Michael Addition-Elimination Ring-Opening Polymerization.

A cyclic thioenone system capable of controlled ring-opening polymerization (ROP) is presented that leverages a reversible Michael addition-elimination (MAE) mechanism. The cyclic thioenone monomers are easy to access and modify and for the first time incorporate the dynamic reversibility of MAE with chain-growth polymerization. This strategy features mild polymerization conditions, tunable functionalities, controlled molecular weights (Mn), and narrow dispersities. The obtained polythioenones exhibit excellent optical transparency and good mechanical properties and can be depolymerized to recover the original monomers. Density functional theory (DFT) calculations of model reactions offer insights into the role of monomer conformation in the polymerization process, as well as explaining divergent reactivity observed in seven-membered thiepane (TP) and eight-membered thiocane (TC) ring systems. Collectively, these findings demonstrate the feasibility of MAE mechanisms in ring-opening polymerization and provide important guidelines toward future monomer designs.

Chemically Recyclable Polymer System Based on Nucleophilic Aromatic Ring-Opening Polymerization.

The development of chemically recyclable polymers with desirable properties is a long-standing but challenging goal in polymer science. Central to this challenge is the need for reversible chemical reactions that can equilibrate at rapid rates and provide efficient polymerization and depolymerization cycles. Based on the dynamic chemistry of nucleophilic aromatic substitution (SNAr), we report a chemically recyclable polythioether system derived from readily accessible benzothiocane (BT) monomers. This system represents the first example of a well-defined monomer platform capable of chain-growth ring-opening polymerization through an SNAr manifold. The polymerizations reach completion in minutes, and the pendant functionalities are easily customized to tune material properties or render the polymers amenable to further functionalization. The resulting polythioether materials exhibit comparable performance to commercial thermoplastics and can be depolymerized to the original monomers in high yields.

Reshaping sub-millimetre bubbles from spheres to tori.

Shape-changing objects are prized for applications ranging from acoustics to robotics. We report sub-millimetre bubbles that reversibly and rapidly change not only their shape but also their topological class, from sphere to torus, when subjected to a simple pressure treatment. Stabilized by a solid-like film of nanoscopic protein "particles", the bubbles may persist in toroidal form for several days, most of them with the relative dimensions expected of Clifford tori. The ability to cross topological classes reversibly and quickly is enabled by the expulsion of protein from the strained surfaces in the form of submicron assemblies. Compared to structural modifications of liquid-filled vesicles, for example by slow changes in solution osmolality, the rapid inducement of shape changes in bubbles by application of pressure may hasten experimental investigations of surface mechanics, even as it suggests new routes to lightweight materials with high surface areas.

Influence of treating parameters on thermomechanical properties of recycled epoxy-acid vitrimers.

Vitrimers have the characteristics of shape-reforming and surface-welding, and have the same excellent mechanical properties as thermosets; so vitrimers hold the promise of a broad alternative to traditional plastics. Since their initial introduction in 2011, vitrimers have been applied to many unique applications such as reworkable composites and liquid crystal elastomer actuators. A series of experiments have investigated the effects of reprocessing conditions (such as temperature, time, and pressure) on recycled materials. However, the effect of particle size on the mechanical properties of recycled materials has not been reported. In this paper, we conducted an experimental study on the recovery of epoxy-acid vitrimers of different particle sizes. Epoxy-acid vitrimer powders with different particle size distributions were prepared and characterized. The effects of particle size on the mechanical properties of regenerated epoxy-acid vitrimers were investigated by dynamic mechanical analysis and uniaxial tensile tests. In addition, other processing parameters such as temperature, time, and pressure are discussed, as well as their interaction with particle size. This study helped to refine the vitrimer reprocessing condition parameter toolbox, providing experimental support for the easy and reliable control of the kinetics of the bond exchange reaction.

A finite deformation theory of desolvation and swelling in partially photo-cross-linked polymer networks for 3D/4D printing applications.

