD) and radial distribution function (RDF) calculation was elaborately presented. Ultimately, the results indicated that the diffusion effect and the increasing transition rate of liquid atoms are responsible for thermal conductivity enhancement. Full article

Supercritical carbon dioxide (sCO₂) has great potential for displacing shale oil as a result of its high solubility and low surface tension and viscosity, but the underlying mechanisms have remained unclear up to now. By conducting equilibrium molecular dynamics (EMD) simulations, we found that the displacing process could be divided into three steps: the CO₂ molecules were firstly injected in the central region of shale slit, then tended to adsorb on the SiO₂-OH wall surface and mix with hexane, resulting in loose hexane layer on the shale surface, and finally displaced hexane from the wall due to strong interactions between CO₂ and wall. In that process, the displacing velocity and efficiency of hexane exhibit parabolic and increased trends with pressure, respectively. To gain deep insights into this phenomenon, we further performed non-equilibrium molecular dynamics (NEMD) simulations and found that both the Onsager coefficients of CO₂ and hexane were correlated to increase with pressure, until the diffusion rate of hexane being suppressed by the highly dense distribution of CO₂ molecules at 12 MPa. The rapid transportation of CO₂ molecules in the binary components (CO₂ and hexane) actually promoted the hexane diffusion, which facilitated hexane flowing out of the nanochannel and subsequently enhanced oil recovery efficiency. The displacing process could occur effectively at pressures higher than 7.5 MPa, after which the interaction energies of the CO₂-wall were stronger than that of the hexane-wall. Taking displacing velocity and efficiency and hexane diffusion rate into consideration, the optimal injection pressure was found at 10.5 MPa in this work. This study provides detailed insights into CO₂ displacing shale oil and is in favor of deepening the understanding of shale oil exploitation and utilization. Full article

In this article, two main approaches to the prediction of thermal conductivities by molecular dynamics (MD) simulations are discussed, namely non-equilibrium molecular dynamics simulations (NEMD) and the application of the Green–Kubo formula, i.e., EMD. NEMD methods are more affected by size effects than EMD methods. The thermal conductivities of silicone rubbers in special were found as a function of the degree of crosslinking. Moreover, the thermal conductivities of thermoplastic polyurethane as function of the mass fraction of soft segments were obtained by those MD simulations. All results are in good agreement with data from the experimental literature. After the analysis of normalized heat flux autocorrelation functions, it has been revealed that heat in the polymers is mainly transferred by low-frequency phonons. Simulation details as well as advantages and disadvantages of the single methods are discussed in the article. Full article

Size and thermal effect on molar heat capacity of liquid at constant volume (C_v) on a nanometer scale have been investigated by controlling the temperature and density of the liquid domain using equilibrium molecular dynamics (EMD) simulations. Lennard-Jones (LJ) type molecular model with confinement gap thickness (h) 0.585 nm to 27.8 nm has been used with the temperature (T) ranging from 100 K to 140 K. The simulation results revealed that the heat capacity of the nanoconfined liquid surpasses that of the bulk liquid within a defined interval of gap thickness; that the temperature at which maximum heat capacity occurs for a nanoconfined liquid vary with gap thickness following a power law, T_Cv,max = 193.4 × (h/a)^−0.3431, ‘a’ being the lattice constant of Argon (solid) at 300 K; and that for a specified gap thickness and temperature, the confined liquid can exhibit a heat capacity that can be more than twice the heat capacity of the bulk liquid. The increase in heat capacity is underpinned by an increase in non-configurational (phonon and anharmonic modes of vibration) and configurational (non-uniform density distribution, enhanced thermal resistance, guided molecular mobility, etc.) contributions. Full article

