Piezoelectric textile structures based on 100% poly(vinylidene fluoride) (PVDF) were developed and characterised. Multifilaments of 246 tex were produced by melt spinning. The mechanical stretching during the process provides PVDF fibres with a piezoelectric β-phase of up to 97% has been measured by FTIR experiments. Several studies have been carried out on piezoelectric PVDF-based flexible structures (films or textiles), the aim of the study being the investigation of the differences between 2D and 3D woven fabrics from 100% optimised (by optimising piezoelectric crystalline phase) piezoelectric PVDF multifilament yarns. The textile structures were poled after the weaving process, and a maximum output voltage of 2.3 V was observed on 3D woven under compression by DMA tests. Energy harvesting is optimised in a 3D interlock thanks to the stresses of the multifilaments in the thickness. The addition of a resistor makes it possible to measure energy of 10.5 μJ.m−2 during 10 cycles of stress in compression of 5 s each.

Poly(vinylidene fluoride) (PVDF) fibres used to develop sensors or energy harvesters have great potential in the sector of portable electronic devices and especially in the development of smart textiles. This polymorphic polymer is known for several years for its excellent piezoelectric properties related to its different crystalline phases and more particularly to the polar β‐phase is the subject of studies dedicated to the development, optimization, and characterization of β‐PVDF fibres. The presence and the evolution of the different crystalline phases are linked to different factors and can be controlled for example by changing some parameters during the process. In the case of the spinning process, the influence of the operating conditions, such as temperature and drawing on the crystalline structure is currently determined by post‐mortem analyses. Development of ‘mimetic’ tests to characterize in situ the evolution of the crystalline structure of a mechanically stretched polymer is a possible way. Nevertheless, this cannot totally reproduce a real process. For the first time, phase transformations and evolutions of PVDF during a melt‐spinning process were studied online thanks to in situ Raman spectroscopy measurements. Performed at different stages of the spinning line, this method allows us to follow the evolution of the crystalline phases in real time, during the key steps of the process and to conclude on the conditions for obtaining the piezoelectric phase. The successful online characterization of PVDF crystalline phases by Raman spectroscopy opens new perspectives for the optimization of these fibres by controlling the evolution of the structure when changing process parameters.

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