Effects of molecular architecture on two‐step,melt‐spun poly(lactic acid) fibers

Fibers of poly(lactic acid) (PLA) produced by two‐step melt spinning have been studied. The PLA resins used contain a 96:04 ratio of L:D stereochemical centers; however, one of the materials is branched by a peroxide treatment. The thermal, mechanical, and morphological properties of the fibers are compared for the two different molecular architectures. In the branched material, at least some of the branches exceed the entanglement molecular weight. The branched material is accordingly characterized by greater shear and extensional viscosity than the linear material. Fiber properties are highly influenced by the draw ratio; both branched and linear materials reach a plateau of about 35% crystallinity. The branched polymer reaches the plateau at a lower draw ratio, and this is indicative of faster crystallization kinetics. Both materials shrink in boiling water, and the amount of shrinkage decreases with increasing draw ratio. At an intermediate draw ratio of 6, the branched material is characterized by significantly larger shrinkage. With small‐angle X‐ray scattering and atomic force microscopy, the morphology is found to be fibrillar. Microfibril diameters range from approximately 20 to 30 nm and are almost identical for the two molecular architectures studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2839–2846, 2002