Memory effect of spider major ampullate silk in loading-unloading cycles and the structural connotations.

Spider silk is repeatedly stretched while performing biological functions. There is a close relationship between the shape change of the fibre materials and their mechanical properties. However, the effect of the deformation and interval time on the structure and tensile behaviour properties of spider silk after repeatedly stretching by given strain value has been rarely reported. Here we found that major ampullate silk (MAS) can revert its tensile behaviour independent of its previous loading history via intervals of approximately 8 s to 5 min with constant and increased elongation, respectively, after being subjected to yield and hardening regions. The true stress-true strain curve beyond a given value of true strain is independent from the previous loading history of the sample. Even after longer intervals (≥1 h), MAS can reproduce the last tensile behaviour via one stretched. Despite recognizing the development of irreversible deformations in the material when tested in air, the reversible change in tensile behaviour outside the spider silk's elastic region has rarely been observed before. MAS has at least one proper ground state that allows it to present good shape and mechanical behaviour memory in terms of longitudinal stretching, functioning as a new strategy to achieve certain tensile properties. The analysis of the true stress-true strain curves was performed from a series of loading‒unloading tests to evaluate the evolution of those mechanical parameters with the cycle number. The elastic modulus measured in the loading steps increases monotonously with increasing values of true strain reached in the cycles. In contrast, a marginal variation is found in the values of the yield stress measured in the different cycles. The memory and variation in the mechanical behaviour and performance of MAS can be accounted for through the irreversible and reversible deformation micromechanisms and its combination in which the viscoelasticity of the material plays a leading role. These findings may be helpful to guide the biomimetic design of novel fibre materials such as spider silk gut via artificially stretching spider silk glands.