High-performance, all-aromatic, insoluble, engineering thermoplastic polyimides, such as pyromellitic dianhydride and 4,4'-oxydianiline (PMDA-ODA) (Kapton), exhibit exceptional thermal stability (up to ≈600 °C) and mechanical properties (Young's modulus exceeding 2 GPa). However, their thermal resistance, which is a consequence of the all-aromatic molecular structure, prohibits processing using conventional techniques. Previous reports describe an energy-intensive sintering technique as an alternative technique for processing polyimides with limited resolution and part fidelity. This study demonstrates the unprecedented 3D printing of PMDA-ODA using mask-projection stereolithography, and the preparation of high-resolution 3D structures without sacrificing bulk material properties. Synthesis of a soluble precursor polymer containing photo-crosslinkable acrylate groups enables light-induced, chemical crosslinking for spatial control in the gel state. Postprinting thermal treatment transforms the crosslinked precursor polymer to PMDA-ODA. The dimensional shrinkage is isotropic, and postprocessing preserves geometric integrity. Furthermore, large-area mask-projection scanning stereolithography demonstrates the scalability of 3D structures. These unique high-performance 3D structures offer potential in fields ranging from water filtration and gas separation to automotive and aerospace technologies.
Vat photopolymerization (VP) additive manufacturing fabricates intricate geometries with excellent resolution; however, high molecular weight polymers are not amenable to VP due to concomitant high solution and melt viscosities. Thus, a challenging paradox arises between printability and mechanical performance. This report describes concurrent photopolymer and VP system design to navigate this paradox with the unprecedented use of polymeric colloids (latexes) that effectively decouple the dependency of viscosity on molecular weight. Photocrosslinking of a continuous-phase scaffold, which surrounds the latex particles, combined with in situ computer-vision print parameter optimization, which compensates for light scattering, enables high-resolution VP of high molecular weight polymer latexes as particle-embedded green bodies. Thermal post-processing promotes coalescence of the dispersed particles throughout the scaffold, forming a semi-interpenetrating polymer network without loss in part resolution. Printing a styrene-butadiene rubber latex, a previously inaccessible elastomer composition for VP, exemplified this approach and yielded printed elastomers with precise geometry and tensile extensibilities exceeding 500%.
The ubiquitous biomacromolecule DNA has an axial rigidity persistence length of ~50 nm, driven by its elegant double helical structure. While double and multiple helix structures appear widely in nature, only rarely are these found in synthetic non-chiral macromolecules. Here we report a double helical conformation in the densely charged aromatic polyamide poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) or PBDT. This double helix macromolecule represents one of the most rigid simple molecular structures known, exhibiting an extremely high axial persistence length (~1 micrometer). We present X-ray diffraction, NMR spectroscopy, and molecular dynamics (MD) simulations that reveal and confirm the double helical conformation. The discovery of this extreme rigidity in combination with high charge density gives insight into the self-assembly of molecular ionic composites with high mechanical modulus (~ 1 GPa) yet with liquid-like ion motions inside, and provides fodder for formation of other 1D-reinforced composites.
Polymer electrolyte membranes (PEMs) with high volume fractions of ionic liquids (IL) and high modulus show promise for enabling next-generation gas separations, and electrochemical energy storage and conversion applications. Herein, we present a conductive polymer-IL composite based on a sulfonated all-aromatic polyamide (sulfo-aramid, PBDT) and a model IL, which we term a PBDT-IL composite. The polymer forms glassy and high-aspect-ratio hierarchical nanofibrils, which enable fabrication of PEMs with both high volume fractions of IL and high elastic modulus. We report direct evidence for nanofibrillar networks that serve as matrices for dispersed ILs using atomic force microscopy and small- and wide-angle X-ray scattering. These supramolecular nanofibrils form through myriad noncovalent interactions to produce a physically cross-linked glassy network, which boasts the best combination of room-temperature modulus (0.1–2 GPa) and ionic conductivity (8–4 mS cm–1) of any polymer-IL electrolyte reported to date. The ultrahigh thermomechanical properties of our PBDT-IL composites provide high moduli (∼1 GPa) at temperatures up to 200 °C, enabling a wide device operation window with stable mechanical properties. Together, the high-performance nature of sulfo-aramids in concert with the inherent properties of ILs imparts PBDT-IL composites with nonflammability and thermal stability up to 350 °C. Thus, nanofibrillar ionic networks based on sulfo-aramids and ILs represent a new design paradigm affording PEMs with exceptionally high moduli at exceedingly low polymer concentrations. This new design strategy will drive the development of new high-performance conductive membranes that can be used for the design of gas separation membranes and in electrochemical applications, such as fuel cells and Li-metal batteries.
Due to continued health and safety concerns surrounding isocyanates, alternative synthetic routes to obtain urea-containing polymers is gaining much attention.
We have selected two amorphous all-aromatic poly(ether imide)s with similar chemical structures but with different backbone geometries as matrices for SWCNT-based nanocomposites. Up to 4.4 vol %, SWCNTs could be incorporated using an in situ polymerization method. Nanocomposites prepared from aBPDA-P3, a nonlinear matrix polymer with a T g of 230 °C, remains amorphous, and the presence of the SWCNTs reduces the T g by 11 °C. No effect on E′ or stress−strain behavior was observed. When ODPA-P3 was used as the matrix, the SWCNTs appear to be highly compatible with this more linear polymer host. The SWCNTs act as a nucleating agent at concentrations as low as 0.1 vol %. XRD and TEM measurements show that the SWCNTs become embedded in a highly crystalline polymer matrix. The result is a significant change in thermomechanical properties. The polymer T g was increased by 12 °C, from 196 to 208 °C, and due to the induced crystallinity, the modulus above T g showed a dramatic increase. The neat polymer fails at T g , but the 4.4 vol % nanocomposite shows a storage modulus of 1 GPa at 280 °C. Stress−strain measurements show a noticeable improvement in strain and toughness at low SWCNT loadings (0.1−0.3 wt %), which is indicative of good stress transfer between the SWCNTs and polymer matrix. At higher loadings the yield strength increases from 80 to 126 MPa at 4.5% strain. Our findings show that the poly(ether imide) backbone geometry determines whether the polymer is good host for SWCNTs. The more linear ODPA-P3 is able to maximize its interaction with the SWCNT surface. To the best of our knowledge, this is the first time that an amorphous polymer has been shown to develop a semicrystalline morphology in the presence of SWCNTs. Steric factors in aBPDA-P3 seem to inhibit favorable π−π interactions and prevent the polymer chains from adapting low-energy conformations that readily interact with the SWCNT surface.
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