Smart and Multifunctional Materials Based on Electroactive Poly(vinylidene fluoride): Recent Advances and Opportunities in Sensors, Actuators, Energy, Environmental, and Biomedical Applications.

From scientific and technological points of view, poly(vinylidene fluoride), PVDF, is one of the most exciting polymers due to its overall physicochemical characteristics. This polymer can crystalize into five crystalline phases and can be processed in the form of films, fibers, membranes, and specific microstructures, being the physical properties controllable over a wide range through appropriate chemical modifications. Moreover, PVDF-based materials are characterized by excellent chemical, mechanical, thermal, and radiation resistance, and for their outstanding electroactive properties, including high dielectric, piezoelectric, pyroelectric, and ferroelectric response, being the best among polymer systems and thus noteworthy for an increasing number of technologies. This review summarizes and critically discusses the latest advances in PVDF and its copolymers, composites, and blends, including their main characteristics and processability, together with their tailorability and implementation in areas including sensors, actuators, energy harvesting and storage devices, environmental membranes, microfluidic, tissue engineering, and antimicrobial applications. The main conclusions, challenges and future trends concerning materials and application areas are also presented.

Enhanced Electrochemiluminescence at the Gas/Liquid Interface of Bubbles Propelled into Solution.

Electrochemiluminescence (ECL) is typically confined to a micrometric region from the electrode surface. This study demonstrates that ECL emission can extend up to several millimeters away from the electrode employing electrogenerated chlorine bubbles. The mechanism behind this bubble-enhanced ECL was investigated using an Au microelectrode in chloride-containing and chloride-free electrolyte solutions. We discovered that ECL emission at the gas/solution interface is driven by two parallel effects. First, the bubble corona effect facilitates the generation of hydroxyl radicals capable of oxidizing luminol while the bubble is attached to the surface. Second, hypochlorite generated from chlorine sustains luminol emission for over 200 s and extends the emission range up to 5 mm into the solution, following bubble detachment. The new approach can increase the emission intensity of luminol-based assays 5-fold compared to the conventional method. This is demonstrated through a glucose bioassay, using a midrange mobile phone camera for detection. These findings significantly expand the potential applications of ECL by extending its effective range in time and space.

Ionic Thermoelectric Generators in Vertical and Planar Topologies Based on Fluorinated Polymer Hybrid Materials with Ionic Liquids.

Ionic thermoelectrics (TEs), in which voltage generation is based on ion migration, are suitable for applications based on their low cost, high flexibility, high ionic conductivity, and wide range of Seebeck coefficients. This work reports on the development of ionic TE materials based on the poly(vinylidene fluoride-trifluoroethylene), Poly(VDF-co-TrFE), as host polymer blended with different contents of the ionic liquid, IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The morphology, physico-chemical, thermal, mechanical, and electrical properties of the samples are evaluated together with the TE response. It is demonstrated that the IL acts as a nucleating agent for polymer crystallization. The mechanical properties and ionic conductivity values are dependent on the IL content. A high room temperature ionic conductivity of 0.008 S cm-1 is obtained for the sample with 60 wt% of [EMIM][TFSI] IL. The TE properties depend on both IL content and device topology-vertical or planar-the largest generated voltage range being obtained for the planar topology and the sample with 10 wt% of IL content, characterized by a Seebeck coefficient of 1.2 mV K-1. Based on the obtained maximum power density of 4.9 µW m-2, these materials are suitable for a new generation of TE devices.

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.

Development of Silk Fibroin Scaffolds for Vascular Repair.

Silk fibroin (SF) is a biocompatible natural protein with excellent mechanical characteristics. SF-based biomaterials can be structured using a number of techniques, allowing the tuning of materials for specific biomedical applications. In this study, SF films, porous membranes, and electrospun membranes were produced using solvent-casting, salt-leaching, and electrospinning methodologies, respectively. SF-based materials were subjected to physicochemical and biological characterizations to determine their suitability for tissue regeneration applications. Mechanical analysis showed stress-strain curves of brittle materials in films and porous membranes, while electrospun membranes featured stress-strain curves typical of ductile materials. All samples showed similar chemical composition, melting transition, hydrophobic behavior, and low cytotoxicity levels, regardless of their architecture. Finally, all of the SF-based materials promote the proliferation of human umbilical vein endothelial cells (HUVECs). These findings demonstrate the different relationship between HUVEC behavior and the SF sample's topography, which can be taken advantage of for the design of vascular implants.

