Fabrication of multiscale, multimaterial 3D structures at high resolution is difficult using current technologies. This is especially significant when working with mechanically weak hydrogels. Here, a new hybrid laser printing (HLP) technology is reported to print complex, multiscale, multimaterial, 3D hydrogel structures with microscale resolution. This technique utilizes sequential additive and subtractive modes of fabrication, that are typically considered as mutually exclusive due to differences in their material processing conditions. Further, compared to current laser writing systems that enforce stringent processing depth limits, HLP is shown to fabricate structures at any depth inside the material. As a proof‐of‐principle, a Mayan pyramid with embedded cube frame is printed using synthetic polyethylene glycol diacrylate (PEGDA) hydrogel. Printing of ready‐to‐use open‐well chips with embedded microchannels is also demonstrated using PEGDA and gelatin methacrylate (GelMA) hydrogels for potential applications in biomedical sciences. Next, HLP is used in additive–additive modes to print multiscale 3D structures spanning in size from centimeter to micrometers within minutes, which is followed by printing of 3D, multimaterial, multiscale structures using this technology. Overall, this work demonstrates that HLP's fabrication versatility can potentially offer a unique opportunity for a range of applications in optics and photonics, biomedical sciences, microfluidics, etc.
A Power Compensation Strategy for Achieving Homogeneous Microstructures for 4D Printing Shape-Adaptive PNIPAM Hydrogels: Out-of-Plane Variations
In the last decade, 3D printing has attracted significant attention and has resulted in benefits to many research areas. Advances in 3D printing with smart materials at the microscale, such as hydrogels and liquid crystalline polymers, have enabled 4D printing and various applications in microrobots, micro-actuators, and tissue engineering. However, the material absorption of the laser power and the aberrations of the laser light spot will introduce a decay in the polymerization degree along the height direction, and the solution to this problem has not been reported yet. In this paper, a compensation strategy for the laser power is proposed to achieve homogeneous and high aspect ratio hydrogel structures at the microscale along the out-of-plane direction. Linear approximations for the power decay curve are adopted for height steps, discretizing the final high aspect ratio structures. The strategy is achieved experimentally with hydrogel structures fabricated by two-photon polymerization. Moreover, characterizations have been conducted to verify the homogeneity of the printed microstructures. Finally, the saturation of material property is investigated by an indirect 3D deformation method. The proposed strategy is proved to be effective and can be explored for other hydrogel materials showing significant deformation. Furthermore, the strategy for out-of-plane variations provides a critical technique to achieve 4D-printed homogeneous shape-adaptive hydrogels for further applications.
more »
« less
- NSF-PAR ID:
- 10444269
- Date Published:
- Journal Name:
- Gels
- Volume:
- 8
- Issue:
- 12
- ISSN:
- 2310-2861
- Page Range / eLocation ID:
- 828
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Abstract Microscale machines are able to perform a number of tasks like micromanipulation, drug‐delivery, and noninvasive surgery. In particular, microscale polymer machines that can perform intelligent work for manipulation or transport, adaptive locomotion, or sensing are in‐demand. To achieve this goal, shape‐morphing smart polymers like hydrogels, liquid crystalline polymers, and other smart polymers are of great interest. Structures fabricated by these materials undergo mechanical motion under stimulation such as temperature, pH, light, and so on. The use of these materials renders microscale machines that undergo complex stimuli‐responsive transformation such as from planar to 3D by combining spatial design like introducing in‐plane or out‐plane differences. During the past decade, many techniques have been developed or adopted for fabricating structures with smart polymers including microfabrication methods and the well‐known milestone of 4D printing, starting in 2013. In this review, the existing or potential active smart polymers that could be used to fabricate active microscale machines to accomplish complex tasks are summarized.
