Polymer-based actuators: back to the future.

Polymer-based actuators play a key role in the area of smart materials and devices, and for this reason different polymer-based actuators have appeared in recent years and are implemented in a broad range of fields, including biomedical, optical or electronics, among others. Although it is possible to find more types, they are mainly classified into two main groups according to their different working principles: electromechanical - with electrical to mechanical energy conversion - and magnetomechanical - with magnetic to mechanical energy conversion. The present work provides a comprehensive and critical review of the recent studies in this field. The operating principles, some representative designs, performance analyses and practical applications will be presented. The future development perspectives of this interesting field will be also discussed. Thus, the present work provides a comprehensive understanding of the effects reported in the past, introduces solutions to the present limitations and, back to the future, serves as a useful guidance for the design of new polymer-based actuators aiming to improve their output performances.

Human Mesenchymal Stem Cells Growth and Osteogenic Differentiation on Piezoelectric Poly(vinylidene fluoride) Microsphere Substrates.

The aim of this work was to determine the influence of the biomaterial environment on human mesenchymal stem cell (hMSC) fate when cultured in supports with varying topography. Poly(vinylidene fluoride) (PVDF) culture supports were prepared with structures ranging between 2D and 3D, based on PVDF films on which PVDF microspheres were deposited with varying surface density. Maintenance of multipotentiality when cultured in expansion medium was studied by flow cytometry monitoring the expression of characteristic hMSCs markers, and revealed that cells were losing their characteristic surface markers on these supports. Cell morphology was assessed by scanning electron microscopy (SEM). Alkaline phosphatase activity was also assessed after seven days of culture on expansion medium. On the other hand, osteoblastic differentiation was monitored while culturing in osteogenic medium after cells reached confluence. Osteocalcin immunocytochemistry and alizarin red assays were performed. We show that flow cytometry is a suitable technique for the study of the differentiation of hMSC seeded onto biomaterials, giving a quantitative reliable analysis of hMSC-associated markers. We also show that electrosprayed piezoelectric poly(vinylidene fluoride) is a suitable support for tissue engineering purposes, as hMSCs can proliferate, be viable and undergo osteogenic differentiation when chemically stimulated.

Inkjet printed IGZO memristors with volatile and non-volatile switching.

Solution-based memristors deposited by inkjet printing technique have a strong technological potential based on their scalability, low cost, environmentally friendlier processing by being an efficient technique with minimal material waste. Indium-gallium-zinc oxide (IGZO), an oxide semiconductor material, shows promising resistive switching properties. In this work, a printed Ag/IGZO/ITO memristor has been fabricated. The IGZO thickness influences both memory window and switching voltage of the devices. The devices show both volatile counter8wise (c8w) and non-volatile 8wise (8w) switching at low operating voltage. The 8w switching has a SET and RESET voltage lower than 2 V and - 5 V, respectively, a retention up to 105 s and a memory window up to 100, whereas the c8w switching shows volatile characteristics with a low threshold voltage (Vth < - 0.65 V) and a characteristic time (τ) of 0.75 ± 0.12 ms when a single pulse of - 0.65 V with width of 0.1 ms is applied. The characteristic time alters depending on the number of pulses. These volatile characteristics allowed them to be tested on different 4-bit pulse sequences, as an initial proof of concept for temporal signal processing applications.

Electroactive poly(vinylidene fluoride-trifluoroethylene)/graphene composites for cardiac tissue engineering applications.

Electroactive materials are increasingly being used in strategies to regenerate cardiac tissue. These materials, particularly those with electrical conductivity, are used to actively recreate the electromechanical nature of the cardiac tissue. In the present work, we describe a novel combination of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), a highly electroactive polymer, with graphene (G), exhibiting high electrical conductivity. G/P(VDF-TrFE) films have been characterized in terms of topographical, physico-chemical, mechanical, electrical, and thermal properties, and studied the response of cardiomyocytes adhering to them. The results indicate that the crystallinity and the wettability of the composites remain almost unaffected after G incorporation. In turn, surface roughness, Young modulus, and electric properties are higher in G/P(VDF-TrFE). Finally, the composites are highly biocompatible and able to support cardiomyocyte adhesion and proliferation, particularly surface treated ones, demonstrating the suitability of these materials for cardiac tissue engineering applications.

Ternary composites of poly(vinylidene fluoride-co-hexafluoropropylene) with silver nanowires and titanium dioxide nanoparticles as separator membranes for lithium-ion batteries.

