Infrared laser ablation of poly(vinylidene fluoride): The Loss of HF

•PVDF laser ablation mass loss increases linearly with time after induction period.•HF loss and polymer backbone destruction occur.•Double bonds, cumulated double bonds, and triple bonds form in the backbone.•Fine ∼100 nm powder and dendritic structures form on ablation.•G3MP2 calculations support mechanism of HF loss followed by backbone cleavage.