3D-Printed Graphene Nanoplatelets/Polymer Foams for Low/Medium-Pressure Sensors.

The increasing interest in wearable devices for health monitoring, illness prevention, and human motion detection has driven research towards developing novel and cost-effective solutions for highly sensitive flexible sensors. The objective of this work is to develop innovative piezoresistive pressure sensors utilizing two types of 3D porous flexible open-cell foams: Grid and triply periodic minimal surface structures. These foams will be produced through a procedure involving the 3D printing of sacrificial templates, followed by infiltration with various low-viscosity polymers, leaching, and ultimately coating the pores with graphene nanoplatelets (GNPs). Additive manufacturing enables precise control over the shape and dimensions of the structure by manipulating geometric parameters during the design phase. This control extends to the piezoresistive response of the sensors, which is achieved by infiltrating the foams with varying concentrations of a colloidal suspension of GNPs. To examine the morphology of the produced materials, field emission scanning electron microscopy (FE-SEM) is employed, while mechanical and piezoresistive behavior are investigated through quasi-static uniaxial compression tests. The results obtained indicate that the optimized grid-based structure sensors, manufactured using the commercial polymer Solaris, exhibit the highest sensitivity compared to other tested samples. These sensors demonstrate a maximum sensitivity of 0.088 kPa-1 for pressures below 10 kPa, increasing to 0.24 kPa-1 for pressures of 80 kPa. Furthermore, the developed sensors are successfully applied to measure heartbeats both before and after aerobic activity, showcasing their excellent sensitivity within the typical pressure range exerted by the heartbeat, which typically falls between 10 and 20 kPa.

Wearable Graphene-based smart face mask for Real-Time human respiration monitoring.

After the pandemic of SARS-CoV-2, the use of face-masks is considered the most effective way to prevent the spread of virus-containing respiratory fluid. As the virus targets the lungs directly, causing shortness of breath, continuous respiratory monitoring is crucial for evaluating health status. Therefore, the need for a smart face mask (SFM) capable of wirelessly monitoring human respiration in real-time has gained enormous attention. However, some challenges in developing these devices should be solved to make practical use of them possible. One key issue is to design a wearable SFM that is biocompatible and has fast responsivity for non-invasive and real-time tracking of respiration signals. Herein, we present a cost-effective and straightforward solution to produce innovative SFMs by depositing graphene-based coatings over commercial surgical masks. In particular, graphene nanoplatelets (GNPs) are integrated into a polycaprolactone (PCL) polymeric matrix. The resulting SFMs are characterized morphologically, and their electrical, electromechanical, and sensing properties are fully assessed. The proposed SFM exhibits remarkable durability (greater than1000 cycles) and excellent fast response time (∼42 ms), providing simultaneously normal and abnormal breath signals with clear differentiation. Finally, a developed mobile application monitors the mask wearer's breathing pattern wirelessly and provides alerts without compromising user-friendliness and comfort.

New Sensing and Radar Absorbing Laminate Combining Structural Damage Detection and Electromagnetic Wave Absorption Properties.

Within the paradigm of smart mobility, the development of innovative materials aimed at improving resilience against structural failure in lightweight vehicles and electromagnetic interferences (EMI) due to wireless communications in guidance systems is of crucial relevance to improve safety, sustainability, and reliability in both aeronautical and automotive applications. In particular, the integration of intelligent structural health monitoring and electromagnetic (EM) shielding systems with radio frequency absorbing properties into a polymer composite laminate is still a challenge. In this paper, we present an innovative system consisting of a multi-layered thin panel which integrates nanostructured coatings to combine EM disturbance suppression and low-energy impact monitoring ability. Specifically, it is composed of a stack of dielectric and conductive layers constituting the sensing and EM-absorbing laminate (SEAL). The conductive layers are made of a polyurethane paint filled with graphene nanoplatelets (GNPs) at different concentrations to tailor the effective electrical conductivity and the functionality of the material. Basically, the panel includes a piezoresistive grid, obtained by selectively spraying onto mylar a low-conductive paint with 4.5 wt.% of GNPs and an EM-absorbing lossy sheet made of the same polyurethane paint but properly modified with a higher weight fraction (8 wt.%) of graphene. The responses of the grid's strain sensors were analyzed through quasi-static mechanical bending tests, whereas the absorbing properties were evaluated through free-space and waveguide-based measurement techniques in the X, Ku, K, and Ka bands. The experimental results were also validated by numerical simulations.