In the realm of polymer composites, there is growing interest in the use of more than one filler for achieving multifunctional properties. In this work, a composite separator membrane has been developed for lithium-ion battery application, by incorporating conductive silver nanowires (AgNWs) and titanium dioxide (TiO2) nanoparticles into a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer matrix. The composite membranes were manufactured by solvent casting and thermally induced phase separation, with total filler content varying up to 10 wt%. The ternary composites composites present improved mechanical characteristics, ionic conductivity and lithium transfer number compared to the neat polymer matrix. On the other hand, the filler type and content within the composite has little bearing on the morphology, polymer phase, or thermal stability. Once applied as a separator in lithium-ion batteries, the highest discharge capacity value was obtained for the 5 wt% AgNWs/5 wt% TiO2/PVDF-HFP membrane at different C-rates, benefiting from the synergetic effect from both fillers. This work demonstrates that higher battery performance can be achieved for next-generation lithium-ion batteries by using separator membranes based on ternary composites.

Osteogenic differentiation of human mesenchymal stem cells on electroactive substrates.

This study investigates the effect of electroactivity and electrical charge distribution on the biological response of human bone marrow stem cells (hBMSCs) cultured in monolayer on flat poly(vinylidene fluoride), PVDF, substrates. Differences in cell behaviour, including proliferation, expression of multipotency markers CD90, CD105 and CD73, and expression of genes characteristic of different mesenchymal lineages, were observed both during expansion in basal medium before reaching confluence and in confluent cultures in osteogenic induction medium. The crystallisation of PVDF in the electrically neutral α-phase or in the electroactive phase ß, both unpoled and poled, has been found to have an important influence on the biological response. In addition, the presence of a permanent positive or negative surface electrical charge distribution in phase ß substrates has also shown a significant effect on cell behaviour.

Osteoblast, fibroblast and in vivo biological response to poly(vinylidene fluoride) based composite materials.

Electroactive materials can be taken to advantage for the development of sensors and actuators as well as for novel tissue engineering strategies. Composites based on poly(vinylidene fluoride), PVDF, have been evaluated with respect to their biological response. Cell viability and proliferation were performed in vitro both with Mesenchymal Stem Cells differentiated to osteoblasts and Human Fibroblast Foreskin 1. In vivo tests were also performed using 6-week-old C57Bl/6 mice. It was concluded that zeolite and clay composites are biocompatible materials promoting cell response and not showing in vivo pro-inflammatory effects which renders both of them attractive for biological applications and tissue engineering, opening interesting perspectives to development of scaffolds from these composites. Ferrite and silver nanoparticle composites decrease osteoblast cell viability and carbon nanotubes decrease fibroblast viability. Further, carbon nanotube composites result in a significant increase in local vascularization accompanied an increase of inflammatory markers after implantation.

Improving the Performance of Paper-Based Dipole Antennas by Electromagnetic Flux Concentration.

One of the essential issues in modern advanced materials science is to design and manufacture flexible devices, in particular in the framework of the Internet of Things (IoT), to improve integration into applications. An antenna is an essential component of wireless communication modules and, in addition to flexibility, compact dimensions, printability, low cost, and environmentally friendlier production strategies, also represent relevant functional challenges. Concerning the antenna's performance, the optimization of the reflection coefficient and maximum range remain the key goals. In this context, this work reports on screen-printed paper@Ag-based antennas and optimizes their functional properties, with improvements in the reflection coefficient (S11) from -8 to -56 dB and maximum transmission range from 208 to 256 m, with the introduction of a PVA-Fe3O4@Ag magnetoactive layer into the antenna's structure. The incorporated magnetic nanostructures allow the optimization of the functional features of antennas with possible applications ranging from broadband arrays to portable wireless devices. In parallel, the use of printing technologies and sustainable materials represents a step toward more sustainable electronics.

Relaxation dynamics of poly(vinylidene fluoride) studied by dynamical mechanical measurements and dielectric spectroscopy.