Photopolymerization is a process strongly dependent on the light field in the resin. This typically results in a non-uniformly crosslinked network where some parts of the network are fully cross-linked while other parts are partially crosslinked. The partially crosslinked part could exhibit a high volume expansion upon swelling and a high volume shrinkage upon desolvation. Through control over the light field in the photopolymer resin, this feature has been used to create solvent responsive shape changing structures as well as 3D/4D printed smart devices, showing promising application potential. In this paper, we develop a finite deformation theory to consider the nonuniform crosslink density of the network and the interaction between different species inside the network. The mechanical properties of the network are correlated with the reaction process and the existence of residual uncrosslinked monomers is included in the partially crosslinked network. The efficiency of the theory is proved by the finite element simulations of two special applications of the partially crosslinked network.

Mechanics of shape distortion of DLP 3D printed structures during UV post-curing.

Digital light processing (DLP) three-dimensional (3D) printing technology has advantages of fast printing speed and high printing precision. It can print objects with small and complex geometrical features and has been widely used in jewelry manufacturing and dentistry. In DLP printing, it is common to use post-treatment with UV light irradiation to improve the final mechanical properties. However, it was found that the UV post-curing process can lead to shape distortion and thus reduction of dimension accuracy. In this paper, we combined photopolymerization reaction kinetics and Euler-Bernoulli beam theory to study UV post-curing induced shape distortion of thin structures prepared by DLP 3D printing. Experiments were conducted to characterize the evolution of mechanical behavior of printed samples during the post-printing process, which was correlated to printing parameters (printing time of single-layer, height of single-layer and printing UV intensity), post-curing UV light intensity and the thickness of the strip. Moreover, post-curing induced distortion was used for the fabrication of 3D structures.

Fabrication of tough epoxy with shape memory effects by UV-assisted direct-ink write printing.

3D printing of epoxy-based shape memory polymers with high mechanical strength, excellent thermal stability and chemical resistance is highly desirable for practical applications. However, thermally cured epoxy in general is difficult to print directly. There have been limited numbers of successes in printing epoxy but they suffer from relatively poor mechanical properties. Here, we present an ultraviolet (UV)-assisted 3D printing of thermally cured epoxy composites with high tensile toughness via a two-stage curing approach. The ink containing UV curable resin and epoxy oligomer is used for UV-assisted direct-ink write (DIW)-based 3D printing followed by thermal curing of the part containing the epoxy oligomer. The UV curable resin forms a network by photo polymerization after the 1st stage of UV curing, which can maintain the printed architecture at an elevated temperature. The 2nd stage thermal curing of the epoxy oligomer yields an interpenetrating polymer network (IPN) composite with highly enhanced mechanical properties. It is found that the printed IPN epoxy composites enabled by the two-stage curing show isotropic mechanical properties and high tensile toughness. We demonstrated that the 3D-printed high-toughness epoxy composites show good shape memory properties. This UV-assisted DIW 3D printing via a two-stage curing method can broaden the application of 3D printing to fabricate thermoset materials with enhanced tensile toughness and tunable properties for high-performance and functional applications.

Viscoelastic multistable architected materials with temperature-dependent snapping sequence.

When an architected material with snap-through instabilities is loaded, the unit cells of the architected material snap sequentially to a series of deformed configurations. In this paper, we propose the novel concept of multimaterial viscoelastic architected materials whose snapping sequence can be tuned using temperature as a control parameter. Because different polymers have different temperature-dependent properties, it is possible that one polymer that is stiffer than another polymer at one temperature becomes softer at a higher temperature. A 3D printing inverse molding process is used to fabricate soft multimaterial architected materials that consist of two different polymers. Using finite element simulations and experiments, we demonstrate that the snapping sequence of these multimaterial architected materials depends on temperature. The influence of the geometrical parameters of the design on the critical temperature at which the snapping sequence switches from one sequence to another sequence is systematically analyzed using simulations and experiments. Being able to tune the snapping sequence using temperature makes it possible to obtain a large number of distinct stable configurations in response to compressive loads. To illustrate a potential application, we demonstrate that these materials can be used as soft reconfigurable metamaterials with tunable stiffness.

3D printing of complex origami assemblages for reconfigurable structures.

