Non-isothermal crystallization kinetics of polydioxanone (PDO), a polymer with well-established applications as bioabsorbable monofilar suture, was investigated by Avrami, Mo, and isoconversional methodologies. Results showed Avrami exponents appearing in a relatively narrow range (i.e., between 3.76 and 2.77), which suggested a three-dimensional spherulitic growth and instantaneous nucleation at high cooling rates. The nucleation mechanism changed to sporadic at low rates, with both crystallization processes being detected in the differential scanning calorimetry (DSC) cooling traces. Formation of crystals was hindered as the material crystallized because of a decrease in the motion of molecular chains. Two secondary nucleation constants were derived from calorimetric data by applying the methodology proposed by Vyazovkin and Sbirrazzuoli through the estimation of effective activation energies. In fact, typical non-isothermal crystallization analysis based on the determination of crystal growth by optical microscopy allowed secondary nucleation constants of 3.07 × 105 K2 and 1.42 × 105 K2 to be estimated. Microstructure of sutures was characterized by a stacking of lamellae perpendicularly oriented to the fiber axis and the presence of interlamellar and interfibrillar amorphous regions. The latter became enhanced during heating treatments due to loss of partial chain orientation and decrease of electronic density. Degradation under various pH media revealed different macroscopic morphologies and even a distinct evolution of lamellar microstructure during subsequent heating treatments.

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