Understanding the Seeded Heteroepitaxial Growth of Crystallizable Polymers: The Role of Crystallization Thermodynamics

Seeded heteroepitaxial growth is a "living" crystallization-driven self-assembly (CDSA) method that has emerged as a promising route to create uniform segmented nanoparticles with diverse core chemistries by using chemically distinct core-forming polymers. Our previous results have demonstrated that crystallization kinetics is a key factor that determines the occurrence of heteroepitaxial growth, but an in-depth understanding of controlling heteroepitaxy from the perspective of crystallization thermodynamics is yet unknown. Herein, we select crystallizable aliphatic polycarbonates (PxCs) with a different number of methylene groups (xCH2, x = 4, 6, 7, 12) in their repeating units as model polymers to explore the effect of lattice match and core compatibility on the seeded growth behavior. Seeded growth of PxCs-containing homopolymer/block copolymer blend unimers from poly(ε-caprolactone) (PCL) core-forming seed platelet micelles exhibits distinct crystal growth behavior at subambient temperatures, which is governed by the lattice match and core compatibility. A case of seeded growth with better core compatibility and a smaller lattice mismatch follows epitaxial growth, where the newly created crystal domain has the same structural orientation as the original platelet substrate. In contrast, a case of seeded growth with better core compatibility but a larger lattice mismatch shows nonepitaxial growth with less-defined crystal orientations in the platelet plane. Additionally, a case of seeded growth with poor core compatibility and larger lattice mismatch results in polydisperse platelet micelles, whereby crystal formation is not nucleated from the crystalline substrate. These findings reveal important factors that govern the specific crystal growth during a seeded growth approach by using compositionally distinct cores, which would further guide researchers in designing 2D segmented materials via polymer crystallization approaches.