Polymorphism is one of the fascinating characteristics
of polymer
crystallization. In this work, we report a new crystal modification
of poly(glycolic acid) (PGA), the β-form, to
be distinguished from the already known α-form PGA crystal reported
in 1968. The β-form with a relatively high amount (X
β = 43%) is obtained during isothermal crystallization
in a particular temperature domain, i.e., T
c
around 60 °C, after prestretching the amorphous
samples. The orientation of PGA amorphous chains is expected to better
fit the chain conformation in the β-form, i.e., two chains each
with a 7/2 helical conformation in the unit cell, and thus, the extended
PGA macromolecules feature a lower energy barrier for β-form
formation (ΔG
β) than that
of the α-form (ΔG
α).
Moreover, the low crystallization temperature could not provide the
extended macromolecules enough energy to overcome the higher ΔG
α, thus forming predominantly the β-form.
The β-form is stable at ambient temperatures, but it is a metastable
crystal modification at elevated temperatures compared to the α-form.
Consequently, an obvious β–α transition occurs
in the temperature range of 80–120 °C via a solid–solid
mechanism, while the crystalline orientation degree remains consistent
during the transition. This study enables a better understanding on
the polymorphism and phase transition of PGA, providing a potential
route to tune its final performance via crystalline structure control.