Cellulose Nanocrystal-Based All-3D-Printed Pyro-Piezoelectric Nanogenerator for Hybrid Energy Harvesting and Self-Powered Cardiorespiratory Monitoring toward the Human-Machine Interface.

Biomaterials with spontaneous piezoelectric property are highly emerging in recent times for the generation of electricity from mechanical energy sources that are amply available in nature. In this context, pyroelectricity, an integral property of piezoelectric materials, might be an interesting tool in harvesting thermal energy from the fluctuations of temperature. On the other hand, respiration and heart pulse are the significant human vital signs that can be used for early detection and prevention of cardiorespiratory diseases. Here, we report an all-three-dimensional (3D)-printed pyro-piezoelectric nanogenerator (Py-PNG) based on the most abundant and completely biodegradable biopolymer on earth, i.e., cellulose nanocrystal (CNC) for hybrid (mechanical as well as thermal) energy harvesting, and interestingly, the NG could be used as an e-skin sensor for application in self-powered noninvasive cardiorespiratory monitoring for personal healthcare. Notably, the CNC-based device will be biocompatible and economically advantageous due to its biomaterial-based supremacy and huge availability. This is an original approach with 3D geometrical advancement in designing a NG/sensor, where the unique all-3D-printed manner is adopted, and certainly, it has promising potential in reducing the number of processing steps to required equipment during the multilayer fabrication. The all-3D-printed NG/sensor shows outstanding mechano-thermal energy harvesting performance along with sensitivity and is capable of accurate detection of heart pulse as well as respiration, whenever and whichever required without the need of any battery or an external power supply. In addition, we have also extended its application in demonstrating a smart mask-based breath monitoring system. Thus, the real-time cardiorespiratory monitoring provides notable and fascinating information in medical diagnosis, stepping toward biomedical device development and human-machine interface.

Three-Dimensional Printed Highly Porous and Flexible Conductive Polymer Nanocomposites with Dual-Scale Porosity and Piezoresistive Sensing Functions.

Highly flexible, deformable, and ultralightweight structures are required for advanced sensing applications, such as wearable electronics and soft robotics. This study demonstrates the three-dimensional (3D) printing of highly flexible, ultralightweight, and conductive polymer nanocomposites (CPNCs) with dual-scale porosity and piezoresistive sensing functions. Macroscale pores are established by designing structural printing patterns with adjustable infill densities, while the microscale pores are developed by phase separation of the deposited polymer ink solution. A conductive polydimethylsiloxane solution is prepared by mixing polymer/carbon nanotubes with non-solvent and solvent phases. Silica nanoparticles are utilized to modify the rheological properties of the ink, making direct ink writing (DIW) feasible. 3D geometries with various structural infill densities and polymer concentrations are deposited using DIW. The solvent is evaporated during a stepping heat treatment, leading to non-solvent droplet nucleation and growth. The microscale cellular network is developed by removing the droplets and curing the polymer. Up to 83% tunable porosity is achieved by independently controlling the macro- and microscale porosity. The effect of macroscale/microscale porosity and printing nozzle sizes on the mechanical and piezoresistive behavior of the CPNC structures is explored. The electrical and mechanical tests demonstrate a durable, extremely deformable, and sensitive piezoresistive response without sacrificing mechanical performance. The flexibility and sensitivity of the CPNC structure are enhanced up to 900 and 67% with the development of dual-scale porosity. The application of the developed porous CPNCs as piezoresistive sensors for detecting human motion is also evaluated.

Funnel-Shaped Floating Vessel Oil Skimmer with Joule Heating Sorption Functionality.

Floating vessel-type oil collecting devices based on sorbent materials present potential solutions to oil spill cleanup that require a massive amount of sorbent material and manual labor. Additionally, continuous oil extraction from these devices presents opportunities for highly energy-efficient oil skimmers that use gravity as the oil/water separation mechanism. Herein, a sorbent-based oil skimmer (SOS) is developed with a novel funnel-shaped sorbent and vessel design for efficient and continuous extraction of various oils from the water surface. A carbon black (CB) embedded polydimethylsiloxane (PDMS) sponge material is characterized and used as the sorbent in the SOS. The nanocomposite sponge formulation is optimized for high reusability, hydrophobicity, and rapid oil absorption. Joule heating functionality of the sponge is also explored to rapidly absorb highly viscous oils that are a significant challenge for oil spill cleanup. The optimized sponge material with the highest porosity and 15 wt% CB loading is tested in the SOS for large-scale oil spill extraction tests and shows effective cleaning of oil spilled on the water surface. The SOS demonstrates a high maximum extraction rate of 200 mL/min for gasoline and maintains a high extraction rate performance upon reuse when the sponge funnel is cleaned and dried.

