Ternary composites of flexible thermoplastic polyurethane (TPU), lead zirconate titanate (PZT), and multiwalled carbon nanotubes (MWCNTs) with very high dielectric permittivity (ε_r) and low dielectric loss (tan δ) are reported. To assess the evolution of dielectric properties with the interactions between conductive and dielectric fillers, composites were designed with a range of content for PZT (0–30 vol%) and MWCNT (0–1 vol%). The microstructure was composed of PZT-rich and segregated MWCNT-rich regions, which could effectively prevent the formation of macroscopic MWCNT conductive networks and thus reduce the high ohmic loss. Therefore, ε_r increased by a maximum of tenfold, reaching up to 166 by the addition of up to 1 vol% MWCNT to TPU/PZT. More importantly, tan δ remained relatively unchanged at 0.06–0.08, a similar range to that of pure TPU. ε_r/tan δ ratio reached 2870 at TPU/30 vol% PZT/0.5 vol% MWCNT, exceeding most of the reported values. This work demonstrates the potential of three-phase polymer/conductive filler/dielectric filler composites for efficient charge storage applications.

The sensitivity enhancement of piezocomposites can realize new applications. Introducing a cellular structure into these materials decreases the permittivity and thus increases their sensitivity. However, foaming of piezocomposites is challenging because of the high piezoceramic loading required. In this work, heat-expandable microspheres were used to fabricate thermoplastic polyurethane (TPU)/lead zirconate titanate (PZT) composite foams with a wide range of PZT content (0 vol % to 40 vol %) and expansion ratio (1–4). The microstructure, thermal behavior, and dielectric properties of the foams were investigated. Composite foams exhibited a fine dispersion of PZT particles in the solid phase and a uniform cellular structure with cell sizes of 50–100 μm; cell size decreased with an increase in the PZT content. The total crystallinity of the composites was also decreased as the foaming degree increased. The results showed that the relative permittivity (ε_r) can be effectively decreased by an increase in the expansion ratio. A maximum of 7.7 times decrease in ε_r was obtained. An extended Yamada model to a three-phase system was also established and compared against the experimental results with a relatively good agreement. This work demonstrates a method to foam highly loaded piezocomposites with a potential to enhance the voltage sensitivity.

Additive manufacturing (AM) is an emerging field experiencing rapid growth. This paper presents a feasibility study of using fused-deposition modeling (FDM) techniques with smart materials to fabricate objects with sensing and actuating capabilities. The fabrication of objects with sensing typically requires the integration and assembly of multiple components. Incorporating sensing elements into a single FDM process has the potential to significantly simplify manufacturing. The integration of multiple materials, especially smart materials and those with multi-functional properties, into the FDM process is challenging and still requires further development. Previous works by the authors have demonstrated a good printability of thermoplastic polyurethane/multiwall carbon nanotubes (TPU/MWCNT) while maintaining conductivity and piezoresistive response. This research explores the effects of layer height, nozzle temperature, and bed temperature on the electrical conductivity and piezoresistive response of printed TPU/MWCNT nanocomposites. An impedance analyzer was used to determine the conductivity of printed samples under different printing conditions from 5Hz-13MHz. The samples were then tested under compression loads to measure the piezoresistive response. Results show the conductivity and piezoresistive response are only slightly affected by the print parameters and they can be largely considered independent of the print conditions within the examined ranges of print parameters. This behavior simplifies the printing process design for TPU/MWCNT complex structures. This work demonstrates the possibility of manufacturing embedded and multidirectional flexible strain sensors using an inexpensive and versatile method, with potential applications in soft robotics, flexible electronics, and health monitoring.

The sensitivity of piezoelectric/polymer composite materials is inversely proportional to their dielectric permittivity. Introducing a cellular structure into these composites can decrease the permittivity while enhancing their mechanical flexibility. Foaming of highly filled polymer composites is however challenging. Polymers filled with high content of dense additives such as lead zirconate titanate (PZT) exhibit significantly decreased physical foaming ability. This can be attributed to difficulty in gas diffusion, decreased fraction of the matrix available, the reduced number of nucleated cells and the difficulty in cell growth. Here, both CO₂ foaming and Expancel foaming were examined as potential methods to fabricate low-density thermoplastic polyurethane (TPU)/ PZT composite foams. While composites containing up to only 10vol.% PZT could be foamed using CO₂, Expancel foaming could successfully yield highly-expanded composite foams containing up to 40vol.% (80wt.%) PZT. Dispersed Expancel particles in TPU/PZT composites acted as the blowing agent, activated by subjecting the samples to high temperatures using a hot press. Using Expancel, foams with expansion ratios of up to 9 were achieved. However, expansion ratios of greater than 4 were not of interest due to their poor structural integrity. The density of solid samples ranged from 1.8 to 3.3 g.cm⁻³ and dropped by a maximum of 80%, even for the highest PZT content, at an expansion ratio of 4. As the expansion increased, the dielectric permittivity of both CO₂-foamed and Expancel-foamed TPU/PZT composites decreased significantly (up to 7.5 times), while the dielectric loss and electrical conductivity were affected only slightly. This combination of properties is suitable for high-sensitivity and flexible piezoelectric applications.