-
Abstract 2D material hydrogels have recently sparked tremendous interest owing to their potential in diverse applications. However, research on the emerging 2D MXene hydrogels is still in its infancy. Herein, we show a universal 4D printing technology for manufacturing MXene hydrogels with customizable geometries, which suits a family of MXenes such as Nb 2 CT x , Ti 3 C 2 T x , and Mo 2 Ti 2 C 3 T x . The obtained MXene hydrogels offer 3D porous architectures, large specific surface areas, high electrical conductivities, and satisfying mechanical properties. Consequently, ultrahigh capacitance (3.32 F cm −2 (10 mV s −1 ) and 233 F g −1 (10 V s −1 )) and mass loading/thickness-independent rate capabilities are achieved. The further 4D-printed Ti 3 C 2 T x hydrogel micro-supercapacitors showcase great low-temperature tolerance (down to –20 °C) and deliver high energy and power densities up to 93 μWh cm −2 and 7 mW cm −2 , respectively, surpassing most state-of-the-art devices. This work brings new insights into MXene hydrogel manufacturing and expands the range of their potential applications.more » « less
-
Conventional lithium-ion batteries are unable to meet the increasing demands for high-energy storage systems, because of their limited theoretical capacity. 1 In recent years, intensive attention has been paid to enhancing battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next generation high energy storage systems, the lithium sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and potential cost reduction. In addition, sulfur is a cost effective and environmentally friendly material due to its abundance and low-toxicity. 2 Despite all of these advantages, the practical application of lithium sulfur batteries to date has been hindered by a series of obstacles, including low active material loading, poor cycle life, and sluggish sulfur conversion kinetics. 3 Achieving high mass loading cathode in the traditional 2D planar thick electrode has been challenged. The high distorsion of the traditional planar thick electrodes for ion/electron transfer leads to the limited utilization of active materials and high resistance, which eventually results in restricted energy density and accelerated electrode failure. 4 Furthermore, of the electrolyte to pores in the cathode and utilization ratio of active materials. Catalysts such as MnO 2 and Co dopants were employed to accelerate the sulfur conversion reaction during the charge and discharge process. 5 However, catalysts based on transition metals suffer from poor electronic conductivity. Other catalysts such as transition metal dopants are also limited due to the increased process complexities. . In addition, the severe shuttle effects in Li-S batteries may lead to fast failures of the battery. Constructing a protection layer on the separator for limiting the transmission of soluble polysulfides is considered an effective way to eliminate the shuttle phenomenon. However, the soluble sulfides still can largely dissolve around the cathode side causing the sluggish reaction condition for sulfur conversion. 5 To mitigate the issues above, herein we demonstrate a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative vapor deposition (oCVD). Specifically, the electrode is strategically designed into a hierarchal hollow structure via stereolithography technique to increase sulfur usage. The active material concentration loaded to the battery cathode is controlled precisely during 3D printing by adjusting the number of printed layers. Owing to its freedom in geometry and structure, the suggested design is expected to improve the Li ions and electron transport rate considerably, and hence, the battery power density. The printed cathode is sintered at 700 °C at N 2 atmosphere to achieve carbonization of the cathode during which intrinsic carbon defects (e.g., pentagon carbon) as catalytic defect sites are in-situ generated on the cathode. The intrinsic carbon defects equipped with adequate electronic conductivity. The sintered 3D cathode is then transferred to the oCVD chamber for depositing a thin PEDOT layer as a protection layer to restrict dissolutions of sulfur compounds in the cathode. Density functional theory calculation reveals the electronic state variance between the structures with and without defects, the structure with defects demonstrates the higher kinetic condition for sulfur conversion. To further identify the favorable reaction dynamic process, the in-situ XRD is used to characterize the transformation between soluble and insoluble polysulfides, which is the main barrier in the charge and discharge process of Li-S batteries. The results show the oCVD coated 3D printed sulfur cathode exhibits a much higher kinetic process for sulfur conversion, which benefits from the highly tailored hierarchal hollow structure and the defects engineering on the cathode. Further, the oCVD coated 3D printed sulfur cathode also demonstrates higher stability during long cycling enabled by the oCVD PEDOT protection layer, which is verified by an absorption energy calculation of polysulfides at PEDOT. Such modeling and analysis help to elucidate the fundamental mechanisms that govern cathode performance and degradation in Li-S batteries. The current study also provides design strategies for the sulfur cathode as well as selection approaches to novel battery systems. References: Bhargav, A., (2020). Lithium-Sulfur Batteries: Attaining the Critical Metrics. Joule 4 , 285-291. Chung, S.-H., (2018). Progress on the Critical Parameters for Lithium–Sulfur Batteries to be Practically Viable. Advanced Functional Materials 28 , 1801188. Peng, H.-J.,(2017). Review on High-Loading and High-Energy Lithium–Sulfur Batteries. Advanced Energy Materials 7 , 1700260. Chu, T., (2021). 3D printing‐enabled advanced electrode architecture design. Carbon Energy 3 , 424-439. Shi, Z., (2021). Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives. Advanced Energy Materials 11 . Figure 1more » « less
-
Hydrogels are candidate building blocks in a wide range of biomaterial applications including soft and biohybrid robotics, microfluidics, and tissue engineering. Recent advances in embedded 3D printing have broadened the design space accessible with hydrogel additive manufacturing. Specifically, the Freeform Reversible Embedding of Suspended Hydrogels (FRESH) technique has enabled the fabrication of complex 3D structures using extremely soft hydrogels, e.g., alginate and collagen, by assembling hydrogels within a fugitive support bath. However, the low structural rigidity of FRESH printed hydrogels limits their applications, especially those that require operation in nonaqueous environments. In this study, we demonstrated long-fiber embedded hydrogel 3D printing using a multihead printing platform consisting of a custom-built fiber extruder and an open-source FRESH bioprinter with high embedding fidelity. Using this process, fibers were embedded in 3D printed hydrogel components to achieve significant structural reinforcement (e.g., tensile modulus improved from 56.78 ± 8.76 to 382.55 ± 25.29 kPa and tensile strength improved from 9.44 ± 2.28 to 45.05 ± 5.53 kPa). In addition, we demonstrated the versatility of this technique by using fibers of a wide range of sizes and material types and implementing different 2D and 3D embedding patterns, such as embedding a conical helix using electrochemically aligned collagen fiber via nonplanar printing. Moreover, the technique was implemented using low-cost material and is compatible with open-source software and hardware, which facilitates its adoption and modification for new research applications.more » « less
