as dynamers by Lehn, [ 25,26 ] are stimuli-responsive polymers, most notably exhibiting macroscopic responses to changes in pH. [ 27,28 ] Several imine-containing polymers have been demonstrated, including pH-responsive hydrogels [ 20 ] and a working organic light-emitting diode (OLED). [ 23 ] However, the potential of polyimines as malleable, mechanically resilient polymeric materials, as well as their processability, have remained largely unexplored. We envision that imine-linked polymers can take malleability in covalent network polymers to the next level of simplicity, affordability and practicality. Herein, we present the fi rst catalyst-free malleable polyimine which fundamentally behaves like a classic thermoset at ambient conditions yet can be reprocessed by application of either heat or water. This means that green, room temperature processing conditions are accessible for this important class of functional polymers.A crosslinked polyimine network was prepared from commercially available monomers: terephthaldehyde, diethylene triamine, and triethylene tetramine ( Figure 1 a). A polyimine fi lm was obtained by simply mixing the three above components in a 3:0.9:1.4 stoichiometry in the absence of any catalyst in a mixture of organic solvents (1:1:8, v/v/v, CH 2 Cl 2 /EtOAc/EtOH), then allowing the volatiles to evaporate slowly. Alternatively, the polymer can be obtained as a powder by using ethyl acetate as the only solvent. The polymerization reaction was confi rmed by infrared spectroscopy, which revealed that aldehyde end groups were consumed while imine linkages were formed ( Figure S2, Supporting Information). The resulting translucent polymer is hard and glassy at room temperature ( T g is 56 °C) ( Figure S1, Supporting Information) and has a modulus of near 1 GPa with stress at break of 40 MPa ( Figure S3, Supporting Information).The time and temperature dependent relaxation modulus of the polyimine fi lm was tested to characterize the heat-induced malleability. Figure 1 b depicts the results of a series of relaxation tests over a wide range of temperatures (50-127.5 °C) on a double logarithmic plot. Specifi cally, at 80 °C, the bond exchange reaction is initiated and the normalized relaxation modulus is decreased from 1 to 0.11 within 30 min, indicating an 89% release of the internal stress within the thermoset polymer. By shifting each relaxation curve horizontally with respect to a reference temperature at 80 °C, a master relaxation curve was constructed (Figure 1 c), which indicates the stress relaxation of the polyimine follows the classic time-temperature superposition (TTSP) behavior. The plot of time-temperature shift factors as a function of temperature (Figure 1 d) shows that the polyimine's stress-relaxation behavior exhibits Arrheniuslike temperature dependence. Using the extrapolation, we calculated that while it takes 30 min for the stress to be relaxed by ca. 90% at 80 °C, the same process would take ca. 480 days at room temperature. The polyimine is thus the fi rst reported
Carbon-fiber reinforced composites are prepared using catalyst-free malleable polyimine networks as binders. An energy neutral closed-loop recycling process has been developed, enabling recovery of 100% of the imine components and carbon fibers in their original form. Polyimine films made using >21% recycled content exhibit no loss of mechanical performance, therefore indicating all of the thermoset composite material can be recycled and reused for the same purpose.
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.
An epoxy ink and its 3D printing method were developed to allow printed parts to be recycled and reprinted.
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.
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.
Shape memory polymers are at the forefront of recent materials research. Although the basic concept has been known for decades, recent advances in the research of shape memory polymers demand a unified approach to predict the shape memory performance under different thermo-temporal conditions. Here we report such an approach to predict the shape fixity and free recovery of thermo-rheologically simple shape memory polymers. The results show that the influence of programming conditions to free recovery can be unified by a reduced programming time that uniquely determines shape fixity, which consequently uniquely determines the shape recovery with a reduced recovery time. Furthermore, using the time-temperature superposition principle, shape recoveries under different thermo-temporal conditions can be extracted from the shape recovery under the reduced recovery time. Finally, a shape memory performance map is constructed based on a few simple standard polymer rheology tests to characterize the shape memory performance of the polymer.
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