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This study investigates a neoteric approach in manufacturing lunar regolith-filled shape memory vitrimer (SMV) composites for extraterrestrial applications. A SMV with robust mechanical properties was combined with locally available lunar regolith to form a composite material. Fourier Transfer Infrared Spectroscopy (FTIR), Scanning Electron Microscope (SEM), Thermogravimetric Analysis (TGA), and X-ray fluorescence (XRF) were used to characterize the resin, the regolith simulant, and the prepared SMV-regolith composites. We explored conventional synthesis as well as 3D printing methods for manufacturing the composite. Glass fabric-reinforced laminated composites were also prepared to evaluate the impact tolerance and damage healing efficiency. Compressive strength, flexural strength, and impact resistance of the composite were tested at both room and elevated temperatures. A compressive strength of 96.0 MPa and 5.4 MPa were recorded for composite with 40 wt% regolith ratio at room and elevated temperatures, respectively. The glass fabric reinforced SMV-regolith laminate exhibited a bending strength of 232.7 MPa, good impact tolerance under low-velocity impact test, and good healing efficiency up to two damage healing cycles. The 3D printed SMV-regolith composite using a liquid crystal display (LCD)-based printer exhibited a good thermomechanical property with a compressive and tensile strength of 139.16 MPa and 13.99 MPa, respectively, and a good shape memory effect. However, the LCD-based printing using vat-photopolymerization limits the size of the printed samples. Nonetheless, this study shows that utilization of regolith to form advanced composite is possible. SMV regolith composite is a promising material for lunar base applications due to its simple manufacturing process, excellent mechanical properties, and low energy consumption. 

Here we introduce the synthesis and thermal properties of a series of sophisticated imidazolium ionenes with alternating amide-amide or amide-imide backbone functionality, and investigate the structural effects of mono(imidazolium) and unprecedented tris(imidazolium) ionic liquids (ILs) in these ionenes. The new set of poly(amide-amide) (PAA) and poly(amide-imide) (PAI) ionenes represent the intersection of conventional high-performance polymers with the ionene archetype–presenting polymers with alternating functional and ionic elements precisely sequenced along the backbone. The effects of polymer composition on the thermal properties and morphology were analyzed. Five distinct polymer backbones were synthesized and combined with a stoichiometric equivalent of the IL 1-benzyl-3-methylimidazolium bistriflimide ([Bnmim][Tf2N]), which were studied to probe the self-assembly, structuring, and contributions of intermolecular forces when IL is added. Furthermore, three polyamide (PA) or polyimide (PI) ionenes with simpler xylyl linkages were interfaced with [Bnmim][Tf2N] as well as a novel amide-linked tris(imidazolium) IL, to demonstrate the structural changes imparted by the inclusion of functional, ionic additives dispersed within the ionene matrix. This work highlights the possibilities for utilizing concepts from small molecules which exhibit supramolecular self-assembly to guide creative design and manipulate the structuring of ionenes. 

Three new isomeric 6FDA-based polyimide-ionenes, with imidazolium moieties and varying regiochemistry (para-, meta-, and ortho- connectivity), and composites with three different ionic liquids (ILs) have been developed as gas separation membranes. The structural-property relationships and gas separation behaviors of the newly developed 6FDA polyimide-ionene + IL composites have been extensively studied. All the 6FDA-based polyimide-ionenes exhibited good compatibility with the ILs and produced homogeneous hybrid membranes with the high thermal stability of ~380 °C. Particularly, [6FDA I4A pXy][Tf2N] ionene + IL hybrids having [C4mim][Tf2N] and [Bnmim][Tf2N] ILs offered mechanically stable matrixes with high CO2 affinity. The permeability of CO2 was increased by factors of 2 and 3 for C4mim and Bnmim hybrids (2.15 to 6.32 barrers), respectively, compared to the neat [6FDA I4A pXy][Tf2N] without sacrificing their permselectivity for CO2/CH4 and CO2/N2 gas pairs. 

Here, we report the synthesis and thermophysical properties of seven primarily aromatic, imidazolium-based polyamide ionenes. The effects of varied para-, meta-, and ortho-connectivity, and spacing of ionic and amide functional groups, on structural and thermophysical properties were analyzed. Suitable, robust derivatives were cast into thin films, neat, or with stoichiometric equivalents of the ionic liquid (IL) 1-benzy-3-methylimidazolium bistriflimide ([Bnmim][Tf2N]), and the gas transport properties of these membranes were measured. Pure gas permeabilities and permselectivities for N2, CH4, and CO2 are reported. Consistent para-connectivity in the backbone was shown to yield the highest CO2 permeability and suitability for casting as a very thin, flexible film. Derivatives containing terephthalamide segments exhibited the highest CO2/CH4 and CO2/N2 selectivities, yet CO2 permeability decreased with further deviation from consistent para-linkages. 

Abstract Polyimides (PI) synthesized from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with various diamines have been frequently studied as gas separation membranes. The use of 6FDA in polyimides creates a bent structure than can increase fractional free volume (FFV) and gas permeability. Here, we demonstrate that 6FDA is also a useful building block for PI‐ionene materials, which contain cations directly within the polymer backbone. These new 6FDA‐containing PI‐ionenes were combined with several different imidazolium ionic liquids (ILs) to form thin membranes. The thermal properties of all the derivatives were investigated to determine the relationship between regiochemistry and degradation as well as the intermolecular forces that are present within these structures. The gas separation properties of these 6FDA‐containing PI‐ionene + IL materials were investigated, showing modest CO₂permeabilities similar to other polyimide‐ionenes and CO₂/CH₄and CO₂/N₂permselectivities that were relatively higher than other polyimide‐ionenes.