On the Performance of Confined Deep Eutectic Solvents and Ionic Liquids for Separations of Carbon Dioxide from Methane: Molecular Dynamics Simulations.

Classical molecular dynamics simulations were used to investigate the performance of slit graphite and titania (rutile) pores of 5.2 nm in width, partially and completely filled with deep eutectic solvents (DESs) or ionic liquids (ILs), for gas separations of a carbon dioxide-methane mixture of 5:95 molar ratio and temperatures and pressures on the order of 318 K and 100 bar, respectively. The DESs studied were ethaline and levuline (1:2 molar mixtures of choline chloride with ethylene glycol or levulinic acid), and the IL considered was 1- n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim+][NTf2-]. The performance of these systems in terms of solubility selectivity, diffusion selectivity, and permselectivity was compared against the performance of the bulk solvents (which could also be viewed as a model system for the micrometer-sized pores of a supported IL or DES membrane) and against carbon and rutile pores without preadsorbed solvent. The best performance in terms of permselectivity is obtained for bulk levuline and by rutile pores fully filled by ethaline, followed by graphite pores filled by ethaline and the IL. Empty rutile pores have the largest value of solubility selectivity, followed by bulk ethaline and rutile pores completely filled by the IL. The largest values of diffusivity selectivity were observed for bulk levuline, followed by ethaline completely filling a rutile nanopore and a graphite nanopore completely filled with the IL. These observations are rationalized by examining local density profiles and interaction energies among the different entities in our systems. In general, systems of nanopores fully filled by solvents, as well as the bulk solvents, have larger permselectivities than pores partially filled by the IL or the DESs. Drops of 2-3 orders of magnitude are observed in the gas diffusivity in pores filled with solvents with respect to systems of empty pores, which may be problematic if gas permeation is mainly controlled by diffusion. However, if adsorption dominates the gas permeation within the membrane, our results suggest that systems of levuline in the micrometer-sized pores of a supported DES membrane or ethaline confined in the rutile nanopores of a supported DES phase material might represent promising systems for gas separation.

Computational Evaluation of Mixtures of Hydrofluorocarbons and Deep Eutectic Solvents for Absorption Refrigeration Systems.

We used computational tools to evaluate three working fluid mixtures for single-effect absorption refrigeration systems, where the generator (desorber) is powered by waste or solar heat. The mixtures studied here resulted from combining a widely used hydrofluorocarbon (HFC) refrigerant, R134a, with three common deep eutectic solvents (DESs) formed by mixing choline chloride (hydrogen bond acceptor, HBA) with urea, glycerol, or ethylene glycol as the hydrogen bond donor (HBD) species. The COSMOtherm/TmoleX software package was used in combination with refrigerant data from NIST/REFPROP, to perform a thermodynamic evaluation of absorption refrigeration cycles using the proposed working fluid mixtures. Afterward, classical MD simulations of the three mixtures were performed to gain insight on these systems at the molecular level. Larger cycle efficiencies are obtained when R134a is combined with choline chloride and ethylene glycol, followed by the system where glycerol is the HBD, and finally that where the HBD is urea. MD simulations indicate that the local density profiles of all species exhibit very sharp variations in systems containing glycerol or urea; furthermore, the Henry's law constants of R134a in these two systems are larger than those observed for the HFC in choline chloride and ethylene glycol, indicating that R134a is more soluble in the latter DES. Interaction energies indicate that the R134a-R134a interactions are weaker in the system where ethylene glycol is the HBD, as compared to in the other DES. Radial distribution functions confirm that in all systems, the DES species do not form strong directional interactions (e.g., hydrogen bonds) with the R134a molecules. Relatively strong interactions are observed between the Cl anions and the hydrogen atoms in R134a; however, the atom-atom interactions between R134a and the cation and HBD species are weaker and do not play a significant role in the solvation of the refrigerant. In all systems, R134a has the largest diffusion coefficients, followed by the HBD, the anion and the cation; the diffusion coefficients are the largest in the systems containing ethylene glycol, followed by those having glycerol and urea. This work is our first step toward our long-term goal of designing and demonstrating optimal working fluid mixtures for use in absorption refrigeration systems. Our results suggest that COSMO-RS can be used to perform a rapid screening of a large number of working fluid mixtures, and select a few candidates for further exploration using molecular simulations and experiments. These latter approaches can be used to refine the accuracy of the COSMO-RS predictions, and to optimize the selection of optimal working fluid mixtures for demonstration in absorption refrigeration systems powered by solar or waste heat sources.

