This paper outlines the shrinkage of electrospun polyvinylpyrrolidone (PVP) fiber mats during thermal treatment. The thermal behavior and phase changes within the fibers were investigated by DSC and TGA/DTA. Five precursors with different PVP loading in ethanol were electrospun. The mats shrinkage as function of temperature was measured in the RT–200 °C range. Shrinkage rate drastically increased above the polymer glass transition point, Tg (150–180 °C), due to increase in polymer chain mobility. Mats shrinkage at 200 °C as function of PVP concentration showed a minimum at ∼10%wt. Below 10% PVP the mats morphology is non‐uniform, consisting of beads and fibers. Above 10% PVP, only flat and uniform fibers were observed. This paper outlines the dominant mechanism governing the mats shrinkage during heating. In addition, the effect of PVP concentration on the expansion of fibers diameter was investigated and found to be consistent with the linear shrinkage observing a minimum at ∼10% PVP. The effect of applied voltage on mat shrinkage was investigated, and showed a minimum at 12 kV. Understanding the interplay between fibers morphology and thermal shrinkage allows precursor composition and system optimization needed for minimizing shrinkage negative effects on the structure and properties of electrospun fiber mats. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 248–254

This paper focuses on the deformation origin of PbZr 0.52 Ti 0.48 O 3 (PZT) fiber mats obtained by electrospinning. The main cause of deformation of the green mats during heating was found to be a nonuniform relaxation of the stretched PVP polymer, due to nonuniform thermal decomposition of the Pb-hexanoate in the fibers. This relaxation starts under 100°C, well below the polymer decomposition temperature. The shrinkage was found to accelerate above the polymer glass transition point, giving rise to an overall linear change of almost 50%. The "green" PZT mats were easily separated from the collector by first depositing a pure PVP sublayer on the collector. An optimal fabrication and slow multistep thermal treatment process that provides fiber mats with desired PZT phase and overcomes the nonuniform deformation is described.