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Poly(vinilidene fluoride) was characterized before and after stress relaxation by tensile tests and time-domain nuclear magnetic resonance (TD-NMR). Tensile tests were performed to provide mechanical properties, focused on the data of elastic modulus for this matter. The TD-NMR technique was used to calculate the fraction of crystalline, constrained amorphous and free amorphous phase, and the transversal relaxation time of each of these phases.