Origami engineering principles have recently been applied to a wide range of applications, including soft robots, stretchable electronics, and mechanical metamaterials. In order to achieve the 3D nature of engineered structures (e.g. load-bearing capacity) and capture the desired kinematics (e.g., foldability), many origami-inspired engineering designs are assembled from smaller parts and often require binding agents or additional elements for connection. Attempts at direct fabrication of 3D origami structures have been limited by available fabrication technologies and materials. Here, we propose a new method to directly 3D print origami assemblages (that mimic the behavior of their paper counterparts) with acceptable strength and load-bearing capacity for engineering applications. Our approach introduces hinge-panel elements, where the hinge regions are designed with finite thickness and length. The geometrical design of these hinge-panels, informed by both experimental and theoretical analysis, provides the desired mechanical behavior. In order to ensure foldability and repeatability, a novel photocurable elastomer system is developed and the designs are fabricated using digital light processing-based 3D printing technology. Various origami assemblages are produced to demonstrate the design flexibility and fabrication efficiency offered by our 3D printing method for origami structures with enhanced load bearing capacity and selective deformation modes.

Temperature dependent evolution of wrinkled single-crystal silicon ribbons on shape memory polymers.

Shape memory polymers (SMPs) can remember two or more distinct shapes, and thus can have a lot of potential applications. This paper presents combined experimental and theoretical studies on the wrinkling of single-crystal Si ribbons on SMPs and the temperature dependent evolution. Using the shape memory effect of heat responsive SMPs, this study provides a method to build wavy forms of single-crystal silicon thin films on top of SMP substrates. Silicon ribbons obtained from a Si-on-insulator (SOI) wafer are released and transferred onto the surface of programmed SMPs. Then such bilayer systems are recovered at different temperatures, yielding well-defined, wavy profiles of Si ribbons. The wavy profiles are shown to evolve with time, and the evolution behavior strongly depends on the recovery temperature. At relatively low recovery temperatures, both wrinkle wavelength and amplitude increase with time as evolution progresses. Finite element analysis (FEA) accounting for the thermomechanical behavior of SMPs is conducted to study the wrinkling of Si ribbons on SMPs, which shows good agreement with experiment. Merging of wrinkles is observed in FEA, which could explain the increase of wrinkle wavelength observed in the experiment. This study can have important implications for smart stretchable electronics, wrinkling mechanics, stimuli-responsive surface engineering, and advanced manufacturing.

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

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.

Desolvation Induced Origami of Photocurable Polymers by Digit Light Processing.

Self-folding origami is of great interest in current research on functional materials and structures, but there is still a challenge to develop a simple method to create freestanding, reversible, and complex origami structures. This communication provides a feasible solution to this challenge by developing a method based on the digit light processing technique and desolvation-induced self-folding. In this new method, flat polymer sheets can be cured by a light field from a commercial projector with varying intensity, and the self-folding process is triggered by desolvation in water. Folded origami structures can be recovered once immersed in the swelling medium. The self-folding process is investigated both experimentally and theoretically. Diverse 3D origami shapes are demonstrated. This method can be used for responsive actuators and the fabrication of 3D electronic devices.

Cyclic behaviors of amorphous shape memory polymers.

Cyclic loading conditions are commonly encountered in the applications of shape memory polymers (SMPs), where the cyclic characteristics of the materials determine their performance during the service life, such as deformation resistance, shape recovery speed and shape recovery ratio. Recent studies indicate that in addition to the physical damage or some other irreversible softening effects, the viscoelastic nature could also be another possible reason for the degraded cyclic behavior of SMPs. In this paper, we explore in detail the influence of the viscoelastic properties on the cyclic tension and shape memory (SM) behavior of an epoxy based amorphous thermosetting polymer. Cyclic experiments were conducted first, which show that although the epoxy material does not have any visible damage or irreversible softening effect during deformation, it still exhibits obvious degradation in the cyclic tension and SM behaviors. A linear multi-branched model is utilized to assist in the prediction and understanding of the mechanical responses of amorphous SMPs. Parametric studies based on the applied model suggest that the shape memory performance can be improved by adjusting programming and recovery conditions, such as lowering the loading rate, increasing the programming temperature, and reducing the holding time.

