Effect of Anodic Alumina Oxide Pore Diameter on the Crystallization of Poly(butylene adipate)

Poly(butylene adipate) (PBA) was infiltrated into the anodic alumina oxide (AAO) templates with the pore diameter of around 30, 70, and 100 nm and PBA nanotubes with different diameters were prepared. The crystallization and phase transition behavior of the obtained PBA nanotubes capped in the nanopores have been explored by using X-ray diffraction and differential scanning calorimetry. Only α-PBA crystals form in the bulk sample during nonisothermal crystallization. By contrast, predominant β-PBA crystals form in the AAO templates. The β-PBA crystals formed in the nanopores with pore diameter less than 70 nm prefer to adopt an orientation with their b-axis parallel to the long axis of the pore. During the melt recrystallization, it was found that the critical temperature (Tβ), below which pure β-crystals form, is 20 °C for bulk PBA. It drops down significantly with the pore diameter for the PBA in the AAO template. Moreover, the β-crystals in the porous template exhibit larger lattice parameters compared with the bulk crystals. By monitoring the change of β-crystals in the heating process, it was found that β-crystals in the AAO template with the pore diameter of 30 nm (D30) melt directly while the β-crystals transform to α-crystals in the template with the pore diameter of 100 nm (D100). The intensity of (020) Bragg peak of β-crystals decreases at a similar rate in both D30 and D100 but disappears at a relatively lower temperature in D30. On the other hand, the β(110) peak intensity of β-PBA crystals formed in the D100 template decreases first at slower rate before α crystals appear, and then at a faster rate once the β to α phase transition takes place.