In Vitro Degradation Studies of 3D-Printed Thermoplastic Polyurethane for the Design of Vascular Implant

Three-dimensional printing has emerged as a promising technology in endovascular surgery for the production of patient-specific stent-grafts. Thermoplastic polyurethane (TPU) is widely used for this purpose due to its favourable biocompatibility, hemocompatibility, and mechanical properties. However, its long-term stability under physiological conditions remains uncertain. This study evaluates the ageing behaviour of 3D-printed TPU stent-grafts under accelerated oxidative conditions (20% H₂O₂-0.1 M CoCl₂) over three months, corresponding to approximately 45 months in vivo, and during three months in hydrolytic (0.1 M NaOH) conditions. Mechanical, physicochemical, thermal, and surface properties were periodically analysed. Differential scanning calorimetry revealed a decrease in crystallisation enthalpy of 41% and a reduction in melting enthalpy of 29% after hydrolytic ageing, whereas no decrease was observed after oxidative ageing. Despite these chemical changes, size exclusion chromatography indicated minimal chain scission. However, spectroscopy and microscopy showed minor chain scission and additive migration (antioxidant and lubricant). Nevertheless, tensile testing highlighted that mechanical performance remained within clinically acceptable ranges. These findings demonstrate that 3D-printed TPU vascular implants retain essential properties under prolonged simulated ageing, supporting their safety and durability for vascular applications.