Improving force field accuracy by training against condensed phase mixture properties

Developing a sufficiently accurate classical force field representation of molecules is key to realizing the full potential of molecular simulation as a route to gaining fundamental insight into a broad spectrum of chemical and biological phenomena. This is only possible, however, if the many complex interactions between molecules of different species in the system are accurately captured by the model. Historically, the intermolecular van der Waals (vdW) interactions have primarily been trained against densities and enthalpies of vaporization of pure (single-component) systems, with occasional usage of hydration free energies. In this study, we demonstrate how including physical property data of binary mixtures can better inform these parameters, encoding more information about the underlying physics of the system in complex chemical mixtures. To demonstrate this, we re-train a select number of the Lennard-Jones parameters describing the vdW interactions of the OpenFF 1.0.0 (Parsley) fixed charge force field against training sets composed of densities and enthalpies of mixing for binary liquid mixtures as well as densities and enthalpies of vaporization of pure liquid systems, and assess the performance of each of these combinations. We show that retraining against the mixture data almost universally improves the force field's ability to reproduce both pure and mixture properties, reducing some systematic errors that exist when training vdW interactions against properties of pure systems only.

Deep Penetration Resin Systems Overcome Annular Gas Migration: Case History

Well Integrity is a critical compliance requirement during oil and gas operations. Abandonment procedures must ensure that all hydrocarbon sources are properly isolated and effective barriers are placed. This paper describes the use of resin systems to isolate annular gas migration identified during the Obiwan – 1 well abandonment in Colombia. The main challenge was to select and design fluid systems capable to fill tight spaces and isolate the annular channel. Resin systems are high-strength, elastic polymers which act as dependable barriers to isolate fluid flow. They can be designed as a solid-free, pure liquid or may contain solids (cement with a formulated percent of resin). Solid-free formulations are ideal for remedial operations, such as isolating annular gas. Acoustic logging enabled identification of the influx zones. Annular isolation was achieved by executing two cementing remedial operations using the bradenhead squeeze technique. A tailored resin system was selected to deliver the proper barrier addressing the influx zones after injectivity tests were performed in each interval. For the first intervention a solids-free resin system was used, and for the second one a resin-cement composite system was applied. During cementing remedial operations, it was determined that the resin systems were able to achieve deep penetration into the channels more readily and form a seal. The correct system was selected for each case, and during execution, the required volume was injected to intersect and properly isolate the annular gas channel. As a result, the tailored resin systems isolated the gas channel eliminating annular pressure and gas migration to surface. In addition, a post remedial operation acoustic log indicated that the influx zones were successfully isolated. Well abandonment was accomplished according to country regulatory requirements and delivered dependable barriers both annular and interior pipe sections. Use of resin to repair channels of this type exhibited a higher success rate and improved reliability in comparison to conventional particulate-laden fluids, which helps to decrease costs for additional remedial treatments.

Improving force field accuracy by training against condensed phase mixture properties

Developing a sufficiently accurate classical force field representation of molecules is key to realizing the full potential of molecular simulation as a route to gaining fundamental insight into a broad spectrum of chemical and biological phenomena. This is only possible, however, if the many complex interactions between molecules of different species in the system are accurately captured by the model. Historically, the intermolecular van der Waals (vdW) interactions have primarily been trained against densities and enthalpies of vaporization of pure (single-component) systems, with occasional usage of hydration free energies. In this study, we demonstrate how including physical property data of binary mixtures can better inform these parameters, encoding more information about the underlying physics of the system in complex chemical mixtures. To demonstrate this, we re-train a select number of the Lennard-Jones parameters describing the vdW interactions of the OpenFF 1.0.0 (Parsley) fixed charge force field against training sets composed of densities and enthalpies of mixing for binary liquid mixtures as well as densities and enthalpies of vaporization of pure liquid systems, and assess the performance of each of these combinations. We show that retraining against the mixture data almost universally improves the force field's ability to reproduce both pure and mixture properties, reducing some systematic errors that exist when training vdW interactions against properties of pure systems only.