Exploring the Capabilities of a Piezoresistive Graphene-Loaded Waterborne Paint for Discrete Strain and Spatial Sensing.

The development of a piezoresistive coating produced from dispersing graphene nanoplatelets (GNPs) inside a commercial water-based polyurethane paint is presented. The feasibility of its exploitation for realizing highly sensitive discrete strain sensors and to measure spatial strain distribution using linear and two-dimensional depositions was investigated. Firstly, the production process was optimized to achieve the best electromechanical response. The obtained materials were then subjected to different characterizations for structural and functional investigations. Morphological analyses showed a homogenous dispersion of GNPs within the host matrix and an average thickness of about 75 µm of the obtained nanostructured films. By several adhesion tests, it was demonstrated that the presence of the nanostructures inside the paint film lowered the adhesion strength by only 20% in respect to neat paint. Through electrical tests, the percolation curve of the nanomaterial was acquired, showing an effective electrical conductivity ranging from about 10-4 S/m to 3.5 S/m in relation to the different amounts of filler dispersed in the neat paint: in particular, samples with weight fractions of 2, 2.5, 3, 3.5, 4, 5 and 6 wt% of GNPs were produced and characterized. Next, the sensitivity to flexural strain of small piezoresistive sensors deposited by a spray-coating technique on a fiberglass-reinforced epoxy laminate beam was measured: a high gauge factor of 33 was obtained at a maximum strain of 1%. Thus, the sensitivity curve of the piezoresistive material was successively adopted to predict the strain along a multicontact painted strip on the same beam. Finally, for a painted laminate plate subjected to a mechanical flexural load, we demonstrated, through an electrical resistance tomography technique, the feasibility to map the electrical conductivity variations, which are strictly related to the induced strain/stress field. As a further example, we also showed the possibility of using the coating to detect the presence of conducting objects and damage.

Waterproof Graphene-PVDF Wearable Strain Sensors for Movement Detection in Smart Gloves.

In this work, new highly sensitive graphene-based flexible strain sensors are produced. In particular, polyvinylidene fluoride (PVDF) nanocomposite films filled with different amounts of graphene nanoplatelets (GNPs) are produced and their application as wearable sensors for strain and movement detection is assessed. The produced nanocomposite films are morphologically characterized and their waterproofness, electrical and mechanical properties are measured. Furthermore, their electromechanical features are investigated, under both stationary and dynamic conditions. In particular, the strain sensors show a consistent and reproducible response to the applied deformation and a Gauge factor around 30 is measured for the 1% wt loaded PVDF/GNP nanocomposite film when a deformation of 1.5% is applied. The produced specimens are then integrated in commercial gloves, in order to realize sensorized gloves able to detect even small proximal interphalangeal joint movements of the index finger.

Flexible Ecoflex®/Graphene Nanoplatelet Foams for Highly Sensitive Low-Pressure Sensors.

The high demand for multifunctional devices for smart clothing applications, human motion detection, soft robotics, and artificial electronic skins has encouraged researchers to develop new high-performance flexible sensors. In this work, we fabricated and tested new 3D squeezable Ecoflex® open cell foams loaded with different concentrations of graphene nanoplatelets (GNPs) in order to obtain lightweight, soft, and cost-effective piezoresistive sensors with high sensitivity in a low-pressure regime. We analyzed the morphology of the produced materials and characterized both the mechanical and piezoresistive response of samples through quasi-static cyclic compression tests. Results indicated that sensors infiltrated with 1 mg of ethanol/GNP solution with a GNP concentration of 3 mg/mL were more sensitive and stable compared to those infiltrated with the same amount of ethanol/GNP solution but with a lower GNP concentration. The electromechanical response of the sensors showed a negative piezoresistive behavior up to ~10 kPa and an opposite trend for the 10-40 kPa range. The sensors were particularly sensitive at very low deformations, thus obtaining a maximum sensitivity of 0.28 kPa-1 for pressures lower than 10 kPa.

