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Cold sintering enabled the upcycling of polypropylene with gypsum (CaSO₄) into a fully recyclable composite, paving the way for the integration of waste into high-performance, recyclable composites.

 

The tunable properties of thermoplastic elastomers (TPEs), through polymer chemistry manipulations, enable these technologically critical materials to be employed in a broad range of applications. The need to “dial-in” the mechanical properties and responses of TPEs generally requires the design and synthesis of new macromolecules. In these designs, TPEs with nonlinear macromolecular architectures outperform the mechanical properties of their linear copolymer counterparts, but the differences in deformation mechanism providing enhanced performance are unknown. Here, in situ small-angle X-ray scattering (SAXS) measurements during uniaxial extension reveal distinct deformation mechanisms between a commercially available linear poly(styrene)-poly(butadiene)-poly(styrene) (SBS) triblock copolymer and the grafted SBS version containing grafted poly(styrene) (PS) chains from the poly(butadiene) (PBD) mid-block. The neat SBS (φSBS = 100%) sample deforms congruently with the macroscopic dimensions with the domain spacing between spheres increasing and decreasing along and traverse to the stretch direction, respectively. At high extensions, end segment pullout from the PS-rich domains is detected, which is indicated by a disordering of SBS. Conversely, the PS-grafted SBS that is 30 vol% SBS and 70% styrene (φSBS = 30%) exhibits a lamellar morphology and in situ SAXS measurements reveal an unexpected deformation mechanism. During deformation there are two simultaneous processes: significant lamellar domain rearrangement to preferentially orient the lamellae planes parallel to the stretch direction and crazing. The samples whiten at high strains as expected for crazing, which corresponds with the emergence of features in the two-dimensional SAXS pattern during stretching consistent with fibril-like structures that bridge the voids in crazes. The significant domain rearrangement in the grafted copolymers is attributed to the new junctions formed across multiple PS domains by the grafts of a single chain. The in situ SAXS measurements provide insights into the enhanced mechanical properties of grafted copolymers that arise through improved physical crosslinking that leads to nanostructured domain reorientation for self-reinforcement and craze formation where fibrils help to strengthen the polymer. 

The effect of nanoconfinement on the kinetics of benzyl methacrylate radical polymerization is investigated using differential scanning calorimetry. Controlled pore glass (CPG), ordered mesoporous carbons, and mesoporous silica are used as confinement media with pore sizes from 2 to 8 nm. The initial polymerization rate in CPG and mesoporous silica increases relative to the bulk and increases linearly with reciprocal pore size; whereas, the rate in the carbon mesopores decreases linearly with reciprocal pore size; the changes are consistent with the rate being related to the ratio of the pore surface area to pore volume. Induction times are longer for nanoconfined polymerizations, and in the case of CPG and carbon mesopores, autoacceleration occurs earlier, presumably due to the limited diffusivity and lower termination rates for the confined polymer chains. The molecular weight of the polymer synthesized in the nanopores is generally higher than that obtained in the bulk except at the lowest temperatures investigated. The equilibrium conversion under nanoconfinement decreases with decreasing temperature and with confinement size, exhibiting what appears to be a floor temperature at low temperatures.

 

Print conditions for thermoplastics by filament-based material extrusion (MatEx) are commonly optimized to maximize the elastic modulus. However, these optimizations tend to ignore the impact of thermal history that depends on the specimen size and print path selection. Here, we investigate the effect of size print path (raster angle and build orientation) and print sequence on the mechanical properties of polycarbonate (PC) and polypropylene (PP). Examination of parallel and series printing of flat (XY) and stand-on (YZ) orientation of Type V specimens demonstrated that to observe statistical differences in the mechanical response that the interlayer time between printed roads should be approximately 5 s or less. The print time for a single layer in XY orientation is much longer than that for a single layer in YZ orientation, so print sequence only impacts the mechanical response in the YZ orientation. However, the specimen size and raster angle did influence the mechanical properties in XY orientation due to the differences in thermal history associated with intralayer time between adjacent roads. Moreover, all of these effects are significantly larger when printing PC than PP. These differences between PP and PC are mostly attributed to the mechanism of interface consolidation (crystallization vs. glass formation), which changes the requirements for a strong interface between roads (crystals vs. entanglements). These results illustrate how the print times dictated by the print path layout impact observed mechanical properties. This work also demonstrated that the options available in some standards developed for traditional manufacturing will change the quantitative results when applied to 3D printed parts. 

Thermoplastic elastomers based on ABA triblock copolymers are typically limited in modulus and strength due to crack propagation within the brittle regions when the hard end-block composition favors morphologies that exhibit connected domains. Increasing the threshold end-block composition to achieve enhanced mechanical performance is possible by increasing the number of junctions or bridging points per chain, but these copolymer characteristics also tend to increase the complexity of the synthesis. Here, we report an in situ polymerization method to successfully increase the number of effective junctions per chain through grafting of poly(styrene) (PS) to a commercial thermoplastic elastomer, poly(styrene)–poly(butadiene)–poly(styrene) (SBS). The strategy described here transforms a linear SBS triblock copolymer–styrene mixture into a linear-comb-linear architecture in which poly(styrene) (PS) grafts from the mid-poly(butadiene) (PBD) block during the polymerization of styrene. Through systematic variation in the initial SBS/styrene content, nanostructural transitions from disordered spheres to lamellar through reaction-induced phase transitions (RIPT) were identified as the styrene content increased. Surprisingly, maximum mechanical performance (Young's modulus, tensile strength, and elongation at break) was obtained with samples exhibiting lamellar nanostructures, corresponding to overall PS contents of 61–77 wt% PS (including the original PS in SBS). The PS grafting from the PBD block increases the modulus and the strength of the thermoplastic elastomer while preventing brittle fracture due to the greater number of junctions afforded by the PS grafts. The work presented here demonstrates the use of RIPT to transform standard SBS materials into polymer systems with enhanced mechanical properties. 

Acoustic/elastic metamaterials that rely on engineered microstructures instead of chemical composition enable a rich variety of extraordinary effective properties that are suited for various applications including vibration/noise isolation, high-resolution medical imaging, and energy harvesting and mitigation. However, the static nature of these elastic wave guides limits their potential for active elastic-wave guiding, as microstructure transformation remains a challenge to effectively apply in traditional elastic metamaterials due to the interplay of polarization and structural sensitivity. Here, a tunable, locally resonant structural waveguide is proposed and demonstrated for active vibration bandgap switching and elastic-wave manipulation between 1000–4000 Hz based on 3D printed building blocks of zinc-neutralized poly(ethylene- co -methacrylic acid) ionomer (Surlyn 9910). The ionomer exhibits shape memory behavior to enable rearrangement into new shape patterns through application of thermal stimuli that tunes mechanical performance in both space and time dimensions (4D metamaterial). The thermally induced shape-reorganization is programed to flip a series of frequency bands from passbands to bandgaps and vice versa . The continuously switched bandwidth can exceed 500 Hz. Consequently, altering the bandgap from “on” to “off” produces programmable elastic-wave propagation paths to achieve active wave guiding phenomena. An anisotropic cantilever-in-mass model is demonstrated to predict the self-adaptive dynamic responses of the printed structures with good agreement between the analytical work and experimental results. The tunable metamaterial-based waveguides illustrate the potential of 4D printed shape memory polymers in the designing and manufacturing of intelligent devices for elastic-wave control and vibration isolation.