Experimental Investigation of the Atmosphere-Regolith Water Cycle on Present-Day Mars

The water content of the upper layers of the surface of Mars is not yet quantified. Laboratory simulations are the only feasible way to investigate this in a controlled way on Earth, and then compare it with remote and in situ observations of spacecrafts on Mars. Describing the processes that may induce changes in the water content of the surface is critical to determine the present-day habitability of the Martian surface, to understand the atmospheric water cycle, and to estimate the efficiency of future water extraction procedures from the regolith for In Situ Resource Utilization (ISRU). This paper illustrates the application of the SpaceQ facility to simulate the near-surface water cycle under Martian conditions. Rover Environmental Monitoring Station (REMS) observations at Gale crater show a non-equilibrium situation in the atmospheric H2O volume mixing ratio (VMR) at night-time, and there is a decrease in the atmospheric water content by up to 15 g/m2 within a few hours. This reduction suggests that the ground may act at night as a cold sink scavenging atmospheric water. Here, we use an experimental approach to investigate the thermodynamic and kinetics of water exchange between the atmosphere, a non-porous surface (LN2-chilled metal), various salts, Martian regolith simulant, and mixtures of salts and simulant within an environment which is close to saturation. We have conducted three experiments: the stability of pure liquid water around the vicinity of the triple point is studied in experiment 1, as well as observing the interchange of water between the atmosphere and the salts when the surface is saturated; in experiment 2, the salts were mixed with Mojave Martian Simulant (MMS) to observe changes in the texture of the regolith caused by the interaction with hydrates and liquid brines, and to quantify the potential of the Martian regolith to absorb and retain water; and experiment 3 investigates the evaporation of pure liquid water away from the triple point temperature when both the air and ground are at the same temperature and the relative humidity is near saturation. We show experimentally that frost can form spontaneously on a surface when saturation is reached and that, when the temperature is above 273.15 K (0 °C), this frost can transform into liquid water, which can persist for up to 3.5 to 4.5 h at Martian surface conditions. For comparison, we study the behavior of certain deliquescent salts that exist on the Martian surface, which can increase their mass between 32% and 85% by absorption of atmospheric water within a few hours. A mixture of these salts in a 10% concentration with simulant produces an aggregated granular structure with a water gain of approximately 18- to 50-wt%. Up to 53% of the atmospheric water was captured by the simulated ground, as pure liquid water, hydrate, or brine.

A NONHOMOGENEOUS BULK FLOW MODEL FOR GAS IN LIQUID FLOW ANNULAR SEALS: AN EFFORT TO PRODUCE ENGINEERING RESULTS

Seals in multiple phase rotordynamic pumps must operate without compromising system efficiency and stability. Both field operation and laboratory experiments show that seals supplied with a gas in liquid mixture (bubbly flow) can produce rotordynamic instability and excessive rotor vibrations. This paper advances a nonhomogeneous bulk flow model (NHBFM) for the prediction of the leakage and dynamic force coefficients of uniform clearance annular seals lubricated with gas in liquid mixtures. Compared to a homogeneous BFM (HBFM), the current model includes diffusion coefficients in the momentum transport equations and a field equation for the transport of the gas volume fraction (GVF). Published experimental leakage and dynamic force coefficients for two seals supplied with an air in oil mixture whose GVF varies from 0 (pure liquid) to 20% serve to validate the novel model as well as to benchmark it against predictions from a HBFM. The first seal withstands a large pressure drop (~ 38 bar) and the shaft speed equals 7.5 krpm. The second seal restricts a small pressure drop (1.6 bar) as the shaft turns at 3.5 krpm. The first seal is typical as a balance piston whereas the second seal is found as a neck-ring seal in an impeller. For the high pressure seal and inlet GVF = 0.1, the flow is mostly homogeneous as the maximum diffusion velocity at the seal exit plane is just ~0.1% of the liquid flow velocity. Thus, both the NHBFM and HBFM predict similar flow fields, leakage (mass flow rate) and drag torque. The difference between the predicted leakage and measurement is less than 5%. The NHBFM direct stiffness (K) agrees with the experimental results and reduces faster with inlet GVF than the HBFM K. Both direct damping (C) and cross-coupled stiffness (k) increase with inlet GVF < 0.1.Compared to the test data, the two models generally under predict C and k by ~ 25%. Both models deliver a whirl frequency ratio (fw) ~ 0.3 for the pure liquid seal, hence closely matching the test data. fw raises to ~0.35 as the GVF approaches 0.1. For the low pressure seal the flow is laminar, the experimental results and both NHBFM and HBFM predict a null direct stiffness (K). At an inlet GVF = 0.2, the NHBFM predicted added mass (M) is ~30 % below the experimental result while the HBFM predicts a null M. C and k predicted by both models are within the uncertainty of the experimental results. For operation with either a pure liquid or a mixture (GVF = 0.2), both models deliver fw = 0.5 and equal to the experimental finding. The comparisons of predictions against experimental data demonstrate the NHBFM offers a marked improvement, in particular for the direct stiffness (K). The predictions reveal the fluid flow maintains the homogeneous character known at the inlet condition.