Griffith criterion for brittle fracture in graphene.

There are prevailing concerns with the critical dimensions when conventional theories break down. Here we find that the Griffith criterion remains valid for cracks down to 10 nm but overestimates the strength of shorter cracks. We observe the preferred crack extension along the zigzag edge in graphene, and explain this phenomenon by local strength-based failure rather than energy-based Griffith criterion. These results provide a mechanistic basis for reliable applications of graphene in miniaturized devices and nanocomposites.

Photo-induced bending in a light-activated polymer laminated composite.

Light activated polymers (LAPs) have attracted increasing attention since these materials change their shape and/or behavior in response to light exposure, which serves as an instant, remote and precisely controllable stimulus that enables non-contact control of the material shape and behavior through simple variation in light intensity, wavelength and spatially controlled exposure. These features distinguish LAPs from other active polymers triggered by other stimuli such as heat, electrical field or humidity. Previous examples have resulted in demonstrations in applications such as surface patterning, photo-induced shape memory behavior, and photo-origami. However, in many of these applications, an undesirable limitation has been the requirement to apply and maintain an external load during light irradiation. In this paper, a laminated structure is introduced to provide a pre-programmed stress field, which is then used for photo-induced deformation. This laminated structure is fabricated by bonding a stretched elastomer (NOA65) sheet between two LAP layers. Releasing the elastomer causes contraction and introduces a compressive stress in the LAPs, which are relaxed optically to trigger the desired deformation. A theoretical model is developed to quantitatively examine the laminated composite system, allowing exploration of the design space and optimum design of the laminate.

A molecular dynamics study of bond exchange reactions in covalent adaptable networks.

Covalent adaptable networks are polymers that can alter the arrangement of network connections by bond exchange reactions where an active unit attaches to an existing bond then kicks off its pre-existing peer to form a new bond. When the polymer is stretched, bond exchange reactions lead to stress relaxation and plastic deformation, or the so-called reforming. In addition, two pieces of polymers can be rejoined together without introducing additional monomers or chemicals on the interface, enabling welding and reprocessing. Although covalent adaptable networks have been researched extensively in the past, knowledge about the macromolecular level network alternations is limited. In this study, molecular dynamics simulations are used to investigate the macromolecular details of bond exchange reactions in a recently reported epoxy system. An algorithm for bond exchange reactions is first developed and applied to study a crosslinking network formed by epoxy resin DGEBA with the crosslinking agent tricarballylic acid. The trace of the active units is tracked to show the migration of these units within the network. Network properties, such as the distance between two neighboring crosslink sites, the chain angle, and the initial modulus, are examined after each iteration of the bond exchange reactions to provide detailed information about how material behaviors and macromolecular structure evolve. Stress relaxation simulations are also conducted. It is found that even though bond exchange reactions change the macroscopic shape of the network, microscopic network characteristic features, such as the distance between two neighboring crosslink sites and the chain angle, relax back to the unstretched isotropic state. Comparison with a recent scaling theory also shows good agreement.

Mechanically programmed shape change in laminated elastomeric composites.

Soft, anisotropic materials, such as myocardium in the heart and the extracellular matrix surrounding cells, are commonly found in nature. This anisotropy leads to specialized responses and is imperative to material functionality, yet few soft materials exhibiting similar anisotropy have been developed. Our group introduced an anisotropic shape memory elastomeric composite (A-SMEC) composed of non-woven, aligned polymer fibers embedded in an elastomeric matrix. The composite exhibited shape memory (SM) behavior with significant anisotropy in room-temperature shape fixing. Here, we exploit this anisotropy by bonding together laminates with oblique anisotropy such that tensile deformation at room temperature - mechanical programming - results in coiling. This response is a breakthrough in mechanical programming, since non-affine shape change is achieved by simply stretching the layered A-SMECs at room temperature. We will show that pitch and curvature of curled geometries depend on fiber orientations and the degree of strain programmed into the material. To validate experimental results, a model was developed that captures the viscoplastic response of A-SMECs. Theoretical results correlated well with experimental data, supporting our conclusions and ensuring attainability of predictable curling geometries. We envision these smart, soft, shape changing materials will have aerospace and medical applications.

