Strategies for Improving Sustainability in the Development of High-Performance Styrenic Block Copolymers by Developing Blends with Cellulose Derivatives.

Next-generation high-performance polymers require consideration as sustainable solutions. Here, to satisfy these criteria, we propose to combine high-performance styrenic block copolymers, a class of thermoplastic elastomer, with cellulose derivatives as a reinforcing agent with the aim of maintaining and/or improving structural and surface properties. A great advantage of the proposed blends is, besides their biocompatibility, a decrease in environmental impact due to blending with a natural polymer. Particularly, we focus on identifying the effect of different blending compounds and blend ratios on the morphological, structural, thermal, mechanical, electrical and cytotoxic characteristics of materials. This research provides, together with novel material formulations, practical guidelines for the design and fabrication of next-generation sustainable high-performance polymers.

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.

Environmentally Friendlier Printable Conductive and Piezoresistive Sensing Materials Compatible with Conformable Electronics.

Flexible and conformable conductive composites have been developed using different polymers, including water-based polyvinylpyrrolidone (PVP), chemical-resistant polyvinylidene fluoride (PVDF), and elastomeric styrene-ethylene-butylene-styrene (SEBS) reinforced with nitrogen-doped reduced graphene oxide with suitable viscosity in composites for printable solutions with functional properties. Manufactured by screen-printing using low-toxicity solvents, leading to more environmentally friendly conductive materials, the materials present an enormous step toward functional devices. The materials were enhanced in terms of filler/binder ratio, achieving screen-printed films with a sheet resistance lower than Rsq < 100 Ω/sq. The materials are biocompatible and support bending deformations up to 10 mm with piezoresistive performance for the different polymers up to 100 bending cycles. The piezoresistive performance of the SEBS binder is greater than double that the other composites, with a gauge factor near 4. Thermoforming was applied to all materials, with the PVP-based ones showing the lowest electrical resistance after the bending process. These conductive materials open a path for developing sustainable and functional devices for printable and conformable electronics.

Magnetic Polymer Actuators with Self-Sensing Resistive Bending Response Based on Ternary Polymer Composites.

A multifunctional polymer-based composite has been designed based on poly(vinylidene fluoride) (PVDF) as polymer matrix and cobalt ferrite (CoFe2O4, CFO) and multiwalled carbon nanotubes (MWCNTs) as fillers, allowing to combine magnetic and electrical responses. The composites were prepared by solvent casting with a fixed 20 wt % concentration of CFO and varying the MWCNTs content between 0 and 3 wt %, allowing to tailor the electrical behavior. The morphology, polymer phase, and thermal and magnetic properties are nearly independent of the MWCNT filler content within the polymer matrix. On the other hand, the mechanical and electrical properties strongly depend on the MWCNT content and a maximum d.c. electrical conductivity value of 4 × 10-4 S·cm-1 has been obtained for the 20 wt %CFO-3 wt %MWCNT/PVDF sample, which is accompanied by an 11.1 emu·g-1 magnetization. The suitability of this composite for magnetic actuators with self-sensing strain characteristics is demonstrated with excellent response and reproducibility.

Acrylonitrile Butadiene Styrene-Based Composites with Permalloy with Tailored Magnetic Response.

This work reports on tailoring the magnetic properties of acrylonitrile butadiene styrene (ABS)-based composites for their application in magnetoactive systems, such as magnetic sensors and actuators. The magnetic properties of the composites are provided by the inclusion of varying permalloy (Py-Ni75Fe20Mo5) nanoparticle content within the ABS matrix. Composites with Py nanoparticle content up to 80 wt% were prepared and their morphological, mechanical, thermal, dielectric and magnetic properties were evaluated. It was found that ABS shows the capability to include high loads of the filler without negatively influencing its thermal and mechanical properties. In fact, the thermal properties of the ABS matrix are basically unaltered with the inclusion of the Py nanoparticles, with the glass transition temperatures of pristine ABS and its composites remaining around 105 °C. The mechanical properties of the composites depend on filler content, with the Young's modulus ranging from 1.16 GPa for the pristine ABS up to 1.98 GPa for the sample with 60 wt% filler content. Regarding the magnetic properties, the saturation magnetization of the composites increased linearly with increasing Py content up to a value of 50.9 emu/g for the samples with 80 wt% of Py content. A numerical model has been developed to support the findings about the magnetic behavior of the NP within the ABS. Overall, the slight improvement in the mechanical properties and the magnetic properties provides the ABS composites new possibilities for applications in magnetoactive systems, including magnetic sensors, actuators and magnetic field shielding.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Blends with Poly(caprolactone) and Poly(lactic acid): A Comparative Study.

