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.

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.

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.

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.

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.

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.

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.

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.

Immunomodulatory and regenerative effects of the full and fractioned adipose tissue derived stem cells secretome in spinal cord injury.

Adipose tissue derived stem cells (ASCs) are recognized to secret a myriad of molecules (secretome) know to modulate inflammatory response, promote axonal growth as well vascular remodeling and cellular survival. In previous works we have reported the benefit effects of ASCs transplanted to the injury site in a rat model of spinal cord injury (SCI). Emerging evidence have shown that the therapeutic actions of these cells are a consequence of their intense paracrine activity mediated by their secretome, which includes soluble bioactive molecules and vesicles. In this study, we intended to dissect the vesicular and protein individual function, comparing with whole secretome therapeutic effect. Therefore, we identified a beneficial effect of the whole secretome on neurite growth compared with protein or vesicular fraction alone and characterized their impact on microglia in vitro. Moreover, in a compression SCI mice model, from the motor tests performed, a statistical difference was found on beam balance test revealing differences in motor recovery between the use of the whole the secretome or their protein fraction. Finally, two different delivery methods, local or peripheral (IV), of ASC secretome were tested in vivo. Results indicate that when injected intravenously the secretome of ASCs has a beneficial effect on motor recovery of spinal cord injury animals compared with a single local injection and respective controls. Overall, our results showed that the whole secretome performed better than the fractions individually, raising ASC secretome mode of action as a synergy of proteic and vesicular fraction on SCI context. Also, when intravenously delivered, ASC secretome can promote SCI animal's motor recovery highlighting their therapeutic potential.

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.

Silk fibroin and sericin polymer blends for sustainable battery separators.

Natural polymers are a promising alternative for reducing the environmental impact of batteries. For this reason, it is still necessary to study their behavior and implement its use in these devices, especially in separator membranes. This work reports on new separator membranes based on silk fibroin (SF) and silk sericin (SS) prepared by salt leaching method. The effect of the different SS relative content on the physiochemical properties of the membranes and on the electrochemical performance of the corresponding batteries with lithium iron phosphate (LFP) as cathodes has been reported. It is observed that the increasing of SS content leads to a decrease of the overall crystallinity of the membranes. All SF/SS membranes presented a well-defined porosity above 75% with a uniform distribution of interconnected micropores. The electrolyte uptake and the ionic conductivity are dependent on the relative SS content. The addition of 10 wt% of SS into SF membranes, induce a high ionic conductivity of 4.09 mS.cm-1 and high lithium transference number (0.52), due to the improvement of the Li+ ions conduction paths within the blended structure. Charge/discharge tests performed in Lithium/C-LFP half-cells reveal a discharge capacity of 85 mAh.g-1 at 2C after 100 cycles for batteries with a SF/SS separator, containing a 10 wt% of SS, which suggests a stabilizing effect of Sericin on discharge capacity. Further, a 50% and 35% of capacity of retention and capacity fade, respectively, is observed. The presented SF/SS membrane show high electrochemical stability, being suitable for implementation in a next generation of sustainable battery systems. This could allow the SS valorization considering that 150,000 tons of SS are abandoned each year, reducing the contamination of environmental effluents.

Magnetic materials: a journey from finding north to an exciting printed future.

The potential implications/applications of printing technologies are being recognized worldwide across different disciplines and industries. Printed magnetoactive smart materials, whose physical properties can be changed by the application of external magnetic fields, are an exclusive class of smart materials that are highly valuable due to their magnetically activated smart and/or multifunctional response. Such smart behavior allows, among others, high speed and low-cost wireless activation, fast response, and high controllability with no relevant limitations in design, shape, or dimensions. Nevertheless, the printing of magnetoactive materials is still in its infancy, and the design apparatus, the material set, and the fabrication procedures are far from their optimum features. Thus, this review presents the main concepts that allow interconnecting printing technologies with magnetoactive materials by discussing the advantages and disadvantages of this joint field, trying to highlight the scientific obstacles that still limit a wider application of these materials nowadays. Additionally, it discusses how these limitations could be overcome, together with an outlook of the remaining challenges in the emerging digitalization, Internet of Things, and Industry 4.0 paradigms. Finally, as magnetoactive materials will play a leading role in energy generation and management, the magnetic-based Green Deal is also addressed.

Patterned separator membranes with pillar surface microstructures for improved battery performance.