On the lifespan of recirculating suspensions with pulsatile flow

A Lagrangian analysis is performed to measure the rate at which recirculating fluid is replaced (depleted) in pulsatile flows. Based on this approach, we then investigate how depletion is affected in dense suspensions. Experiments are conducted for pure liquid as well as suspensions with volume fractions of $\varPhi =5\,\%$ , 10 % and 20 %. Using Lagrangian tracking and pathline extension techniques, the depletion of the recirculation region is quantified via the trajectories of individual fluid parcels exiting the domain. Pulsatile flows with varying concentrations of hydrogel beads, up to a volume fraction of 20 %, are compared at mean Reynolds numbers of $Re=4800$ , 9600 and 14 400, while the Strouhal number ( $St=0.04$ , 0.08 and 0.15) and amplitude ratio ( $\lambda =0.25$ , 0.50 and 0.95) are systematically varied. A so-called ‘depletion efficiency’ is calculated for each test case, which is shown to increase with increasing Strouhal number and amplitude ratio. For most pulsatile cases, periodic vortex formation significantly increases depletion efficiency through enhanced entrainment of recirculating fluid. Conversely, low-amplitude pulsatile flows are dominated by Kelvin–Helmholtz instabilities, which do not penetrate into the recirculation region, and thus their depletion efficiency is markedly lower as a result. The efficiency trends and depletion mechanisms remain virtually unchanged between the pure liquid and each of the suspension concentrations under almost all flow conditions, which forms an unexpected conclusion. The only exception is for low-amplitude and steady flows, where increasing the suspension volume fraction is shown to suppress fluid transport across the shear layer, which in turn slows depletion and decreases the overall depletion efficiency.

Influence of Temperature on Rising Bubble Dynamics in Water and n-pentanol Solutions

Data in the literature on the influence of water temperature on the terminal velocity of a single rising bubble are highly contradictory. Different variations in bubble velocity with temperature are reported even for potentially pure systems. This paper presents a systematic study on the influence of temperature between 5 °C and 45 °C on the motion of a single bubble of practically constant size (equivalent radius 0.74 ± 0.01 mm) rising in a clean water and n-pentanol solution of different concentrations. The bubble velocity was measured by a camera, an ultrasonic sensor reproduced in numerical simulations. Results obtained by image analysis (camera) were compared to the data measured by an ultrasonic sensor to reveal the similar scientific potential of the latter. It is shown that temperature has a significant effect on the velocity of the rising bubble. In pure liquid, this effect is caused only by modifying the physicochemical properties of the water phase, not by changing the hydrodynamic boundary conditions at the bubble surface. In the case of the solutions with surface-active substances, the temperature-change kinetics of the dynamic adsorption layer formation facilitate the immobilization of the liquid/gas interface.

Measuring solute concentration with terahertz time-domain spectroscopy in single and multiphase systems

A versatile setup based on a microfluidics platform allows investigation of liquid samples at various temperatures with terahertz time-domain spectroscopy. The set up is applied to develop a novel method that performs temperature and concentration calibrations of liquid samples at terahertz frequencies. Other than measuring the concentration of pure liquid phase solutions, it enables the studies of local concentration of semi-crystalline systems. An equivalent solute concentration during crystallisation can be calculated from the extracted absorption at low frequencies. The MgSO4-water system is discussed as an example to illustrate the idea of this method.