Among all three-dimensional (3D) printing materials, thermosetting photopolymers claim almost half of the market, and have been widely used in various fields owing to their superior mechanical ...stability at high temperatures, excellent chemical resistance as well as good compatibility with high-resolution 3D printing technologies. However, once these thermosetting photopolymers form 3D parts through photopolymerization, the covalent networks are permanent and cannot be reprocessed, i.e., reshaped, repaired, or recycled. Here, we report a two-step polymerization strategy to develop 3D printing reprocessable thermosets (3DPRTs) that allow users to reform a printed 3D structure into a new arbitrary shape, repair a broken part by simply 3D printing new material on the damaged site, and recycle unwanted printed parts so the material can be reused for other applications. These 3DPRTs provide a practical solution to address environmental challenges associated with the rapid increase in consumption of 3D printing materials.
We present a new 4D printing approach that can create high resolution (up to a few microns), multimaterial shape memory polymer (SMP) architectures. The approach is based on high resolution ...projection microstereolithography (PμSL) and uses a family of photo-curable methacrylate based copolymer networks. We designed the constituents and compositions to exhibit desired thermomechanical behavior (including rubbery modulus, glass transition temperature and failure strain which is more than 300% and larger than any existing printable materials) to enable controlled shape memory behavior. We used a high resolution, high contrast digital micro display to ensure high resolution of photo-curing methacrylate based SMPs that requires higher exposure energy than more common acrylate based polymers. An automated material exchange process enables the manufacture of 3D composite architectures from multiple photo-curable SMPs. In order to understand the behavior of the 3D composite microarchitectures, we carry out high fidelity computational simulations of their complex nonlinear, time-dependent behavior and study important design considerations including local deformation, shape fixity and free recovery rate. Simulations are in good agreement with experiments for a series of single and multimaterial components and can be used to facilitate the design of SMP 3D structures.
4D printing has attracted tremendous interest since its first conceptualization in 2013. 4D printing derived from the fast growth and interdisciplinary research of smart materials, 3D printer, and ...design. Compared with the static objects created by 3D printing, 4D printing allows a 3D printed structure to change its configuration or function with time in response to external stimuli such as temperature, light, water, etc., which makes 3D printing alive. Herein, the material systems used in 4D printing are reviewed, with emphasis on mechanisms and potential applications. After a brief overview of the definition, history, and basic elements of 4D printing, the state‐of‐the‐art advances in 4D printing for shape‐shifting materials are reviewed in detail. Both single material and multiple materials using different mechanisms for shape changing are summarized. In addition, 4D printing of multifunctional materials, such as 4D bioprinting, is briefly introduced. Finally, the trend of 4D printing and the perspectives for this exciting new field are highlighted.
4D printing allows 3D printed structures to change their configurations or functions with time in response to external stimuli. Herein, the material system is reviewed based on the mechanism and potential applications for advances in 4D printing. The trends of 4D printing are discussed and the perspectives for this exciting new field are provided.
3D printing of polymeric materials for various applications has been quickly developed in recent years. In contrast to thermoplastics, 3D printed thermosets, although desirable, are inherently ...non-recyclable due to their permanently crosslinked networks. As 3D printing is becoming more popular, it is desirable to develop recycling approaches for 3D printed parts in view of increasing polymer wastes. Here, we present a new thermosetting vitrimer epoxy ink and a 3D printing method that can 3D print epoxy into parts with complicated 3D geometries, which later can be recycled into a new ink for the next round of 3D printing. In the first printing cycle, a high-viscous ink is first slightly cured and is then printed at an elevated temperature into complicated 3D structures, followed by an oven cure using a two-step approach. To be recycled, the printed epoxy parts are fully dissolved in an ethylene glycol solvent in a sealed container at a high temperature. The dissolved polymer solution is reused for the next printing cycle using similar printing conditions. Our experiments demonstrate that the ink can be printed four times and still retains very good printability. In addition, the vitrimer epoxy can be used for pressure-free repairs for the 3D printed parts.
Covalent adaptable networks (CANs; also known as dynamic covalent networks or vitrimers) are appealing for developing simple and efficient techniques for recycling thermosetting polymers. In this ...paper, ethylene glycol (EG) is used as a solvent to enable pressure-free surface welding, surface repair, and recycling of a malleable epoxy where the transesterification-type bond exchange reaction (BER) imparts a dynamic nature to the covalent network. At a high temperature, the EG molecules participate in the BER, leading to dissolution of the epoxy network. If the EG is allowed to evaporate, the dissolved epoxy can re-form into a solid. The effects of EG content, temperature, and catalyst concentration on EG-assisted BERs are investigated. It is found that the amount of EG can be adjusted to tune the solution/solid transformation: An excessive amount of EG is required to dissolve the epoxy; on the other hand, a shortage of EG can shift the reaction back to re-form the polymer. Furthermore, the catalyst concentration defines the point at which dissolution initiates, while the degradation rate depends on temperature. This new EG-assisted method is further used for surface welding, surface damage repair, and powder-based reprocessing. The EG-assisted method does not require pressure and can achieve the properties of a fresh sample. It also provides potential opportunities to develop facile recycling techniques for thermosetting polymers.