Melt Electrowriting of Nylon-12 Microfibers with an Open-Source 3D Printer.

This study demonstrates how either a heated flat or cylindrical collector enables defect-free melt electrowriting (MEW) of complex geometries from high melting temperature polymers. The open-source "MEWron" printer uses nylon-12 filament and combined with a heated flat or cylindrical collector, produces well-defined fibers with diameters ranging from 33 ± 4 to 95 ± 3 µm. Processing parameters for stable jet formation and minimal defects based on COMSOL thermal modeling for hardware design are optimized. The balance of processing temperature and collector temperature is achieved to achieve auxetic patterns, while showing that annealing nylon-12 tubes significantly alters their mechanical properties. The samples exhibit varied pore sizes and wall thicknesses influenced by jet dynamics and fiber bridging. Tensile testing shows nylon-12 tubes are notably stronger than poly(ε-caprolactone) ones and while annealing has limited impact on tensile strength, yield, and elastic modulus, it dramatically reduces elongation. The equipment described and material used broadens MEW applications for high melting point polymers and highlights the importance of cooling dynamics for reproducible samples.

A Novel Screen-Printed Textile Interface for High-Density Electromyography Recording.

Recording electrical muscle activity using a dense matrix of detection points (high-density electromyography, EMG) is of interest in a range of different applications, from human-machine interfacing to rehabilitation and clinical assessment. The wider application of high-density EMG is, however, limited as the clinical interfaces are not convenient for practical use (e.g., require conductive gel/cream). In the present study, we describe a novel dry electrode (TEX) in which the matrix of sensing pads is screen printed on textile and then coated with a soft polymer to ensure good skin-electrode contact. To benchmark the novel solution, an identical electrode was produced using state-of-the-art technology (polyethylene terephthalate with hydrogel, PET) and a process that ensured a high-quality sample. The two electrodes were then compared in terms of signal quality as well as functional application. The tests showed that the signals collected using PET and TEX were characterised by similar spectra, magnitude, spatial distribution and signal-to-noise ratio. The electrodes were used by seven healthy subjects and an amputee participant to recognise seven hand gestures, leading to similar performance during offline analysis and online control. The comprehensive assessment, therefore, demonstrated that the proposed textile interface is an attractive solution for practical applications.

Size Effect in Hybrid TiO2:Au Nanostars for Photocatalytic Water Remediation Applications.

TiO2:Au-based photocatalysis represents a promising alternative to remove contaminants of emerging concern (CECs) from wastewater under sunlight irradiation. However, spherical Au nanoparticles, generally used to sensitize TiO2, still limit the photocatalytic spectral band to the 520 nm region, neglecting a high part of sun radiation. Here, a ligand-free synthesis of TiO2:Au nanostars is reported, substantially expanding the light absorption spectral region. TiO2:Au nanostars with different Au component sizes and branching were generated and tested in the degradation of the antibiotic ciprofloxacin. Interestingly, nanoparticles with the smallest branching showed the highest photocatalytic degradation, 83% and 89% under UV and visible radiation, together with a threshold in photocatalytic activity in the red region. The applicability of these multicomponent nanoparticles was further explored with their incorporation into a porous matrix based on PVDF-HFP to open the way for a reusable energy cost-effective system in the photodegradation of polluted waters containing CECs.

Magnetic Copper Ferrite Nanoparticles Functionalized by Aromatic Polyamide Chains for Hyperthermia Applications.

A new magnetic nanocomposite with a statistical star polymer structure was designed and synthesized. Nanocomposite fabrication is based on the polymerization of aromatic polyamide chains on the surface of functionalized magnetic copper ferrite nanoparticles (CuFe2O4 MNPs). This magnetic nanostructure was characterized by several analysis methods. All the analytical methods used, for instance, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, thermogravimetric, vibrating-sample magnetometer, and scanning electron microscopy (SEM), confirmed the formation of polyamide chains. The obtained images from SEM imaging showed a unique nanoflower morphology which was the proper orientation results of synthesized nanoplates. Finally, the magnetic nanostructure showed a good potential for hyperthermia applications, with a maximum specific absorption rate of 7 W/g for 1 mg/mL of the sample under a magnetic field in different frequencies (100, 200, 300, and 400 MHz) and 5 to 20 min time intervals.