PDMS Sponges with Embedded Carbon Nanotubes as Piezoresistive Sensors for Human Motion Detection.

Porous piezoresistive sensors offer promising flexible sensing functionality, such as human joint motion detection and gesture identification. Herein, a facile fabrication method is developed using a microwave-based rapid porogen removal technique for the manufacturing of porous nanocomposite sponges consisting of polydimethylsiloxane (PDMS) and well-dispersed carbon nanotubes (CNTs). The porogen amounts and CNT loadings are varied to tailor the porosity and electrical properties of the porous sensors. The sponges are characterized by a scanning electron microscope (SEM) to compare their microstructures, validate the high-quality CNT dispersion, and confirm the successful nanofiller embedding within the elastomeric matrix. Sponges with a 3 wt% CNT loading demonstrate the highest piezoresistive sensitivity. Experimental characterization shows that the sponges with low porosity have long durability and minimal strain rate dependence. Additionally, the developed sponges with 3 wt% CNTs are employed for the human motion detection using piezoresistive method. One experiment includes fingertip compression measurements on a prosthetic hand. Moreover, the sensors are attached to the chest, elbow, and knee of a user to detect breathing, running, walking, joint bending, and throwing motions.

Rapid Microwave Polymerization of Porous Nanocomposites with Piezoresistive Sensing Function.

In this paper, polydimethylsiloxane (PDMS) and multi-walled carbon nanotube (MWCNT) nanocomposites with piezoresistive sensing function were fabricated using microwave irradiation. The effects of precuring time on the mechanical and electrical properties of nanocomposites were investigated. The increased viscosity and possible nanofiller re-agglomeration during the precuring process caused decreased microwave absorption, resulting in extended curing times, and decreased porosity and electrical conductivity in the cured nanocomposites. The porosity generated during the microwave-curing process was investigated with a scanning electron microscope (SEM) and density measurements. Increased loadings of MWCNTs resulted in shortened curing times and an increased number of small well-dispersed closed-cell pores. The mechanical properties of the synthesized nanocomposites including stress-strain behaviors and Young's Modulus were examined. Experimental results demonstrated that the synthesized nanocomposites with 2.5 wt. % MWCNTs achieved the highest piezoresistive sensitivity with an average gauge factor of 7.9 at 10% applied strain. The piezoresistive responses of these nanocomposites were characterized under compressive loads at various maximum strains, loading rates, and under viscoelastic stress relaxation conditions. The 2.5 wt. % nanocomposite was successfully used in an application as a skin-attachable compression sensor for human motion detection including squeezing a golf ball.

Enhanced Electrical Conductivity of Carbon Nanotube-Based Elastomer Nanocomposites Prepared by Microwave Curing

Nanocomposites consisting of polydimethylsiloxane (PDMS) and well-dispersed carbon nanotubes (CNT) can be cured by microwave radiation within a minute, forming a conductive network within the cured materials. Microwave irradiation delivers energy directly to the inner core of the nanocomposites by heating CNTs and initiating rapid polymerization of the elastomer. In this paper, nanocomposites were fabricated with CNT loadings between 0.5 wt.%­2.5 wt.% via microwave irradiation. Key properties of the nanocomposites including electrical conductivity, microstructures, CNT distribution, density, and surface effects were all characterized. The properties of microwave-cured nanocomposites were compared with those manufactured by the thermal method using a conventional oven. The microwave-curing method substantially increased the electrical conductivity of the nanocomposites due to the improved nanoparticle dispersion and likely CNT alignment. Optimal microwave-curing parameters were identified to further improve the conductivity of the nanocomposites with lowest CNT loading. A conductivity enhancement of 142.8% over thermally cured nanocomposites was achieved for nanocomposites with 1 wt.% CNTs cured via one-step microwave irradiation.