The Presence of Ultralow Densities of Nanocrystallites in Amorphous Poly(lactic acid) Microspheres

Ultralow densities of crystalline nanospheres have been detected in amorphous polymer microspheres by utilizing the unique sensitivity of second-order nonlinear optical techniques to anisotropy. Vibrational sum frequency scattering (SFS) and X-ray diffraction (XRD) are used to quantify the crystallinity of amorphous poly(D,L-lactic acid) microspheres. While XRD does not display any crystallinity for the microspheres, SFS spectra and patterns are reminiscent of a heterogeneous microsphere that contains small crystalline domains. Nonlinear light scattering theory was used to model the data, and an average domain radius of 147 ± 65 nm was obtained. The degree of crystallinity (0.2%) was estimated by comparing XRD and SFS data obtained from the amorphous microspheres to similar data obtained from crystalline microspheres. We estimate a detection limit of 0.002% for SFS.