Mimicking the mechanical properties of native tissues is a critical criterion for an ideal tissue engineering scaffold. However, most biodegradable synthetic materials, including polyester-based polyurethanes (PUs), consist of rigid polyester chains and have high crystallinity. They typically lack the elasticity of most human tissues. In this study, a new type of biodegradable PU with excellent elasticity was synthesized based on the controlled crosslinking of poly(ester ether) triblock copolymer diols and polycaprolactone (PCL) triols using urethane linkages. Three-dimensional (3D) porous scaffolds with a defined geometry, tunable microstructures, and adjustable mechanical properties were synthesized in situ using an isocyanate-ended copolymer, a tri-armed PCL, and a chain extender. The mechanical properties of the scaffolds can be easily tuned by changing the ratio of reactants, varying the solution concentration, or using a porogen. Notably, all of these scaffolds, although mostly made of rigid PCL chains, showed remarkable elasticity and cyclical properties. With an optimized molecular design, a maximum recovery rate of 99.8% was achieved. This was because the copolymer provided molecular flexibility while the long chain crosslinking of PCL triol hindered crystallization, thus making the PU behave like an amorphous elastic material. Moreover, the in vitro cell culture of 3T3 fibroblasts and MG63 osteoblast-like cells confirmed the biocompatibility of these PU scaffolds and revealed that scaffolds with different stiffnesses can stimulate the proliferation of different types of cells. All of these attributes make PU scaffolds extremely suitable for the regeneration of tissues that experience dynamic loading.

Ultra‐high‐molecular weight polyethylene (UHMWPE) powder was processed using injection molding (IM) with different cavity thicknesses and injection‐compression molding (ICM). The processing parameters of feeding the powders were optimized to ensure proper dosage and avoid jeopardizing the UHMWPE molecular structure. Dynamic mechanical analysis (DMA) and Fourier‐transform infrared spectroscopy tests confirmed that the thermal and oxidative degradations of the material were avoided but crosslinking was induced during melt processing. Tensile tests and impact tests showed that the ICM samples were superior to those of IM. Increased cavity thickness and ICM were helpful for reducing the injection pressure and improving the mechanical properties due to effective packing of the material. Short shot molding showed that the UHMWPE melt did not exhibit the typical progressive and smooth melt front advancements. Due to its highly entangled polymer chains structure, it entered the cavity as an irregular porous‐like structure, as shown by short shots and micro‐computed tomography scans. A delamination skin layer (around 300‐μm thick and independent of cavity thickness) was formed on all IM sample surfaces while it was absent in the ICM samples, suggesting two different flow behaviors between IM and ICM during the packing phase. POLYM. ENG. SCI., 59:E170–E179, 2019. © 2018 Society of Plastics Engineers

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Abstract:The processability of injection molding ultra-high molecular weight polyethylene (UHMWPE) was improved by introducing supercritical nitrogen (scN 2 ) or supercritical carbon dioxide (scCO 2 ) into the polymer melt, which decreased its viscosity and injection pressure while reducing the risk of degradation. When using the special full-shot option of microcellular injection molding (MIM), it was found that the required injection pressure decreased by up to 30% and 35% when scCO 2 and scN 2 were used, respectively. The mechanical properties in terms of tensile strength, Young's modulus, and elongation-at-break of the supercritical fluid (SCF)-loaded samples were examined. The thermal and rheological properties of regular and SCF-loaded samples were analyzed using differential scanning calorimetry (DSC) and parallel-plate rheometry, respectively. The results showed that the temperature dependence of UHMWPE was very low, suggesting that increasing the processing temperature is not a viable method for reducing injection pressure or improving processability. Moreover, the use of scN 2 and scCO 2 with UHMWPE and MIM retained the high molecular weight, and thus the mechanical properties, of the polymer, while regular injection molding led to signs of degradation.

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Cardiovascular diseases plague human health because of the lack of transplantable small-diameter blood vessel (SDBV) grafts. Although expanded polytetrafluoroethylene (ePTFE) has the potential to be used as a biocompatible material for SDBV grafts, long-term patency is still the biggest challenge. As discussed in this paper, by virtue of a novel material formulation and a new and benign alcohol/water lubricating agent, biofunctionalized ePTFE blood vessel grafts aimed at providing long-term patency were fabricated. Compared to the most prevalent modification of PTFE, namely surface treatment, this method realized bulk treatment, which could guarantee homogeneous and long-lasting performance throughout PTFE products. These blood vessel grafts included embedded functional biomolecules, such as arginylglycylaspartic acid, heparin, and selenocystamine, using water as a solvent in paste extrusion and in the expansion of ePTFE. Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscope results confirmed the existence of these targeting biomolecules in the as-fabricated ePTFE blood vessel grafts. Meanwhile, the greatly improved biological functions of the grafts were demonstrated via live and dead assays, cell morphology, CD31 staining, nitric oxide (NO) release, and anticoagulation tests. This novel and benign material formulation and fabrication method provides an opportunity to produce multibiofunctional ePTFE blood vessel grafts in a single step, thus yielding a potent product with significant commercial and clinical potential.

When ultra‐high‐molecular‐weight polyethylene (UHMWPE) in powder form is injection molded, the so‐called delamination layering occurs near the skin of the parts. This layering defect hampers UHMWPE's superior wear resistance property and part surface quality. The delamination layer was caused by a combination of excessive shear stress near the part surface and high degree of molecular entanglement of UHMWPE. A mold insulation method that delays the rapid cooling of UHMWPE to reduce the shear stress and improve the polymer chain “interdiffusion” across the entangled chain bundles was used to eliminate the delamination layer. When the insulation layer thickness and mold temperature were optimized, the delamination layer was eliminated completely while still maintaining a reasonable cooling/cycle time. The delamination‐free parts were found to regain UHMWPE's superior impact resistance and tensile properties. POLYM. ENG. SCI., 59:2313–2322, 2019. © 2019 Society of Plastics Engineers

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