Influence of cellulose nanocrystal surface functionalization on the bending response of cellulose nanocrystal/ionic liquid soft actuators.

This work reports the development of renewable cellulose nanocrystal (CNC) and ionic liquid (IL) hybrid materials for bending actuator applications. For this purpose, cellulose nanocrystals with different surface charges (neutral, positive and negative) were prepared and increasing amounts of the IL 2-hydroxy-ethyl-trimethylammonium dihydrogen phosphate ([Ch][DHP]) (10 and 25 wt%) were incorporated into the CNC hosting matrix. The morphology of the samples was evaluated, proving that both surface charge and IL incorporation do not affect the characteristic layered structure of the CNC. Atomic force microscopy results reveal a sea-island morphology in the hybrid films, where CNC bundles are surrounded by [Ch][DHP]-rich regions. An increase in the electrical conductivity is observed upon IL incorporation into the CNC matrix, regardless of the CNC surface charge. The highest electrical conductivity values are observed for IL/CNC (+) 25 wt% with an electrical conductivity of 3.18 × 10-5± 2.75 × 10-7 S cm-1 and IL/CNC (-) 10 wt% (1.26 × 10-5± 5.92 × 10-6 S cm-1). The highest bending displacement of 2.1 mm for an applied voltage of 4.0 Vpp at a frequency of 100 mHz was obtained for the IL/CNC (+) 25 wt% composite, demonstrating the suitability of cellulose to develop soft actuators.

Chromium Speciation in Zirconium-Based Metal-Organic Frameworks for Environmental Remediation.

Acute CrVI water pollution due to anthropogenic activities is an increasing worldwide concern. The high toxicity and mobility of CrVI makes it necessary to develop dual adsorbent/ion-reductive materials that are able to capture CrVI and transform it efficiently into the less hazardous CrIII . An accurate description of chromium speciation at the adsorbent/ion-reductive matrix is key to assessing whether CrVI is completely reduced to CrIII , or if its incomplete transformation has led to the stabilization of highly reactive, transient CrV species within the material. With this goal in mind, a dual ultraviolet-visible and electron paramagnetic spectroscopy approach has been applied to determine the chromium speciation within zirconium-based metal-organic frameworks (MOFs). Our findings point out that the generation of defects at Zr-MOFs boosts CrVI adsorption, whilst the presence of reductive groups on the organic linkers play a key role in stabilizing it as isolated and/or clustered CrIII ions.

Tuning Properties of Cerium Dioxide Nanoparticles by Surface Modification with Catecholate-type of Ligands.

Cerium dioxide (CeO2) finds applications in areas such as corrosion protection, solar cells, or catalysis, finding increasing applications in biomedicine. This work reports on surface-modified CeO2 particles in order to tune their applicability in the biomedical field. Stable aqueous CeO2 sol, consisting of 3-4 nm in size crystallites, was synthesized using forced hydrolysis. The coordination of catecholate-type of ligands (catechol, caffeic acid, tiron, and dopamine) to the surface-Ce atoms is followed with the appearance of absorption in the visible spectral range as a consequence of interfacial charge-transfer complex formation. The spectroscopic observations are complemented with the density functional theory calculations using a cluster model. The synthesized samples were characterized by X-ray diffraction analysis, transmission electron microscopy, and nitrogen adsorption-desorption isotherms. The ζ-potential measurements indicated that the stability of CeO2 sol is preserved upon surface modification. The pristine CeO2 nanoparticles (NPs) are nontoxic against pre-osteoblast cells in the entire studied concentration range (up to 1.5 mM). Hybrid CeO2 NPs, capped with dopamine or caffeic acid, display toxic behavior for concentrations ≥0.17 and 1.5 mM, respectively. On the other hand, surface-modified CeO2 NPs with catechol and tiron promote the proliferation of pre-osteoblast cells.

Magnetic Bioreactor for Magneto-, Mechano- and Electroactive Tissue Engineering Strategies.