Both environmental and economic factors have driven the development of recycling routes for the increasing amount of composite waste generated. This paper presents a new paradigm to fully recycle ...epoxy‐based carbon fiber reinforced polymer (CFRP) composites. After immersing the composite in ethylene glycol (EG) and increasing the temperature, the epoxy matrix can be dissolved as the EG molecules participate in bond exchange reactions (BERs) within the covalent adaptable network (CAN), effectively breaking the long polymer chains into small segments. The clean carbon fibers can be then reclaimed with the same dimensions and mechanical properties as those of fresh ones. Both the dissolution rate and the minimum amount of EG required to fully dissolve the CAN are experimentally determined. Further heating the dissolved solution leads to repolymerization of the epoxy matrix, so a new generation of composite can be fabricated by using the recycled fiber and epoxy; in this way a closed‐loop near 100% recycling paradigm is realized. In addition, epoxy composites with surface damage are shown to be fully repaired. Both the recycled and the repaired composites exhibit the same level of mechanical properties as fresh materials.
A new method to fully recycle the carbon fiber reinforced thermoset composites is developed. After immersing the composite in solvent, the polymer matrix can be dissolved and clean carbon fibers are reclaimed; both, matrix material and carbon fibres, can be recycled and reused for the same purpose. The developed method can also be used to repair composite with surface damage.
Straight beams, rods and trusses are common elements in structural and mechanical engineering, but recent advances in additive manufacturing now also enable efficient freeform fabrication of curved, ...deformable beams and beam structures, such as microstructures, metamaterials and conformal lattices. To exploit this new design freedom for applications with nonlinear mechanical behavior, we introduce an isogeometric method for shape optimization of curved 3D beams and beam structures. The geometrically exact Cosserat rod theory is used to model nonlinear 3D beams subject to large deformations and rotations. The initial and current geometry are parameterized in terms of NURBS curves describing the beam centerline and an isogeometric collocation approach is used to discretize the strong form of the balance equations. Then, a nonlinear optimization problem is formulated in order to optimize the positions of the control points of the NURBS curve that describes the beam centerline, i.e., the geometry or shape of the beam. To solve the design problem using gradient-based algorithms, we introduce semi-analytical, inconsistent analytical and fully analytical approaches for calculation of design sensitivities. The methods are numerically validated and their performance is investigated, before the applicability and versatility of our 3D beam shape optimization method is illustrated in various numerical applications, including optimization of an auxetic 3D metamaterial.
•Shape of curved, freeform, nonlinear 3D beams is optimized in terms of centerline curve.•NURBS-based integration of isogeometric collocation for nonlinear analysis and optimization.•Control points of centerline curves serve directly as design variables for optimization.•Incomplete analytical and fully analytical sensitivities are derived for gradient-based optimization.•Numerical validation and application to optimization of an auxetic metamaterial.
This perspective article summarizes recent advancements in extrusion-based 3D printing of continuous fiber-reinforced polymers (CFRPs). It focuses on manufacturing techniques and computational design ...methodologies. While fused deposition modeling has been the primary method for printing thermoplastic CFRPs, recent innovations have enabled the printing of thermoset CFRPs using direct ink writing or similar techniques. These printing processes are also integrated with robotic arms to dramatically enhance manufacturing capabilities. Additionally, there has been notable progress in enhancing computational design methodologies to simultaneously optimize fiber distribution and topology of 3D printed CFRPs. The article also discusses future directions aimed at improving mechanical properties, scalability, multifunctionality, and predictability in CFRP 3D printing, which offer valuable perspectives for the development of this transformative manufacturing approach.
Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change ...their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers - digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications.
Folding is ubiquitous in nature with examples ranging from the formation of cellular components to winged insects. It finds technological applications including packaging of solar cells and space ...structures, deployable biomedical devices, and self-assembling robots and airbags. Here we demonstrate sequential self-folding structures realized by thermal activation of spatially-variable patterns that are 3D printed with digital shape memory polymers, which are digital materials with different shape memory behaviors. The time-dependent behavior of each polymer allows the temporal sequencing of activation when the structure is subjected to a uniform temperature. This is demonstrated via a series of 3D printed structures that respond rapidly to a thermal stimulus, and self-fold to specified shapes in controlled shape changing sequences. Measurements of the spatial and temporal nature of self-folding structures are in good agreement with the companion finite element simulations. A simplified reduced-order model is also developed to rapidly and accurately describe the self-folding physics. An important aspect of self-folding is the management of self-collisions, where different portions of the folding structure contact and then block further folding. A metric is developed to predict collisions and is used together with the reduced-order model to design self-folding structures that lock themselves into stable desired configurations.
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