The aim of this study is to analyze the mobility of polymer chains in semicrystalline poly(vinylidene fluoride) (PVDF). PVDF crystallizes from the melt in the α crystalline phase. The transformation from the α phase to the electroactive ß phase can be induced by stretching at temperatures in the range between 80 and 140 °C. The spherulitic structure of the crystalline phase is deformed during stretching to form fibrils oriented in the direction of the strain. The amorphous phase confined among the crystalline lamellae is distorted as well and some degree of orientation of the polymer chains is expected. Dynamic-mechanical and dielectric spectroscopy measurements were performed in PVDF films stretched to strain ratios up to 5 at temperatures between 80 and 140 °C. Dynamic-mechanical measurements were conducted between -60 °C and melting and in this temperature range the relaxation spectra show the main relaxation of the amorphous phase (called ß-relaxation) and at higher temperatures a relaxation related to crystallites motions (α (c)-relaxation). Although the mean relaxation times of the ß-relaxation are nearly equal in PVDF before and after crystal phase transformation, a significant change of shape of the relaxation spectrum proves the effect of chain distortion due to crystal reorganization. In stretched PVDF the elastic modulus of the polymer in the direction of deformation is significantly higher than in the transversal one, as expected by chain and crystals fibril orientation. The recovery of the deformation when the sample is heated is related with the appearance of the α (c)-relaxation. Dielectric spectroscopy spectrum shows the main relaxation of the amorphous phase and a secondary process (γ-relaxation) at lower temperatures. Stretching produces significant changes in the relaxation processes, mainly in the strength and shape of the main relaxation ß. The Havriliak-Negami function has been applied to analyze the dielectric response.

Nanoparticle dispersion and electroactive phase content in polyvinylidene fluoride/Ni0.5Zn0.5Fe2O4 nanocomposites for magnetoelectric applications.

Ni0.5Zn0.5FeO4 ferrite/polyvinylidene fluoride composite films were prepared by a solution method and melt processing. As nanoparticle dispersion and polymer electroactive phase content are some of the key factors for improving magnetoelectric coupling in the composites, the dispersion of ferrite nanoparticles in the polymeric matrix was studied by preparing samples by two alternative dispersion routes: ultrasound and citric acid nanoparticle surfactation. The nucleation of the electroactive beta-phase of the polymer was observed in composites produced by nanoparticle dispersion by ultrasound. This fact avoids the need of stretching composites at elevated temperature in order to obtain the electroactive phase and obtain magnetoelectric composites. By this method, nevertheless, large nanoparticle agglomerates are obtained. Nanoparticle dispersion is largely improved by citric acid surfactation of the nanoparticles. On the other hand, the beta-phase of the polymer is not nucleated due to the modification of the nanoparticle-polymer interaction due to the presence of the surfactant.

Reversible aggregation and chemical resistance of magnetic nanoclusters for their recycling and repetitive use in industrial bioprocesses.

Magnetic nanoclusters are widely used as carriers for biomedical and bioindustrial applications. The chemical resistance of the nanoclusters is a key factor for the recycling the magnetic beads for a repetitive use in the industrial bioprocesses. In this work, a study of the chemical resistance of Fe2O3 silica-coated nanoclusters at different pH is presented. The use of Horizontal Low Gradient Magnetic Field (HLGMF) for the control and separation of the magnetic nanoclusters at diferent magnetic field gradients is also investigated. For these purposes Fe2O3 silica-coated nanoclusters are synthesised and characreized by SQUID, TEM, Zeta potential techniques. The magnetophoresis study was performed at 15 T/m and 30 T/m magnetic field gradients. Recycling aspects of the nanoclusters were estimated by evaluating their resistance to pH variation from acid to basic solutions of about pH 2.5 and 10.

Fabrication of poly(lactic acid)-poly(ethylene oxide) electrospun membranes with controlled micro to nanofiber sizes.

Biodegradable poly(L-lactide acid) (PLLA) nanofiber membranes were prepared by electrospinning of PLLA and poly(ethylene oxide) (PEO). The selective removal of PEO by water allows to obtain smaller fiber diameters and to increase the porosity of the membranes in comparison to PLLA membranes obtained under the same electrospinning conditions. After removal of PEO membranes with fiber sizes of 260 nm and average porosity close to 80% are obtained. Thermal and infrared results confirm the poor miscibility of PLLA and PEO, with the PEO randomly distributed along the PLLA fibers. On the other, PLLA and PEO mixing strongly affect their respective degradation temperatures. The influence of the PEO in the electrospinning process is discussed and the results are correlated to the evolution of the PLLA fiber diameter.

Effect of zeolite content in the electrical, mechanical and thermal degradation response of poly(vinylidene fluoride)/NaY zeolite composites.

Polymer based composites of a-PVDF doped with different NaY zeolite (Na53Al53Si139O384) content were investigated. A good dispersion of NaY zeolite within the polymer matrix is achieved. The introduction of NaY nanoparticles enhance the storage modulus and the dielectric constant at room temperature. The dielectric constant at room temperature increases up to the value of 500 for the 32 wt% composite, at 1 kHz. The increase of the dielectric constant is mainly attributed to interfacial polarization effects. For increasing zeolite content, the nanocomposite conductivity shows two conducting regimes separted by the so called breaking voltage, which is associated to an intrazeolite charge transport. Thermogravimetric results show that the introduction of zeolites affects the thermal degradation of the polymer for low zeolite contents and also indicate the presence of water that also plays an important role in the electrical response of the materials.

