Effect of nonaffine displacement on the mechanical performance of degraded PCL and its graphene composites: an atomistic investigation

Evaluating the mechanical properties of biodegradable implants can be challenging for in situ experiments and time-consuming for materials with a slow degradation rate, such as polycaprolactone (PCL). In this work, the effects of chain scission and water erosion on the mechanical properties of degraded PCL are investigated by molecular dynamics simulation. The decrease of the mechanical performance is correlated with the increase of the nonaffine displacement during the degradation. The nonaffine squared displacements (NSD) during the tensile deformation are calculated by subtracting the affine squared displacements from the mean squared displacements. After chain scission, short polymer chains increase the NSD of the system and weaken the modulus of the polymer matrix. The effect of the NSD is also observed in a water erosion model. When the bond break ratio is less than 5%, PCL still maintains a well-entangled network, which constrains the diffusion of the water molecules, resulting in a higher modulus of the erosion model than the chain scission model at a low degradation rate. The effect of NSD is also found in the PCL/graphene composites. For the degraded polymer chains, the diffusion of PCL is constrained by the graphene network, and such an effect increases during the degradation. As a result, the addition of graphene nanosheets slows down the decreasing trend of Young's modulus. Such findings can also explain the size effect of the graphene reinforcement on the mechanical properties of the polymer composites. This work provides atomistic insights into the mechanical property evolution during polymer degradation, revealing the possibility of tuning the mechanical performance by controlling the diffusion, which could be beneficial for the design and lifetime prediction of degradable implants.