Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

Soft materials capable of transforming between three-dimensional (3D) shapes in response to stimuli such as light, heat, solvent, electric and magnetic fields have applications in diverse areas such as flexible electronics1,2, soft robotics3,4 and biomedicine5–7. In particular, magnetic fields offer a safe and effective manipulation method for biomedical applications, which typically require remote actuation in enclosed and confined spaces8–10. With advances in magnetic field control
 11
 , magnetically responsive soft materials have also evolved from embedding discrete magnets
 12
 or incorporating magnetic particles
 13
 into soft compounds to generating nonuniform magnetization profiles in polymeric sheets14,15. Here we report 3D printing of programmed ferromagnetic domains in soft materials that enable fast transformations between complex 3D shapes via magnetic actuation. Our approach is based on direct ink writing
 16
 of an elastomer composite containing ferromagnetic microparticles. By applying a magnetic field to the dispensing nozzle while printing
 17
 , we reorient particles along the applied field to impart patterned magnetic polarity to printed filaments. This method allows us to program ferromagnetic domains in complex 3D-printed soft materials, enabling a set of previously inaccessible modes of transformation, such as remotely controlled auxetic behaviours of mechanical metamaterials with negative Poisson’s ratios. The actuation speed and power density of our printed soft materials with programmed ferromagnetic domains are orders of magnitude greater than existing 3D-printed active materials. We further demonstrate diverse functions derived from complex shape changes, including reconfigurable soft electronics, a mechanical metamaterial that can jump and a soft robot that crawls, rolls, catches fast-moving objects and transports a pharmaceutical dose.

Printing ferromagnetic domains for untethered fast-transforming soft materials

Research in soft matter engineering has introduced new approaches in robotics and wearable devices that can interface with the human body and adapt to unpredictable environments. However, many promising applications are limited by the dependence of soft systems on electrical or pneumatic tethers. Recent work in soft actuation and electronics has made removing such cords more feasible, heralding a variety of applications from autonomous field robotics to wireless biomedical devices. Here we review the development of functional untethered soft robotics. We focus on recent advances in soft robotic actuation, sensing and integration as they relate to untethered systems, and consider the key challenges the field faces in engineering systems that could have practical use in real-world conditions. This Review Article examines the development of functional untethered soft robotics, evaluating recent advances in soft robotic actuation, sensing, and integration in relation to untethered systems.

Untethered soft robotics

The field of 3D printing is continuing its rapid development in both academic and industrial research environments. The development of 3D printing technologies has opened new implementations in rapid prototyping, tooling, dentistry, microfluidics, biomedical devices, tissue engineering, drug delivery, etc. Among different 3D printing techniques, photopolymerization-based process (such as stereolithography and digital light processing) offers flexibility over the final properties of the 3D printed materials (such as optical, chemical, and mechanical properties) using versatile polymer chemistry. The strategy behind the 3D photopolymerization is based on using monomers/oligomers in liquid state (in the presence of photoinitiators) that can be photopolymerized (via radical or cationic mechanism) upon exposure to light source of different wavelengths (depending on the photoinitiator system). An overview of recent evolutions in the field of photopolymerization-based 3D printing and highlights of novel 3D print...

Photopolymerization in 3D Printing

Advances in 4D Printing: Materials and Applications

In this work, we advance printed active composites by combining 3D printing, printed electronics, and liquid crystal elastomers (LCEs) to achieve soft actuators with free-standing two-way shape changing behaviors. Incorporated LCE strips are activated by Joule heating produced by printed conductive wires, while uniaxial deformation of the LCE strip is utilized as a driving force to achieve bending in the printed composite. The bending behavior of laminated hinges is first characterized in order to obtain a precise control of actuation, which is then exploited to actuate four demonstrative designs: a morphing airplane, a miura-ori structure, a cubic box, and a soft crawler. The soft morphing airplane and miura-ori structure are designed and fabricated with multiple laminated hinges to demonstrate the synergistic actions during actuation. The cubic box is constructed to show the capability of sequential folding by implementing multiple groups of conductive wires to achieve accurately addressable heating with temporal control. Finally, the two-way transformation is utilized as a driving force for the locomotion of a soft crawler stimulated by a periodic rectangular wave current. These examples show the great potential of using the hybrid 3D printing and pick-and-place method and using LCEs to achieve controllable shape change structures for a variety of potential practical applications.

3D printed reversible shape changing soft actuators assisted by liquid crystal elastomers

A method for fabricating long, soft, and reversibly actuatable liquid crystal elastomer (LCE) fibers by using direct ink write (DIW) printing was developed. Here, the LCE was produced based on a tw...

Long Liquid Crystal Elastomer Fibers with Large Reversible Actuation Strains for Smart Textiles and Artificial Muscles.

https://iopscience.iop.org/article/10.1088/1361-665X/aae96f/pdf

Novel ink for ambient condition printing of liquid crystal elastomers for 4D printing

The advent of additive manufacturing (AM), also often referred to as 3D printing, has enabled the rapid production of parts with complex geometries that are either labor-intensive or unrealizable by traditional manufacturing methods. Many existing 3D printing technologies, however, only allow one material to be printed at one time, while many applications require the integration of different materials, which sometimes cannot be printed by one AM technology. In this paper, a novel multi-material multi-method (m4) 3D printer comprised of multiple AM technologies is presented as a solution to the current limitations. This printer fosters the advancement of AM by combining materials traditionally unable to be printed concurrently while adding functionality to printed parts. The m4 3D printer integrates four AM technologies and two complementary technologies onto one single platform, including inkjet (IJ), fused filament fabrication (FFF), direct ink writing (DIW), and aerosol jetting (AJ), along with robotic arms for pick-and-place (PnP) and photonic curing for intense pulsed light (IPL) sintering. The integration of these AM technologies and PnP into a single platform allows for rapid fabrication of complex devices, providing a wide range of functionalities with applications ranging from soft robotics and flexible electronics to medical devices.

Devin J. Roach

Papers

Advances in 4D Printing: Materials and Applications

3D printed reversible shape changing soft actuators assisted by liquid crystal elastomers

Long Liquid Crystal Elastomer Fibers with Large Reversible Actuation Strains for Smart Textiles and Artificial Muscles.

Novel ink for ambient condition printing of liquid crystal elastomers for 4D printing

The m4 3D printer: A multi-material multi-method additive manufacturing platform for future 3D printed structures