Hygroscopic Behaviour and Diffusion Characteristics of Flexible TPU Materials Fabricated by FDM for Potential Biomedical Applications

Flexible thermoplastic polyurethane (TPU) materials fabricated using fused deposition modeling (FDM) are increasingly used in engineering and biomedical applications where exposure to moisture is unavoidable. However, the relationship between mate-rial hardness, water absorption, diffusion behaviour, and dimensional stability re-mains insufficiently understood and investigated. In this study, the hygroscopic behaviour of eight commercially available TPU filaments (60A–98A Shore hardness) was systematically investigated. Specimens were produced using FDM 3d printer under controlled processing conditions and immersed in physi-ological solution (0,9% NaCl) for up to 96 h. Water absorption, dimensional changes, and diffusion characteristics were analysed. Diffusion coefficients were determined using the Fickian diffusion model based on the initial stage of water uptake. The results revealed a clear transition in behaviour between lower- and high-er-hardness materials. Softer TPU materials (60A–85A) exhibited higher water absorp-tion (up to ~1.80%) and a strong linear relationship between hardness and absorption (R² = 0.999). In contrast, higher-hardness materials (89A–98A) showed lower absorp-tion (~1.18–1.42%) and no clear correlation with hardness (R² = 0.4214). Diffusion coef-ficients ranged from 1.06 × 10⁻¹² to 3.40 × 10⁻¹² m²s-1, with no monotonic dependence on hardness. Additionally, no clear correlation between diffusion kinetics and equilibrium absorption or volumetric expansion was observed. These findings demonstrate that hygroscopic behaviour of FDM-printed TPU materials cannot be reliably predicted based solely on hardness, and that diffusion, absorption, and swelling are governed by different mechanisms. The identified transition from hardness-dependent to structure-controlled behaviour provides new insight for the design and selection of flexible polymer components in moisture-exposed environ-ments, particularly in biomedical applications.