3D Porous Graphene Based Aerogel for Electromagnetic Applications.

Lightweight multifunctional electromagnetic (EM) absorbing materials with outstanding thermal properties, chemical resistance and mechanical stability are crucial for space, aerospace and electronic devices and packaging. Therefore, 3D porous graphene aerogels are attracting ever growing interest. In this paper we present a cost effective lightweight 3D porous graphene-based aerogel for EM wave absorption, constituted by a poly vinylidene fluoride (PVDF) polymer matrix filled with graphene nanoplatelets (GNPs) and we show that the thermal, electrical, mechanical properties of the aerogel can be tuned through the proper selection of the processing temperature, controlled either at 65 °C or 85 °C. The produced GNP-filled aerogels are characterized by exceptional EM properties, allowing the production of absorbers with 9.2 GHz and 6.4 GHz qualified bandwidths with reflection coefficients below -10 dB and -20 dB, respectively. Moreover, such aerogels show exceptional thermal conductivities without any appreciable volume change after temperature variations. Finally, depending on the process parameters, it is shown the possibility to obtain water repellent aerogel composites, thus preventing their EM and thermal properties from being affected by environmental humidity and allowing the realization of EM absorber with a stable response.

Phase Inversion in PVDF Films with Enhanced Piezoresponse Through Spin-Coating and Quenching.

In the present work, poly(vinylidene fluoride) (PVDF) films were produced by spin-coating, and applying different conditions of quenching, in order to investigate the dominant mechanism of the ß-phase formation. The influence of the polymer/solvent mass ratio of the solution, the rotational speed of the spin-coater and the crystallization temperature of the film on both the ß-phase content and the piezoelectric coefficient (d33) were investigated. This study demonstrates that the highest values of d33 are obtained when thinner films, produced with a lower concentration of polymer in the solvent (i.e., 20 wt.%), go through quenching in water, at room temperature. Whereas, in the case of higher polymer concentration (i.e., 30 wt.%), the best value of d33 (~30 pm/V) was obtained through quenching in liquid nitrogen, at the temperature of 77 K. We believe that in the former case, phase inversion is mainly originated by electrostatic interaction of PVDF with the polar molecules of water, due to the low viscosity of the polymer solution. On the contrary, in the latter case, due to higher viscosity of the solution, mechanical stretching induced on the polymer during spin-coating deposition is the main factor inducing self-alignment of the ß-phase. These findings open up a new way to realize highly efficient devices for energy harvesting and wearable sensors.

Piezoelectric Effect and Electroactive Phase Nucleation in Self-Standing Films of Unpoled PVDF Nanocomposite Films.

Novel polymer-based piezoelectric nanocomposites with enhanced electromechanical properties open new opportunities for the development of wearable energy harvesters and sensors. This paper investigates how the dissolution of different types of hexahydrate metal salts affects ß-phase content and piezoelectric response (d33) at nano- and macroscales of polyvinylidene fluoride (PVDF) nanocomposite films. The strongest enhancement of the piezoresponse is observed in PVDF nanocomposites processed with Mg(NO3)2⋅6H2O. The increased piezoresponse is attributed to the synergistic effect of the dipole moment associated with the nucleation of the electroactive phase and with the electrostatic interaction between the CF2 group of PVDF and the dissolved salt through hydrogen bonding. The combination of nanofillers like graphene nanoplatelets or zinc oxide nanorods with the hexahydrate salt dissolution in PVDF results in a dramatic reduction of d33, because the nanofiller assumes a competitive role with respect to H-bond formation between PVDF and the dissolved metal salt. The measured peak value of d33 reaches the local value of 13.49 pm/V, with an average of 8.88 pm/V over an area of 1 cm². The proposed selection of metal salt enables low-cost production of piezoelectric PVDF nanocomposite films, without electrical poling or mechanical stretching, offering new opportunities for the development of devices for energy harvesting and wearable sensors.

Electrical, Mechanical and Electromechanical Properties of Graphene-Thermoset Polymer Composites Produced Using Acetone-DMF Solvents.