Temperature memory effect in amorphous shape memory polymers.

Temperature memory effect (TME) refers to the ability of shape memory polymers (SMPs) to memorize the temperature at which pre-deformation was conducted. In the past few years, this TME was experimentally demonstrated by comparing the applied programming temperature (Td) with a characteristic recovery temperature (Tc), which corresponds to either the maximum recovery stress or free recovery speed. In these well-designed experiments, Tc was observed to be close to Td, which is consistent with the intuitive understanding of 'memorization'. However, since the polymer recovery behavior has been proved to be strongly dependent on various programming and recovery conditions, a new question that whether Tc is always equal to Td in any thermo-temporal conditions remains to be addressed. In this paper, we answered this question by examining the free recovery profile of an acrylate based amorphous SMP. The recovery Tc, which is the temperature with the maximum recovery speed, versus the recovery temperature is shown to be strongly dependent on both programming and recovery conditions. Their detailed influence could be explained by using the reduced time. During a thermomechanical working cycle of SMPs, in addition to the Td, any other thermo-temporal conditions, such as the holding time (th), cooling rate, recovery heating rate (q), etc., can affect the observed Tc by changing the reduced programming or recovery time. In this manner, the relationship between Tc and Td is not uniquely determined. Besides, the TME in SMPs can only be achieved within a given temperature range. Both onset and offset of this temperature range are shown to be influenced by the programming history, but are independent of the recovery conditions.

Active Materials for Functional Origami.

In recent decades, origami has been explored to aid in the design of engineering structures. These structures span multiple scales and have been demonstrated to be used toward various areas such as aerospace, metamaterial, biomedical, robotics, and architectural applications. Conventionally, origami or deployable structures have been actuated by hands, motors, or pneumatic actuators, which can result in heavy or bulky structures. On the other hand, active materials, which reconfigure in response to external stimulus, eliminate the need for external mechanical loads and bulky actuation systems. Thus, in recent years, active materials incorporated with deployable structures have shown promise for remote actuation of light weight, programmable origami. In this review, active materials such as shape memory polymers (SMPs) and alloys (SMAs), hydrogels, liquid crystal elastomers (LCEs), magnetic soft materials (MSMs), and covalent adaptable network (CAN) polymers, their actuation mechanisms, as well as how they have been utilized for active origami and where these structures are applicable is discussed. Additionally, the state-of-the-art fabrication methods to construct active origami are highlighted. The existing structural modeling strategies for origami, the constitutive models used to describe active materials, and the largest challenges and future directions for active origami research are summarized.

Machine-Guided Discovery of Acrylate Photopolymer Compositions.

Additive manufacturing (AM) can be advanced by the diverse characteristics offered by thermoplastic and thermoset polymers and the further benefits of copolymerization. However, the availability of suitable polymeric materials for AM is limited and may not always be ideal for specific applications. Additionally, the extensive number of potential monomers and their combinations make experimental determination of resin compositions extremely time-consuming and costly. To overcome these challenges, we develop an active learning (AL) approach to effectively choose compositions in a ternary monomer space ranging from rigid to elastomeric. Our AL algorithm dynamically suggests monomer composition ratios for the subsequent round of testing, allowing us to efficiently build a robust machine learning (ML) model capable of predicting polymer properties, including Young's modulus, peak stress, ultimate strain, and Shore A hardness based on composition while minimizing the number of experiments. As a demonstration of the effectiveness of our approach, we use the ML model to drive material selection for a specific property, namely, Young's modulus. The results indicate that the ML model can be used to select material compositions within at least 10% of a targeted value of Young's modulus. We then use the materials designed by the ML model to 3D print a multimaterial "hand" with soft "skin" and rigid "bones". This work presents a promising tool for enabling informed AM material selection tailored to user specifications and accelerating material discovery using a limited monomer space.