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Associative surfactants systems involving polar oils have recently been shown to stabilize immiscible liquids by forming nanostructures at the liquid interface and have been used to print soft materials. Although these associating surfactant systems show great promise for creating nanostructured soft materials, a fundamental understanding of the self-assembly process is still unknown. In this study, a ternary phase diagram for a system of cationic surfactant cetylpyridinium chloride monohydrate (CPCl), a polar oil (oleic acid), and water is established using experiment and simulation, to study the equilibrium phase behavior. A combination of visual inspection, small-angle X-ray scattering (SAXS), and rheological measurements was employed to establish the phase behavior and properties of the self-assembled materials. Dissipative particle dynamics (DPD) is used to simulate the formation of the morphologies in this system and support the experimental results. The ternary phase diagram obtained from the simulations agrees with the experimental results, indicating the robustness of the computational simulation as a supplement to the mesoscale experimental systems. We observe that morphological transitions ( e.g. , micelle-to-bilayer and vesicle-to-lamellar) are in agreement between experiments and simulations across the ternary diagram. DPD simulations correctly predict that associative surfactant systems form new nanoscale phases due to the co-assembly of the components. The established ternary phase diagram and the DPD model pave the way towards predicting and controlling the formation of different mesostructures like lamellar or vesicles, opening new avenues to tailor and synthesize desired morphologies for applications related to liquid-in-liquid 3D printing.
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Fabricating Robust Constructs with Internal Phase Nanostructures via Liquid‐in‐Liquid 3D Printing
Abstract The ability to print soft materials into predefined architectures with programmable nanostructures and mechanical properties is a necessary requirement for creating synthetic biomaterials that mimic living tissues. However, the low viscosity of common materials and lack of required mechanical properties in the final product present an obstacle to the use of traditional additive manufacturing approaches. Here, a new liquid‐in‐liquid 3D printing approach is used to successfully fabricate constructs with internal nanostructures using in situ self‐assembly during the extrusion of an aqueous solution containing surfactant and photocurable polymer into a stabilizing polar oil bath. Subsequent photopolymerization preserves the nanostructures created due to surfactant self‐assembly at the immiscible liquid–liquid interface, which is confirmed by small‐angle X‐ray scattering. Mechanical properties of the photopolymerized prints are shown to be tunable based on constituent components of the aqueous solution. The reported 3D printing approach expands the range of low‐viscosity materials that can be used in 3D printing, and enables robust constructs production with internal nanostructures and spatially defined features. The reported approach has broad applications in regenerative medicine by providing a platform to print self‐assembling biomaterials into complex tissue mimics where internal supramolecular structures and their functionality control biological processes, similar to natural extracellular matrices.
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- Award ID(s):
- 1942508
- PAR ID:
- 10360724
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Macromolecular Rapid Communications
- Volume:
- 42
- Issue:
- 22
- ISSN:
- 1022-1336
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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