Direct-Ink-Writing of Electroactive Polymers for Sensing and Energy Storage Applications

Considering the high levels of materials used in the fields of electronics and energy storage systems, it is increasingly necessary to take into consideration environmental impact. Thus, it is important to develop devices based on environmentally friendlier materials and/or processes, such as additive manufacturing techniques. In this work, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) are prepared by direct-ink-writing (DIW) by varying solvent evaporation temperature and fill density percentage. Different morphologies for both polymers are obtained, including dense films and porous membranes, as well as different electroactive β-phase content, thermal and mechanical properties. The dielectric constant and piezoelectric d₃₃ coefficient for dense films reaches up to 16 at 1 kHz and 4 pC N⁻¹, respectively for PVDF-HFP with a fill density of 80 and a solvent evaporation temperature of 50 °C. Porous structures are developed for battery separator membranes in lithium-ion batteries, with a highest ionic conductivity value of 3.8 mS cm⁻¹ for the PVDF-HFP sample prepared with a fill density of 100 and a solvent evaporation temperature of 25 °C, the sample showing an excellent cycling performance. It is demonstrated that electroactive films and membranes can be prepared by direct-ink writing suitable for sensors/actuators and energy storage systems.     

Influence of zeolite structure and chemistry on the electrical response and crystallization phase of poly(vinylidene fluoride)

Zeolites with framework types LTL, LTA, FAU, and MFI were synthesized and used as fillers to prepare PVDF/zeolite composites. The obtained composites showed structural and electrical dependence on the pore system and chemical content of the inorganic host. The larger polymer-zeolite electrostatic interactions of the Y and A zeolites lead the polymer to crystallize in the electroactive γ-phase, which in the case of the L zeolite is prevented due to the reduced interaction area. The solvent and water encapsulation ability of the zeolite as well as improve of the dielectric response of the composite is directly related to the Si/Al ratio, leading zeolites with lower Si/Al ratios to larger dielectric responses and encapsulation efficiencies in the composites. These effects show also some dependency on the dimensionality of the pore system; the zeolite L-containing 1D channels showing superior dielectric performance than the 3D pore system of zeolite Y.     

Electroactive phases of poly(vinylidene fluoride): Determination,processing and applications

Poly(vinylidene fluoride), PVDF, and its copolymers are the family of polymers with the highest dielectric constant and electroactive response, including piezoelectric, pyroelectric and ferroelectric effects. The electroactive properties are increasingly important in a wide range of applications such as in biomedicine, energy generation and storage, monitoring and control, and include the development of sensors and actuators, separator and filtration membranes and smart scaffolds, among others. For many of these applications the polymer should be in one of its electroactive phases. This review presents the developments and summarizes the main characteristics of the electroactive phases of PVDF and copolymers, indicates the different processing strategies as well as the way in which the phase content is identified and quantified. Additionally, recent advances in the development of electroactive composites allowing novel effects, such as magnetoelectric responses, and opening new applications areas are presented. Finally, some of the more interesting potential applications and processing challenges are discussed.     

Piezoresistive silicon thin film sensor array for biomedical applications

N-type hydrogenated nanocrystalline silicon thin film piezoresistors, with gauge factor − 28, were deposited on rugged and flexible polyimide foils by Hot-wire chemical vapor deposition using a tantalum filament heated to 1750 °C. The piezoresistive response under cyclic quasi-static and dynamical (up to 100 Hz) load conditions is reported. Test structures, consisting of microresistors having lateral dimensions in the range from 50 to 100 μm and thickness of 120 nm were defined in an array by reactive ion etching. Metallic pads, forming ohmic contacts to the sensing elements, were defined by a lift-off process. A readout circuit for the array consisting in a mutiplexer on each row and column of the matrix is proposed. The digital data will be processed, interpreted and stored internally by an ultra low-power micro controller, also responsible for the communication of two-way wireless data, e.g. from inside to outside the human body.     

The effect of fibre concentration on the α to β-phase transformation, degree of crystallinity and electrical properties of vapour grown carbon nanofibre/poly(vinylidene fluoride) composites

Vapour growth carbon nanofibres/poly(vinilidene fluoride) - VGCNF/PVDF - composites prepared by solution casting were studied. The spherulitic crystallisation morphology of the pure polymer is maintained for the composites. Mechanical stretching of the composite films induces the α to β-phase transformation within the polymer matrix. This phase transition is accompanied by the destruction of the spherulitic microstructure in favour of a microfibrillar one. The incorporation of the VGCNF in the PVDF matrix increases the degree of crystallinity of the polymer composites for concentrations lower than ∼1%, remaining stable for higher VGCNF concentrations. With respect to the electrical properties, the stretching associated to the phase transformation induces a change in the conduction mechanism: the α-phase composite demonstrates a percolative behaviour on the measured conductivity whereas the β-phase demonstrates typical ionic conduction behaviour. Dielectric measurements in conjunction with the the two exponent percolation phenomenological equation demonstrates that in the β-phase an effective reduction in the ratio VGCNF length/domain length could induce the observed percolation behaviour.     

Electrohydrodynamic 3D Printing of Aqueous Solutions

Among the various electrohydrodynamic (EHD) processing techniques, electrowriting (EW) produces the most complex 3D structures. Aqueous solution EW similarly retains the potential for additive manufacturing well-resolved 3D structures, while providing new opportunities for processing biologically derived polymers and eschewing organic solvents. However, research on aqueous-based EHD processing is still limited. To summarize the field and advocate for increased use of aqueous bio-based materials, this review summarizes the most significant contributions of aqueous solution processing. Special emphasis has been placed on understanding the effects of different printing parameters, the prospects for 3D processing new materials, and future challenges.