3D Printing Hierarchically Nano‐Ordered Structures

Natural materials are composed of a limited number of molecular building blocks and their exceptional properties are governed by their hierarchical structure. However, this level of precision is unattainable with current state-of-the-art materials for 3D printing. Herein, new self-assembled printable materials based on block copolymers (BCPs) enabling precise control of the nanostructure in 3D are presented. In particular, well-defined BCPs consisting of poly(styrene) (PS) and a polymethacrylate-based copolymer decorated with printable units are selected as suitable self-assembled materials and synthesized using controlled radical polymerization. The synthesized library of BCPs are utilized as printable formulations for the fabrication of complex 3D microstructures using two-photon laser printing. By fine-tuning the BCP composition and solvent in the formulations, the fabrication of precise 3D nano-ordered structures is demonstrated for the first time. A key point of this work is the achievement of controlled nano-order within the entire 3D structures. Thus, imaging of the cross-sections of the 3D printed samples is performed, enabling the visualization also from the inside. The presented versatile approach is expected to create new avenues for the precise design of functional polymer materials suitable for high-resolution 3D printing exhibiting tailor-made nanostructures

Deconstructing 3D Structured Materials by Modern Ultramicrotomy for Multimodal Imaging and Volume Analysis across Length Scales

Based on the rapid advances in additive manufacturing, micro-patterned heterostructures of soft materials have become available that need to be characterized down to the nanoscale. Advanced function-structure relationships are designed by direct 3D structuring of the object and – in the future – fine control over material functionality in 3D will produce complex functional objects. To control their design, fabrication and final structure, morphological and spectroscopical imaging in 3D at nanometer resolution are critically required. With examples of carbon-based objects, it is demonstrated how serial ultramicrotomy, that is, cutting a large number of successive ultrathin sections, can be utilized to gain access to the interior of 3D objects. Array tomography, hierarchical imaging and correlative light and electron microscopy can bridge length scales over several orders of magnitude and provide multimodal information of the sample\u27s inner structure. Morphology data derived from scanning electron microscopy are correlated with spectroscopy in analytical transmission electron microscopy and probe microscopy at nanometer resolution, using TEM-electron energy loss spectroscopy and infrared-scanning-near-field microscopy. The correlation of different imaging modalities and spectroscopy of carbon-based materials in 3D provides a powerful toolbox of complementary techniques for understanding emerging functions from nanoscopic structuring

Digital Light 3D Printing of Double Thermoplastics with Customizable Mechanical Properties and Versatile Reprocessability

Digital light processing (DLP) is a 3D printing technology offering high resolution and speed. Printable materials are usually based on multifunctional monomers, resulting in the formation of thermosets that cannot be reprocessed or recycled. Some efforts have been made in DLP 3D printing of thermoplastic materials. However, these materials exhibit limited and poor mechanical properties. Here, we present a new strategy for DLP 3D printing of thermoplastics using two polymers with contrasting mechanical properties, where stiff and flexible linear polymers are sequentially constructed. The inks consist of two vinyl monomers, which lead to the stiff linear polymer, and α-lipoic acid to form the flexible linear polymer via thermal ring-opening polymerization in a second step. By varying the ratio of stiff and flexible polymers, the mechanical properties can be tuned with Young\u27s modulus ranging from 1.1 GPa to 0.7 MPa, while the strain at break increased from 4% to 574%. Furthermore, these 3D-printed thermoplastics allow for a variety of reprocessability pathways including self-healing, solvent casting, reprinting, and closed-loop recycling of the flexible polymer, contributing to the development of a sustainable materials economy. Last, we demonstrate the potential of the new material in applications ranging from soft robotics to electronics