Issue

Vol. 16 (2024)

Engineering Nano/Microscale Chiral Self-Assembly in 3D Printed Constructs

https://doi.org/10.1007/s40820-023-01286-0
Mohsen Esmaeili
Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA
Ehsan Akbari
TA Instruments, Waters LLC, New Castle, DE 19720, USA
Kyle George
Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA
Gelareh Rezvan
Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA
Nader Taheri‑Qazvini
Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA
Monirosadat Sadati
Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA

Corresponding Author: Monirosadat Sadati

sadati@cec.sc.edu

Nano-Micro Letters, Vol. 16 (2024), Article Number: 54

Abstract

Helical hierarchy found in biomolecules like cellulose, chitin, and collagen underpins the remarkable mechanical strength and vibrant colors observed in living organisms. This study advances the integration of helical/chiral assembly and 3D printing technology, providing precise spatial control over chiral nano/microstructures of rod-shaped colloidal nanoparticles in intricate geometries. We designed reactive chiral inks based on cellulose nanocrystal (CNC) suspensions and acrylamide monomers, enabling the chiral assembly at nano/microscale, beyond the resolution seen in printed materials. We employed a range of complementary techniques including Orthogonal Superposition rheometry and in situ rheo-optic measurements under steady shear rate conditions. These techniques help us to understand the nature of the nonlinear flow behavior of the chiral inks, and directly probe the flow-induced microstructural dynamics and phase transitions at constant shear rates, as well as their post-flow relaxation. Furthermore, we analyzed the photo-curing process to identify key parameters affecting gelation kinetics and structural integrity of the printed object within the supporting bath. These insights into the interplay between the chiral inks self-assembly dynamics, 3D printing flow kinematics and photo-polymerization kinetics provide a roadmap to direct the out-of-equilibrium arrangement of CNC particles in the 3D printed filaments, ranging from uniform nematic to 3D concentric chiral structures with controlled pitch length, as well as random orientation of chiral domains. Our biomimetic approach can pave the way for the creation of materials with superior mechanical properties or programable photonic responses that arise from 3D nano/microstructure and can be translated into larger scale 3D printed designs.


Highlights:
1 To precisely engineer complex helical hierarchies at nano/microscales, reactive inks with chiral nematic anisotropy are designed for 3D printing.
2 The phase transformations and chiral evolution in response to parallel and orthogonal shear forces are meticulously investigated to finely adjust the 3D printing parameters for programming oriented chiral assemblies.
3 The interplay between chiral relaxation dynamics and photo-polymerization kinetics is finely tuned to enable well-controlled chiral reformation, while simultaneously ensuring high print quality.

Keywords

Directed chiral self-assembly Cellulose nanocrystals Bioinspired nanocomposite 3D printing Rheology
Esmaeili, Mohsen, Ehsan Akbari, Kyle George, Gelareh Rezvan, Nader Taheri‑Qazvini, and Monirosadat Sadati. 2023. “Engineering Nano/Microscale Chiral Self-Assembly in 3D Printed Constructs”. Nano-Micro Letters 16 (December):54. https://doi.org/10.1007/s40820-023-01286-0.
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