Electrical stimulation: Effective cue to direct osteogenic differentiation of mesenchymal stem cells?

Mesenchymal stem cells (MSCs) play a major role in bone tissue engineering (BTE) thanks to their capacity for osteogenic differentiation and being easily available. In vivo, MSCs are exposed to an electroactive microenvironment in the bone niche, which has piezoelectric properties. The correlation between the electrically active milieu and bone's ability to adapt to mechanical stress and self-regenerate has led to using electrical stimulation (ES) as physical cue to direct MSCs differentiation towards the osteogenic lineage in BTE. This review summarizes the different techniques to electrically stimulate MSCs to induce their osteoblastogenesis in vitro, including general electrical stimulation and substrate mediated stimulation by means of conductive or piezoelectric cell culture supports. Several aspects are covered, including stimulation parameters, treatment times and cell culture media to summarize the best conditions for inducing MSCs osteogenic commitment by electrical stimulation, from a critical point of view. Electrical stimulation activates different signaling pathways, including bone morphogenetic protein (BMP) Smad-dependent or independent, regulated by mitogen activated protein kinases (MAPK), extracellular signal-regulated kinases (ERK) and p38. The roles of voltage gate calcium channels (VGCC) and integrins are also highlighted according to their application technique and parameters, mainly converging in the expression of RUNX2, the master regulator of the osteogenic differentiation pathway. Despite the evident lack of homogeneity in the approaches used, the ever-increasing scientific evidence confirms ES potential as an osteoinductive cue, mimicking aspects of the in vivo microenvironment and moving one step forward to the translation of this approach into clinic.

Electroactive functional microenvironments from bioactive polymers: A new strategy to address cancer.

The present work reports on a new approach based on electroactive microenvironments to mitigate skeletal muscle cancer. For that, piezoelectric films based on poly(vinylidene fluoride) have been applied to evaluate the influence of mechano- and/or electrical stimuli on rhabdomyosarcoma (RMS) proliferation. Human embryonal rhabdomyosarcoma (RD) cells were cultured on PVDF pristine films with different surface charge (non-poled, poled+ and poled-) and magnetic composites (10% and 20% Fe3O4, and 20% CFO filler content) to allow magneto-mechanical and magnetoelectrical stimulation films. Electrospun PVDF pristine (oriented and randomly) and magnetic (10% Fe3O4) fiber mats were also evaluated to take into consideration the morphology effect on cell response. It was found that the mechanical stimuli enhance RMS proliferation whereas the mechano-electrical decreases it. It was also verified that the RD cells proliferate better on randomly oriented fibers, whereas myoblast cells do it better in oriented ones. The obtained results confirm that electroactive microenvironments can be used to develop novel and effective approaches to deal with RMS cancer, that can be extrapolated to others cancer types.

Ionic liquid-based electroactive materials: a novel approach for cardiac tissue engineering strategies.

Cardiac tissue regeneration strategies are increasingly taking advantage of electroactive scaffolds to actively recreate the tissue microenvironment. In this context, this work reports on advanced materials based on two different ionic liquids (ILs), 2-hydroxyethyl-trimethylammonium dihydrogen phosphate ([Ch][DHP]) and choline bis(trifluoromethylsulfonyl)imide ([Ch][TFSI]), combined with poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) for the development of ionic electroactive IL/polymer hybrid materials for cardiac tissue engineering (TE). The morphological, physico-chemical, thermal and electrical properties of the hybrid materials, as well as their potential use as scaffolds for cardiac TE applications, were evaluated. Besides inducing changes in surface topography, roughness and wettability of the composites, the incorporation of [Ch][DHP] and [Ch][TFSI] leads to the increase in surface (σsurface) and volume (σvolume) electrical conductivities. Furthermore, washing the hybrid samples with phosphate-buffered saline solution strongly decreases the σsurface, whereas σsurface and σvolume of the composites remain almost unaltered after exposure to ultraviolet sterilization treatment. Additionally, it is verified that the incorporation of IL influences the P(VDF-TrFE) microstructure and crystallization process, acting as a defect during its crystallization. Cytotoxicity assays revealed that hybrid films based on [Ch][DHP] alone are not cytotoxic. These films also support H9c2 myoblast cell adhesion and proliferation, demonstrating their suitability for cardiac TE strategies based on electroactive microenvironments.