A Thermoset Shape Memory Polymer-Based Syntactic Foam with Flame Retardancy and 3D Printability.

Here we report a thermoset shape memory polymer-based syntactic foam inherently integrated with flame retardancy, good mechanical properties, excellent shape memory effect, and 3D printability. The syntactic foam is fabricated by incorporating a high-temperature shape memory polymer (HTSMP) as the matrix, with 40 vol % hollow glass microspheres (HGM) K20, K15, and K1 as fillers. Compressive behavior, strain-controlled programming followed by free recovery, stress recovery, and flame retardancy of these three syntactic foams were studied. Dynamic mechanical analysis and thermal characterization validate their high glass transition temperature (T g = ∼250 °C) and excellent thermal stability. Our results suggest that the foam consisting of K20 HGM exhibits high compressive strength (81.8 MPa), high recovery stress (6.8 MPa), and excellent flame retardancy. Furthermore, this syntactic foam was used for three-dimensional (3D) printing by an extruder developed in our lab. Honeycomb, sinusoidal shapes, and free-standing helical spring were printed for demonstration. This high-temperature photopolymer-based syntactic foam integrated with high T g, flame retardancy, high recovery stress, and 3D printability can be beneficial in different sectors such as aerospace, construction, oil and gas, automotive, and electronic industries.

Deep Eutectic Solvents Mixed with Fluorinated Refrigerants for Absorption Refrigeration: A Molecular Simulation Study.

Molecular simulations were performed to evaluate mixtures of fluorinated refrigerants with deep eutectic solvents (DESs), for potential use in single-effect absorption refrigeration cycles that use low quality waste heat sources at temperatures of ∼80 °C. The refrigerants considered were the hydrofluorocarbon R245fa and the hydrofluoroolefins R1234zeE and HFO1336mzzE, whereas the DESs evaluated were 1:2 molar mixtures of choline chloride with either ethylene glycol (ethaline) or levulinic acid (levuline) as hydrogen bond donors (HBDs). Assuming the same cycle operating conditions, the waste heat cycle efficiency η was computed for all working fluid mixtures from molecular simulation results of the mixture densities and Henry's law constants of the refrigerants in the DESs, coupled with phase equilibrium calculations and the enthalpies of the pure refrigerants. The largest efficiency was obtained for the mixture R245fa-ethaline (η = 6.82), followed by R245fa-levuline (η = 4.64) and HFO1336mzzE-levuline (η = 2.10). These modest efficiency values could be further increased by tailoring the cycle operating conditions to each particular refrigerant-DES system, as well as optimizing our choice of working fluid mixtures, neither of which we attempted in this study. Strong interactions were observed between the chlorine anions and some of the hydrogen atoms of the refrigerants, but in general the cation-refrigerant and HBD-refrigerant interactions are weaker compared to the refrigerant-refrigerant interactions. Refrigerant molecules have the largest diffusivities and make the cations, anions and HBD to move faster compared to systems of DESs without refrigerant; in general, species in refrigerant-ethaline mixtures have larger diffusivities compared to those for refrigerant-levuline mixtures. We also computed waste heat cycle efficiencies for the same R134a-DES mixtures studied in our previous work, finding significant differences between the efficiencies determined from molecular simulation data and those determined before using the COSMO-RS approach using two standard parametrizations. This observation suggests that further work is needed to improve the accuracy of the COSMO-RS predictions for these systems.