Recently, graphene-polymer composites gained a central role in advanced stress and strain sensing. A fundamental step in the production of epoxy-composites filled with graphene nanoplatelets (GNPs) consists in the exfoliation and dispersion of expanded graphite in a proper solvent, in the mixing of the resulting GNP suspension with the polymer matrix, and in the final removal of the solvent from the composite before curing through evaporation. The effects of traces of residual solvent on polymer curing process are usually overlooked, even if it has been found that even a small amount of residual solvent can affect the mechanical properties of the final composite. In this paper, we show that residual traces of N,N'-Dimethylformamide (DMF) in vinylester epoxy composites can induce relevant variations of the electrical, mechanical and electromechanical properties of the cured GNP-composite. To this purpose, a complete analysis of the morphological and structural characteristics of the composite samples produced using different solvent mixtures (combining acetone and DMF) is performed. Moreover, electrical, mechanical and electromechanical properties of the produced composites are assessed. In particular, the effect on the piezoresistive response of the use of DMF in the solvent mixture is analyzed using an experimental strain dependent percolation law to fit the measured electromechanical data. It is shown that the composites realized using a higher amount of DMF are characterized by a higher electrical conductivity and by a strong reduction of Young's Modulus.

A Flexible and Highly Sensitive Pressure Sensor Based on a PDMS Foam Coated with Graphene Nanoplatelets.

The demand for high performance multifunctional wearable devices is more and more pushing towards the development of novel low-cost, soft and flexible sensors with high sensitivity. In the present work, we describe the fabrication process and the properties of new polydimethylsiloxane (PDMS) foams loaded with multilayer graphene nanoplatelets (MLGs) for application as high sensitive piezoresistive pressure sensors. The effective DC conductivity of the produced foams is measured as a function of MLG loading. The piezoresistive response of the MLG-PDMS foam-based sensor at different strain rates is assessed through quasi-static pressure tests. The results of the experimental investigations demonstrated that sensor loaded with 0.96 wt.% of MLGs is characterized by a highly repeatable pressure-dependent conductance after a few stabilization cycles and it is suitable for detecting compressive stresses as low as 10 kPa, with a sensitivity of 0.23 kPa-1, corresponding to an applied pressure of 70 kPa. Moreover, it is estimated that the sensor is able to detect pressure variations of ~1 Pa. Therefore, the new graphene-PDMS composite foam is a lightweight cost-effective material, suitable for sensing applications in the subtle or low and medium pressure ranges.

Electro-Mechanical Properties of Multilayer Graphene-Based Polymeric Composite Obtained through a Capillary Rise Method.

A new sensor made of a vinyl-ester polymer composite filled with multilayer graphene nanoplatelets (MLG) is produced through an innovative capillary rise method for application in strain sensing and structural health monitoring. The new sensor is characterized by high stability of the piezoresistive response under quasi-static consecutive loading/unloading cycles and monotonic tests. This is due to the peculiarity of the fabrication process that ensures a smooth and clean surface of the sensor, without the presence of filler agglomerates acting as micro- or macro-sized defects in the composite.

Electromagnetic and Dynamic Mechanical Properties of Epoxy and Vinylester-Based Composites Filled with Graphene Nanoplatelets.

Development of epoxy or epoxy-based vinyl ester composites with improved mechanical and electromagnetic properties, filled with carbon-based nanomaterials, is of crucial interest for use in aerospace applications as radar absorbing materials at radio frequency. Numerous studies have highlighted the fact that the effective functional properties of this class of polymer composites are strongly dependent on the production process, which affects the dispersion of the nanofiller in the polymer matrix and the formation of micro-sized aggregations, degrading the final properties of the composite. The assessment of the presence of nanofiller aggregation in a composite through microscopy investigations is quite inefficient in the case of large scale applications, and in general provides local information about the aggregation state of the nanofiller rather than an effective representation of the degradation of the functional properties of the composite due to the presence of the aggregates. In this paper, we investigate the mechanical, electrical, and electromagnetic properties of thermosetting polymer composites filled with graphene nanoplatelets (GNPs). Moreover, we propose a novel approach based on measurements of the dielectric permittivity of the composite in the 8⁻12 GHz range in order to assess the presence of nanofiller aggregates and to estimate their average size and dimensions.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: influence of process parameters on the electrical and optical properties.

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp(2) carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 10(5) S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.