Surface charge and dynamic mechanoelectrical stimuli improves adhesion, proliferation and differentiation of neuron-like cells.

Neuronal diseases and trauma are among the current major health-care problems. Patients frequently develop an irreversible state of neuronal disfunction that lacks treatment, strongly reducing life quality and expectancy. Novel strategies are thus necessary and tissue engineering research is struggling to provide alternatives to current treatments, making use of biomaterials capable to provide cell supports and active stimuli to develop permissive environments for neural regeneration. As neuronal cells are naturally found in electrical microenvironments, the electrically active materials can pave the way for new and effective neuroregenerative therapies. In this work the influence of piezoelectric poly(vinylidene fluoride) with different surface charges and dynamic mechanoelectrical stimuli on neuron-like cells adhesion, proliferation and differentiation was addressed. It is successfully demonstrated that both surface charge and electrically active dynamic microenvironments can be suitable to improve neuron-like cells adhesion, proliferation, and differentiation. These findings provide new knowledge to develop effective approaches for preclinical applications.

Greener Solvent-Based Processing of Magnetoelectric Nanocomposites.

Polymer-based magnetoelectric (ME) nanocomposites are an enabling material technology for a wide range of applications in the area of digitalization strategies. Due to its highest piezoelectric response among polymers, poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) is the piezoelectric matrix most used in polymer-based ME materials with over 80% of the total reports, with the resulting composites typically processed from solutions with N,N-dimethylformamide (DMF), a toxic solvent. Nevertheless, environmentally friendlier approaches and sustainable technologies are increasingly being required. This work demonstrates that P(VDF-TrFE)/Co2Fe2O4 nanocomposites can be successfully prepared from solution using three different environmentally friendlier solvents: dimethyl sulfoxide (DMSO), N,N'-dimethylpropyleneurea (DMPU), and triethyl phosphate (TEP) with different dipole moments. It is shown that the prepared composite films, with a maximum ME voltage coefficient of 35 mV cm-1 Oe-1 and a maximum sensitivity of 2.2 mV T-1, are suitable for applications, highlighting the path for a new generation of more sustainable ME sensors.

Multifunctional hybrid membranes for photocatalytic and adsorptive removal of water contaminants of emerging concern.

This work focuses on the combination of multifunctional photocatalytic and adsorbent materials in a unique polymeric membrane. For this purpose, Au/TiO2 and Y2(CO3)3 nanoparticles were immobilised onto a poly (vinylidene fluoride-hexafluoropropylene), (PVDF-HFP) membrane, and the physical-chemical characterisation of these materials was performed, as well as pollutant removal efficiency. An efficient TiO2 functionalisation with gold nanoparticles was achieved, endowing these particles with the capability to absorb visible radiation absorption. A favourable porous structure was obtained for the membranes, with an average pore size of 4 µm, and the nanoparticles immobilisation did not alter the chemical properties of the polymeric membrane. The produced hybrid materials, including both the Au/TiO2 and Y2(CO3)3 nanoparticles, presented an efficiency of 57% in the degradation of norfloxacin (5 mg/L) under ultraviolet radiation for 120 min, 80% under visible radiation for 300 min, and 58% in arsenic adsorption for 240 min. These membranes represent a new multifunctional platform for removing several pollutants, which may allow their incorporation in more efficient and less energy-consuming water treatment processes favouring its application, even in low energy resources countries.

Reusable composite membranes for highly efficient chromium removal from real water matrixes.

Natural or industrial hexavalent chromium water pollution continues to be a worldwide unresolved threat. Today, there is intense research on new active and cost-effective sorbents for Cr(VI), but most still exhibit a critical limitation: their powdered nature makes their recovery from water cost and energy consuming. In this work, Al(OH)3, MIL-88-B(Fe), and UiO-66-NH2 Cr(VI) sorbents were immobilized into a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymeric substrate to develop an easily reactivable and reusable water filtering technology. The immobilization of the sorbents into the PVDF-HFP porous matrix modified the macro and meso-porous structure of the polymeric matrix, tuning in parallel its wettability. Although a partial blocking of the Cr(VI) adsorptive capacity was observed for of Al(OH)3 and MIL-88-B(Fe) when immobilized into composite membranes, PVDF-HFP/UiO-66-NH2 filter (i) exceeded the full capacity of the non-immobilized sorbent to trap Cr(VI), (ii) could be reactivated and reusable, and (iii) it was fully functional when applied in real water effluents.