Biomimetic bioreactor systems are increasingly being developed for tissue engineering applications, due to their ability to recreate the native cell/tissue microenvironment. Regarding bone-related diseases and considering the piezoelectric nature of bone, piezoelectric scaffolds electromechanically stimulated by a bioreactor, providing the stimuli to the cells, allows a biomimetic approach and thus, mimicking the required microenvironment for effective growth and differentiation of bone cells. In this work, a bioreactor has been designed and built allowing to magnetically stimulate magnetoelectric scaffolds and therefore provide mechanical and electrical stimuli to the cells through magnetomechanical or magnetoelectrical effects, depending on the piezoelectric nature of the scaffold. While mechanical bioreactors need direct application of the stimuli on the scaffolds, the herein proposed magnetic bioreactors allow for a remote stimulation without direct contact with the material. Thus, the stimuli application (23 mT at a frequency of 0.3 Hz) to cells seeded on the magnetoelectric, leads to an increase in cell viability of almost 30% with respect to cell culture under static conditions. This could be valuable to mimic what occurs in the human body and for application in immobilized patients. Thus, special emphasis has been placed on the control, design and modeling parameters governing the bioreactor as well as its functional mechanism.

Patterned Piezoelectric Scaffolds for Osteogenic Differentiation.

The morphological clues of scaffolds can determine cell behavior and, therefore, the patterning of electroactive polymers can be a suitable strategy for bone tissue engineering. In this way, this work reports on the influence of poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) electroactive micropatterned scaffolds on the proliferation and differentiation of bone cells. For that, micropatterned P(VDF-TrFE) scaffolds were produced by lithography in the form of arrays of lines and hexagons and then tested for cell proliferation and differentiation of pre-osteoblast cell line. Results show that more anisotropic surface microstructures promote bone differentiation without the need of further biochemical stimulation. Thus, the combination of specific patterns with the inherent electroactivity of materials provides a promising platform for bone regeneration.

Water-Soluble Cellulose Derivatives as Suitable Matrices for Multifunctional Materials.

This work reports on a simple and environmentally benign route to prepare freestanding magnetic films based on cellulose derivatives through the combination of cobalt ferrite (CoFe2O4) nanoparticles with methyl cellulose (MC), hydroxypropyl cellulose (HPC), and sodium carboxymethyl cellulose (NaCMC). Nanoparticles are able to "shield" hydrogen bonding interactions between polysaccharide chains and lower the viscosity of water-dissolved MC, HPC, and NaCMC, allowing an easy film fabrication. Crack-free films with homogeneously dispersed nanoparticles having concentrations up to 50 wt % are fabricated by mechanical agitation followed by doctor blade casting. All of the nanocomposite films keep a substantial level of flexibility with elongation at break exceeding 5%. Halpin-Tsai equations serve to provide further insights on the character of matrix-CoFe2O4 interfaces. Magnetization saturation increases almost linearly with cobalt ferrite concentration up to a maximum value of ∼24-27 emu g-1 for nanocomposites containing 50 wt % of nanoparticles. The dielectric response of the films demonstrates a strong dependence on both the functional groups attached to the main cellulose chain and the ferrite nanoparticle content. The renewable character of the hosting matrices, together with the fabrication methods that solely uses water as a solvent, the decrease of the viscosity with the inclusion of fillers, particularly suitable for printable materials, and the resulting magnetic performance provide novel avenues for the replacement of traditional magnetoactive composites based on petroleum-derived polymers and avoiding the use of toxic solvents.

A New Approach for the Fabrication of Cytocompatible PLLA-Magnetite Nanoparticle Composite Scaffolds.

Magnetic biomimetic scaffolds of poly(L-lactide) (PLLA) and nanoparticles of magnetite (nFe3O4) are prepared in a wide ratio of compositions by lyophilization for bone regeneration. The magnetic properties, cytotoxicity, and the in vitro degradation of these porous materials are closely studied. The addition of magnetite at 50 °C was found to produce an interaction reaction between the ester groups of the PLLA and the metallic cations of the magnetite, causing the formation of complexes. This fact was confirmed by the analysis of the infrared spectroscopy and the gel permeation chromatography test results. They, respectively, showed a displacement of the absorption bands of the carbonyl group (C=O) of the PLLA and a scission of the polymer chains. The iron from the magnetite acted as a catalyser of the macromolecular scission reaction, which determines the final biomedical applications of the scaffolds-it does so because the reaction shortens the degradation process without appearing to influence its toxicity. None of the samples studied in the tests presented cytotoxicity, even at 70% magnetite concentrations.

Nano-sculptured Janus-like TiAg thin films obliquely deposited by GLAD co-sputtering for temperature sensing.