In order to improve battery performance by tuning battery separator membranes, this work reports on porous poly(vinylidene fluoride-co-trifluoroethylene) - P(VDF-TrFE)- membranes with surface pillar microstructures. Separators with tailored pillar diameter, height and bulk thickness were fabricated by template patterning and computer simulations, allowing to evaluate the effect of the pillar microstructure characteristics on battery performance. It is shown that the different pillar microstructures of the separators affect the uptake value (150-325%), ionic conductivity value (0.8-1.6 mS·cm-1) and discharge capacity of the lithium ion batteries (LIB) when compared with the separator without pillars. The experimental charge-discharge behavior demonstrates that the pillar parameters affect battery performance and the best microstructure leading to 80 mAh·g-1 at 2C. Battery performance can be thus optimized by adjusting pillar diameter, height and bulk thickness of the separators keeping its volume constant, as demonstrated also by the simulation results. The parameter with most influence in battery performance is the bulk thickness of the separator, allowing to obtain a maximum discharge capacity value of 117.8 mAh·g-1 at 90C for a thickness of 0.01 mm. Thus, this work shows that the optimization of the pillar microstructure of the separator membranes allows increasing the capacity towards a new generation of high-performance LIBs.

Processing Strategies to Obtain Highly Porous Silk Fibroin Structures with Tailored Microstructure and Molecular Characteristics and Their Applicability in Water Remediation.

The present work reports on the control of silk fibroin (SF) porous structures performance through various processing methods. The study includes the analysis of two dissolving techniques (CaCl2/H2O/EtOH ternary and LiBr/H2O binary solutions), three regeneration methods (gelation, lyophilization and gas foaming) and one post-processing (EtOH). In all the cases, followed steps lead to SF structures with porosity values above 94% and large surface areas. Also, results about samples microstructure, secondary organization, crystallinity and water behavior, reveal a direct correlation between processing and SF properties. Thanks to the achieved progress, the SF varying porous structures were evaluated for metalloids (As5+ and As3+) and heavy metals (Cr6+ and Cr3+) adsorption, observing a direct relationship between samples processing and ionic species adsorption ability. Thus, it is shown that the control of the properties of SF based porous structures through processing, represents a suitable and ecofriendly approach for the development of bio-based materials for environmental applications.

Enhanced ionic conductivity in poly(vinylidene fluoride) electrospun separator membranes blended with different ionic liquids for lithium ion batteries.

Electrospun poly(vinylidene fluoride) (PVDF) fiber membranes doped with different ionic liquids (ILs) and sharing the same anion were produced and their potential as separator membranes for battery applications was evaluated. Different types of ILs containing the same anion, bis(trifluoromethylsulfonyl)imide [TFSI]-, were used with IL concentrations ranging between 0 and 15 wt% The morphology, microstructure, thermal and electrical properties (ionic conductivity and electrochemical window) of the membranes were evaluated. The presence of ILs in the PVDF polymer matrix influences the fiber diameter and the content of the polar ß phase within the polymer, as well as the degree of crystallinity. The thermal stability of the membranes decreases with the incorporation of IL. Impedance spectroscopy tests show a maximum ionic conductivity of 2.8 mS.cm-1 for 15% of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][TFSI]) at room temperature. The electrochemical stability of the samples ranges from 0.0 to 6.0 V. When evaluated as battery separator membranes in C-LiFePO4 half-cells, a maximum discharge capacity of 119 mAh.g-1 at C-rate was obtained for the PVDF membrane with 15% [Emim][TFSI], with a coulombic efficiency close to 100%. The results demonstrate that the produced electrospun membranes are suitable for applications as separators for lithium ion batteries (LIBs).

Crystal morphology control of synthetic giniite for enhanced photo-Fenton activity against the emerging pollutant metronidazole.

Metronidazole (MNZ) is a recalcitrant antibiotic with toxic and carcinogenic effects in aquatic environments. In this work, Fe5(PO4)4(OH)3·2H2O (giniite) particles were synthesised with three different alkaline cations (Li+, Na+ and K+) and used as Fenton catalysts for MNZ removal. It is shown that the addition of different cations during the hydrothermal synthesis process promote different morphologies from asterisk-like to flower-like and branches-like, maintaining the crystalline structure of pure giniite. The photo-Fenton activity of these particles was then evaluated through the degradation of MNZ under sunlight radiation for 9 h. The results indicate that the alkaline cation has a predominant role in the photo-Fenton efficiency, as demonstrated by the superior degradation efficiencies of Na@giniite particles (91.2% and 72.5% with giniite concentration of 0.2 g L-1 and 0.07 g L-1, respectively), related with its high surface area (10.7 m2 g-1). Thus, it is demonstrated the suitability of Na@giniite particles as Fenton catalyst for MNZ removal from water.