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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 th