Noninvasive high-frequency acoustic microscopy for 3D visualization of microstructure and estimation of elastic properties during hydrolytic degradation of lactide and ε-caprolactone polymers.

The monitoring of degradation processes' kinetics in polymers is one of the attractive possibilities of ultrasound technique applications that provide non-destructive imaging of polymers' internal microstructure and measurements of elastic properties. In this work, biodegradable polymers and copolymers based on L,L-lactide, D,L-lactide and ε-caprolactone have been studied at different stages of hydrolysis at 37 °C by high-frequency (100 and 200 MHz) ultrasound. The acoustic microscopy technique has been developed to reveal changes in the internal microstructure and bulk sound speed in polymer samples over a hydrolysis period of 25 weeks. Ultrasound imaging provides visualization of amorphous and crystalline phases, internal imperfections, variation in packing density, and other microstructural features. Acoustic images demonstrate nucleation, growth, and the changes in internal inhomogeneities in polymers during degradation accompanied by a decrease in the polymers' molecular weight. We associate the changes in the elastic properties (the speed of a longitudinal wave) with crystallinity variations in polymers during hydrothermal aging. The results of the ultrasound investigations are supplemented by gel permeation chromatography, differential scanning calorimetry, and wide-angle X-ray spectroscopy. STATEMENT OF SIGNIFICANCE: Monitoring the kinetics of degradation processes in polymers is one of the attractive possibilities of applying ultrasound techniques that provide non-destructive imaging of the polymers' internal microstructure and measurements of elastic properties. In this work, visualization of nucleation, growth, and evolution of internal inhomogeneities in the volume of polymers and variation of values of speed of longitudinal and transverse sound waves during hydrolysis are compared with measurements of molecular weight, density, data of DSC curves, and X-ray scattering analysis. We discuss several common phenomena that occur in the volume of poly(L-lactide) and poly(D,L-lactide) over the degradation process as well as improvement of elastic properties of the poly(ε -caprolactone) and poly(L-lactide-co-caprolactone) during hydrothermal aging.