Molecular modelling of the thermophysical properties of fluids: expectations, limitations, gaps and opportunities.

This manuscript provides an overview of the current state of the art in terms of the molecular modelling of the thermophysical properties of fluids. It is intended to manage the expectations and serve as guidance to practising physical chemists, chemical physicists and engineers in terms of the scope and accuracy of the more commonly available intermolecular potentials along with the peculiarities of the software and methods employed in molecular simulations while providing insights on the gaps and opportunities available in this field. The discussion is focused around case studies which showcase both the precision and the limitations of frequently used workflows.

Stable Dropwise Condensation of Ethanol and Hexane on Rationally Designed Ultrascalable Nanostructured Lubricant-Infused Surfaces.

Vapor condensation is a widely used industrial process for transferring heat and separating fluids. Despite progress in developing low surface energy hydrophobic and micro/nanostructured superhydrophobic coatings to enhance water vapor condensation, demonstration of stable dropwise condensation of low-surface-tension fluids has not been achieved. Here, we develop rationally designed nanoengineered lubricant-infused surfaces (LISs) having ultralow contact angle hysteresis (<3°) for stable dropwise condensation of ethanol (γ ≈ 23 mN/m) and hexane (γ ≈ 19 mN/m). Using a combination of optical imaging and rigorous heat transfer measurements in a controlled environmental chamber free from noncondensable gases (<4 Pa), we characterize the condensation behavior of ethanol and hexane on ultrascalable nanostructured CuO surfaces impregnated with fluorinated lubricants having varying viscosities (0.496 < µ < 5.216 Pa·s) and chemical structures (branched versus linear, Krytox and Fomblin). We demonstrate stable dropwise condensation of ethanol and hexane on LISs impregnated with Krytox 1525, attaining about 200% enhancement in condensation heat transfer coefficient for both fluids compared to filmwise condensation on hydrophobic surfaces. In contrast to previous studies, we use 7 h of steady dropwise condensation experiments to demonstrate the importance of rational lubricant selection to minimize lubricant drainage and maximize LIS durability. This work not only demonstrates an avenue to achieving stable dropwise condensation of ethanol and hexane, it develops the fundamental design principles for creating durable LISs for enhanced condensation heat transfer of low-surface-tension fluids.

Lubricant-Infused Surfaces for Low-Surface-Tension Fluids: The Extent of Lubricant Miscibility.

Lubricant-infused surfaces (LISs) and slippery liquid-infused porous surfaces (SLIPSs) have shown remarkable success in repelling low-surface-tension fluids. The atomically smooth, defect-free slippery surface leads to reduced droplet pinning and omniphobicity. However, the presence of a lubricant introduces liquid-liquid interactions with the working fluid. The commonly utilized lubricants for LISs and SLIPSs, although immiscible with water, show various degrees of miscibility with organic polar and nonpolar working fluids. Here, we rigorously investigate the extent of miscibility by considering a wide range of liquid-vapor surface tensions (12-73 mN/m) and different categories of lubricants having a range of viscosities (5-2700 cSt). Using high-fidelity analytical chemistry techniques including X-ray photoelectron spectroscopy, nuclear magnetic resonance, thermogravimetric analysis, and two-dimensional gas chromatography, we quantify lubricant miscibility to parts per billion accuracy. Furthermore, we quantify lubricant concentrations in the collected condensate obtained from prolonged condensation experiments with ethanol and hexane to delineate mixing and shear-based lubricant drainage mechanisms and to predict the lifetime of LISs and SLIPSs. Our work not only elucidates the effect of lubricant properties on miscibility with various fluids but also develops guidelines for developing stable and robust LISs and SLIPSs.

The development of a comprehensive toolbox based on multi-level, high-throughput screening of MOFs for CO/N2 separations.

The separation of CO/N2 mixtures is a challenging problem in the petrochemical sector due to the very similar physical properties of these two molecules, such as size, molecular weight and boiling point. To solve this and other challenging gas separations, one requires a holistic approach. The complexity of a screening exercise for adsorption-based separations arises from the multitude of existing porous materials, including metal-organic frameworks. Besides, the multivariate nature of the performance criteria that needs to be considered when designing an optimal adsorbent and a separation process - i.e. an optimal material requires fulfillment of several criteria simultaneously - makes the screening challenging. To address this, we have developed a multi-scale approach combining high-throughput molecular simulation screening, data mining and advanced visualization, as well as process system modelling, backed up by experimental validation. We have applied our recent advances in the engineering of porous materials' morphology to develop advanced monolithic structures. These conformed, shaped monoliths can be used readily in industrial applications, bringing a valuable strategy for the development of advanced materials. This toolbox is flexible enough to be applied to multiple adsorption-based gas separation applications.

Refinement of pore size at sub-angstrom precision in robust metal-organic frameworks for separation of xylenes.

The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal-organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host-guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6-18 for p- and m-xylenes.

Lubricant-Infused Surfaces for Low-Surface-Tension Fluids: Promise versus Reality.

The past few decades have seen substantial effort for the design and manufacturing of hydrophobic structured surfaces for enhanced steam condensation in water-based applications. Such surfaces promote dropwise condensation and easy droplet removal. However, less priority has been given to applications utilizing low-surface-tension fluids as the condensate. Lubricant-infused surfaces (LISs) or slippery liquid-infused porous surfaces (SLIPSs) have recently been developed, where the atomically smooth, defect-free slippery surface leads to reduced pinning of water droplets and omniphobic characteristics. The remarkable results of LISs and SLIPSs with a range of working fluid droplets give hope of their viability with low-surface-tension condensates. However, the presence of the additional liquid in the form of lubricant brings other issues to consider. Here, in an effort to study the dropwise condensation potential of LISs and SLIPSs, we investigate the miscibility of a range of low-surface-tension fluids with widely used lubricants in LIS and SLIPS design. We consider a wide range of condensate surface tensions (12-73 mN/m) and different categories of lubricants with varied viscosities (5-2700 cSt), namely, fluorinated Krytox oils, hydrocarbon silicone oils, mineral oil, and ionic liquids. In addition, we use both theory and pendant drop experiments to predict the cloaking behavior of the lubricants and immiscible condensate working fluid pairs. Our work not only shows that careful attention must be paid to lubricant-condensate selection to create long-lasting LISs or SLIPSs but also develops lubricant selection design guidelines for stable LISs and SLIPSs for enhanced condensation in applications utilizing low-surface-tension working fluids.