Graphene as a type of novel additive significantly enhanced the tribological performance of blended lubricating oil. However, the dispersibility of graphene with long-term stability in lubricating oil is still a challenge. Chemical modification for graphene, rather than using surfactants, provided a better method to improve the dispersibility of graphene in lubricants. In this study, the equilibrium molecular dynamics (EMD) simulations were carried out to investigate the diffusion behavior of graphene nanoplates in poly-α-olefin (PAO) lubricating oil. The effects of graphene-size, edge-functionalization, temperature, and pressure on the diffusion coefficient were studied. In order to understand the influence of edge-functionalization, three different functional groups were grafted to the edge of graphene nanoplates: COOH, COON(CH₃)₂, CONH(CH₂)₈CH₃ (termed GO, MG, and AG, respectively). The EMD simulations results demonstrated that the relationships between diffusion coefficient and graphene-size and number of functional groups were linear while the temperature and pressure had a nonlinear influence on the diffusion coefficient. It was found that the larger dimension and more functional groups provided the lower diffusion coefficient. AG with eight CONH(CH₂)₈CH₃ groups exhibited the lowest diffusion coefficient. Furthermore, the experimental results and radial distribution function for graphene-PAO illustrated that the diffusion coefficient reflected the dispersibility of nanoparticles in nanofluids to some degree. To our best knowledge, this study is the first time the diffusion behavior of graphene in PAO lubricating oil was investigated using EMD simulations. Full article

For the successful development and application of lubricants, a full understanding of their complex nanoscale behavior under a wide range of external conditions is required, but this is difficult to obtain experimentally. Nonequilibrium molecular dynamics (NEMD) simulations can be used to yield unique insights into the atomic-scale structure and friction of lubricants and additives; however, the accuracy of the results depend on the chosen force-field. In this study, we demonstrate that the use of an accurate, all-atom force-field is critical in order to; (i) accurately predict important properties of long-chain, linear molecules; and (ii) reproduce experimental friction behavior of multi-component tribological systems. In particular, we focus on n-hexadecane, an important model lubricant with a wide range of industrial applications. Moreover, simulating conditions common in tribological systems, i.e., high temperatures and pressures (HTHP), allows the limits of the selected force-fields to be tested. In the first section, a large number of united-atom and all-atom force-fields are benchmarked in terms of their density and viscosity prediction accuracy of n-hexadecane using equilibrium molecular dynamics (EMD) simulations at ambient and HTHP conditions. Whilst united-atom force-fields accurately reproduce experimental density, the viscosity is significantly under-predicted compared to all-atom force-fields and experiments. Moreover, some all-atom force-fields yield elevated melting points, leading to significant overestimation of both the density and viscosity. In the second section, the most accurate united-atom and all-atom force-field are compared in confined NEMD simulations which probe the structure and friction of stearic acid adsorbed on iron oxide and separated by a thin layer of n-hexadecane. The united-atom force-field provides an accurate representation of the structure of the confined stearic acid film; however, friction coefficients are consistently under-predicted and the friction-coverage and friction-velocity behavior deviates from that observed using all-atom force-fields and experimentally. This has important implications regarding force-field selection for NEMD simulations of systems containing long-chain, linear molecules; specifically, it is recommended that accurate all-atom potentials, such as L-OPLS-AA, are employed. Full article

The thermal conductivity of graphene nanoribbons (GNRs) has been investigated using equilibrium molecular dynamics (EMD) simulation based on Green-Kubo (GK) method to compare two interatomic potentials namely optimized Tersoff and 2nd generation Reactive Empirical Bond Order (REBO). Our comparative study includes the estimation of thermal conductivity as a function of temperature, length and width of GNR for both the potentials. The thermal conductivity of graphene nanoribbon decreases with the increase of temperature. Quantum correction has been introduced for thermal conductivity as a function of temperature to include quantum effect below Debye temperature. Our results show that for temperatures up to Debye temperature, thermal conductivity increases, attains its peak and then falls off monotonically. Thermal conductivity is found to decrease with the increasing length for optimized Tersoff potential. However, thermal conductivity has been reported to increase with length using 2nd generation REBO potential for the GNRs of same size. Thermal conductivity, for the specified range of width, demonstrates an increasing trend with the increase of width for both the concerned potentials. In comparison with 2nd generation REBO potential, optimized Tersoff potential demonstrates a better modeling of thermal conductivity as well as provides a more appropriate description of phonon thermal transport in graphene nanoribbon. Such comparative study would provide a good insight for the optimization of the thermal conductivity of graphene nanoribbons under diverse conditions. Full article