Inclined, zigzag and spiral TiAg films were prepared by glancing angle co-deposition, using two distinct Ti and Ag targets with a particle incident angle of 80° and Ag contents ranging from 20 to 75 at%. The effect of increasing Ag incorporation and columnar architecture change on the morphological, structural and electrical properties of the films was investigated. It is shown that inclined columnar features (ß = 47°) with high porosity were obtained for 20 at% Ag, with the column angle sharply decreasing (ß = 21°) for 50 at% Ag, and steeply increasing afterwards until ß = 37° for the film with 75 at% Ag. The sputtered films exhibit a rather well-crystallized structure for Ag contents ≥50 at%, with a TiAg (111) preferential growth. No significant oxidation was detected in all films, except for the one with 20 at% Ag, after two 298-473-298 K temperature cycles in air. The calculated temperature coefficient of resistivity (TCR) values vary between 1.4 and 5.5 × 10-4 K-1. Nano-sculptured spiral films exhibit consistently higher resistivity (ρ = 1.5 × 10-6 Ω m) and TCR values (2.9 × 10-4 K-1) than the inclined one with the same Ag content (ρ = 1.2 × 10-6 Ω m and TCR = 2.0 × 10-4 K-1). No significant changes are observed in the zigzag films concerning these properties. The effective anisotropy A eff at 473 K changes from 1.3 to 1.7 for the inclined films. Spiral films exhibit an almost completely isotropic behavior with A eff = 1.1. Ag-rich TiAg core + shell Janus-like columns were obtained with increasing Ag concentrations.

Tailored Biodegradable and Electroactive Poly(Hydroxybutyrate-Co-Hydroxyvalerate) Based Morphologies for Tissue Engineering Applications.

Polymer-based piezoelectric biomaterials have already proven their relevance for tissue engineering applications. Furthermore, the morphology of the scaffolds plays also an important role in cell proliferation and differentiation. The present work reports on poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), a biocompatible, biodegradable, and piezoelectric biopolymer that has been processed in different morphologies, including films, fibers, microspheres, and 3D scaffolds. The corresponding magnetically active PHBV-based composites were also produced. The effect of the morphology on physico-chemical, thermal, magnetic, and mechanical properties of pristine and composite samples was evaluated, as well as their cytotoxicity. It was observed that the morphology does not strongly affect the properties of the pristine samples but the introduction of cobalt ferrites induces changes in the degree of crystallinity that could affect the applicability of prepared biomaterials. Young's modulus is dependent of the morphology and also increases with the addition of cobalt ferrites. Both pristine and PHBV/cobalt ferrite composite samples are not cytotoxic, indicating their suitability for tissue engineering applications.

Local probing of magnetoelectric properties of PVDF/Fe3O4 electrospun nanofibers by piezoresponse force microscopy.

The coupling of magnetic and electric properties in polymer-based magnetoelectric composites offers new opportunities to develop contactless electrodes, effectively without electrical connections, for less-invasive integration into devices such as energy harvesters, sensors, wearable and implantable electrodes. Understanding the macroscale-to-nanoscale conversion of the properties is important, as nanostructured and nanoscale magnetoelectric structures are increasingly fabricated. However, whilst the magnetoelectric effect at the macroscale is well established both theoretically and experimentally, it remains unclear how this effect translates to the nanoscale, or vice versa. Here, PVDF/Fe3O4 polymer-based composite nanofibers are fabricated using electrospinning to investigate their piezoelectric and magnetoelectric properties at the single nanofiber level.

Metallic Glass/PVDF Magnetoelectric Laminates for Resonant Sensors and Actuators: A Review.

Among magnetoelectric (ME) heterostructures, ME laminates of the type Metglas-like/PVDF (magnetostrictive+piezoelectric constituents) have shown the highest induced ME voltages, usually detected at the magnetoelastic resonance of the magnetostrictive constituent. This ME coupling happens because of the high cross-correlation coupling between magnetostrictive and piezoelectric material, and is usually associated with a promising application scenario for sensors or actuators. In this work we detail the basis of the operation of such devices, as well as some arising questions (as size effects) concerning their best performance. Also, some examples of their use as very sensitive magnetic fields sensors or innovative energy harvesting devices will be reviewed. At the end, the challenges, future perspectives and technical difficulties that will determine the success of ME composites for sensor applications are discussed.