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Four-dimensional-printed smart materials have a wide range of applications in areas such as biomedicine, aerospace, and soft robotics. Among 3D printing technologies, fused deposition molding (FDM) is economical, simple, and apply to thermoplastics. Cross-linked polyethylene (XLPE) forms a stable chemical cross-linking structure and shows good shape-memory properties, but the sample is not soluble or fusible, which makes it hard to be applied in FDM printing. Therefore, in this work, a new idea of printing followed by irradiation was developed to prepare 4D-printed XLPE. First, low-density polyethylene (LDPE) was used to print the products using FDM technology and then cross-linked by gamma irradiation was used. The printing parameters were optimized, and the gel content, mechanical properties, and shape-memory behaviors were characterized. After gamma irradiation, the samples showed no new peak in FTIR spectra. And the samples exhibited good shape-memory capabilities. Increasing the irradiation dose increased the cross-linking degree and tensile strength and improved the shape-memory properties. However, it also decreased the elongation at break, and it did not affect the crystallization or melting behaviors of LDPE. With 120 kGy of irradiation, the shape recovery and fixity ratios (Rr and Rf) of the samples were 97.69% and 98.65%, respectively. After eight cycles, Rr and Rf remained at 96.30% and 97.76%, respectively, indicating excellent shape-memory performance.
Four-dimensional-printed smart materials have a wide range of applications in areas such as biomedicine, aerospace, and soft robotics. Among 3D printing technologies, fused deposition molding (FDM) is economical, simple, and apply to thermoplastics. Cross-linked polyethylene (XLPE) forms a stable chemical cross-linking structure and shows good shape-memory properties, but the sample is not soluble or fusible, which makes it hard to be applied in FDM printing. Therefore, in this work, a new idea of printing followed by irradiation was developed to prepare 4D-printed XLPE. First, low-density polyethylene (LDPE) was used to print the products using FDM technology and then cross-linked by gamma irradiation was used. The printing parameters were optimized, and the gel content, mechanical properties, and shape-memory behaviors were characterized. After gamma irradiation, the samples showed no new peak in FTIR spectra. And the samples exhibited good shape-memory capabilities. Increasing the irradiation dose increased the cross-linking degree and tensile strength and improved the shape-memory properties. However, it also decreased the elongation at break, and it did not affect the crystallization or melting behaviors of LDPE. With 120 kGy of irradiation, the shape recovery and fixity ratios (Rr and Rf) of the samples were 97.69% and 98.65%, respectively. After eight cycles, Rr and Rf remained at 96.30% and 97.76%, respectively, indicating excellent shape-memory performance.
In the work presented here, we explore the upcycling of polyethylene terephthalate (PET) that was derived from water bottles. The material was granulated and extruded into a filament compatible with fused filament fabrication (FFF) additive manufacturing platforms. Three iterations of PET combined with a thermoplastic elastomer, styrene ethylene butylene styrene with a maleic anhydride graft (SEBS-g-MA), were made with 5, 10, and 20% by mass elastomer content. The elastomer and specific mass percentages were chosen based on prior successes involving acrylonitrile butadiene styrene (ABS), in which the maleic anhydride graft enabled compatibility between different materials. The rheological properties of PET and the PET/SEBS blends were characterized by the melt flow index and dynamic mechanical analysis. The addition of SEBS-g-MA did not have a significant impact on mechanical properties, as determined by tensile and impact testing, where all test specimens were manufactured by FFF. Delamination of the tensile specimens convoluted the ability to discern differences in the mechanical properties, particularly % elongation. Annealing of the specimens enabled the observation of the effect of elastomer content on the mechanical properties, particularly in the case of impact testing, where the impact strength increased with the increase in SEBS content. However, annealing led to shrinkage of the specimens, detracting from the realized benefits of the thermal process. Scanning electron microscopy of spent tensile specimens revealed that, in the non-annealed condition, SEBS formed nodules that would detach from the PET matrix during the tensile test, indicating that a robust bond was not present. The addition of SEBS-g-MA did allow for shape memory property characterization, where deformation of tensile specimens occurred at room temperature. Specimens from the 20% by mass elastomer content sample group exhibited a shape fixation ratio on the order of 99% and a shape recovery ratio on the order of 80%. This work demonstrates a potential waste reduction strategy to tackle the problem of polymer waste by upcycling discarded plastic into a feedstock material for additive manufacturing with shape memory properties.
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