Poly(hydroxybutyrate-co-hidroxyvalerate) (PHBV) is a biodegradable polymer, which is a potential substitute for plastics made from fossil resources. Due to its practical interest in the field of tissue engineering, packaging, sensors, and electronic devices, the demand for PHBV with specific thermal, electrical, as well as mechanical requirements is growing. In order to improve these properties, we have developed PHBV blends with two thermoplastic biodegradable polyesters, including poly(caprolactone) (PCL) and poly(lactic acid) (PLA). We analysed the effect of these biopolymers on the morphological, wetting, structural, thermal, mechanical, and electrical characteristics of the materials. Further, the biodegradation of the samples in simulated body fluid conditions was evaluated, as well as the antibacterial activity. The results demonstrate that the blending with PCL and PLA leads to films with a dense morphology, increases the hydrophilic character, and induces a reinforcement of the mechanical characteristics with respect to pristine PHBV. In addition, a decrease in dielectric constant and a.c. electrical conductivity was noticed for PHBV/PLA and PHBV/PCL blends compared to neat PHBV polymer. All neat polymers and blends showed antibacterial properties against S. aureus, with more than 40% bacterial reduction, which increased to 72% in the presence of PCL polymer for a blend ratio of 50/50. Thus, it is demonstrated a suitable way to further tailor a variety of functionalities of PHBV for specific applications, by the development of polymer blends with PLA or PCL.

Electrospun Magnetic Ionic Liquid Based Electroactive Materials for Tissue Engineering Applications.

Functional electrospun fibers incorporating ionic liquids (ILs) present a novel approach in the development of active microenviroments due to their ability to respond to external magnetic fields without the addition of magnetic particles. In this context, this work reports on the development of magnetically responsive magneto-ionic fibers based on the electroactive polymer poly(vinylidene fluoride) and the magnetic IL (MIL), bis(1-butyl-3-methylimidazolium) tetrathiocyanatocobaltate ([Bmim]2[(SCN)4Co]). The PVDF/MIL electrospun fibers were prepared incorporating 5, 10 and 15 wt.% of the MIL, showing that the inclusion of the MIL increases the polar ß-phase content of the polymer from 79% to 94% and decreases the crystallinity of the fibers from 47% to 36%. Furthermore, the thermal stability of the fibers decreases with the incorporation of the MIL. The magnetization of the PVDF/MIL composite fibers is proportional to the MIL content and decreases with temperature. Finally, cytotoxicity assays show a decrease in cell viability with increasing the MIL content.

Fiber-Reinforced Polyester Composites with Photoluminescence Sensing Capabilities for UV Degradation Monitoring.

The wide application of fiber-reinforced polymer composite (FRPC) materials has given rise to the problem of their durability and performance over time. These problems are largely associated with their environmental conditions and service procedures, including ultraviolet (UV) irradiation. Here, we propose the production of polyester-based composites with different contents of synthesized Y3Al5O12:Ce3+,Ga (YAG:Ce,Ga) particles to provide sensing abilities towards material degradation. In this regard, the composites were subjected to UV radiation exposure, and its influence on the morphological, mechanical, and optical properties of the materials was investigated. Our findings reveal the self-sensing capabilities of the developed FRPC. The results indicate the potential of the system for the development of highly effective coatings allowing to detect and monitor UV degradation in composite materials for demanding applications.

Fluorinated Polymer Membranes as Advanced Substrates for Portable Analytical Systems and Their Proof of Concept for Colorimetric Bioassays.

Portable analytical systems are increasingly required for clinical analysis or environmental monitoring, among others, being materials with tailored physicochemical properties among the main needs for successful functional implementation. This article describes the processing of fluorinated poly(vinylidene-co-trifluorethylene), P(VDF-TrFE), membranes with tailored morphological and physicochemical properties to be used as microfluidic substrates for portable analytical systems, commonly called point-of-care systems in the medical field. The morphology of the developed membranes includes spherulitic, porous, randomly oriented, and oriented fibers. Furthermore, the processed hydrophobic P(VDF-TrFE) membranes were post-treated by oxygen plasma to make them superhydrophilic. The influence of morphology and plasma treatment on the physicochemical properties and capillary flow rates was evaluated. Microfluidic systems were then designed and printed by wax printing for the colorimetric quantification of glucose. The systems comprise eight reaction chambers, each glucose concentration (25, 50, 75, and 100 mg dL-1) being measured in two reaction chambers separately and at the same time. The results demonstrate the suitability of the developed microfluidic substrates based on their tailorable morphology, improved capillary flow rate, wax print quality, homogeneous generation of colorimetric reaction, and excellent mechanical properties. Finally, the possibility of being reused, along with their electroactive properties, can lead to a new generation of microfluidic substrates based on fluorinated membranes.

Magnetically Activated Electroactive Microenvironments for Skeletal Muscle Tissue Regeneration.

This work reports on magnetoelectric biomaterials suitable for effective proliferation and differentiation of myoblast in a biomimetic microenvironment providing the electromechanical stimuli associated with this tissue in the human body. Magnetoelectric films are obtained by solvent casting through the combination of a piezoelectric polymer, poly(vinylidene fluoride-trifluoro-ethylene), and magnetostrictive particles (CoFe2O4). The nonpoled and poled (with negative and positive surface charge) magnetoelectric composites are used to investigate their influence on C2C12 myoblast adhesion, proliferation, and differentiation. It is demonstrated that the proliferation and differentiation of the cells are enhanced by the application of mechanical and/or electrical stimulation, with higher values of maturation index under mechanoelectrical stimuli. These results show that magnetoelectric cell stimulation is a full potential approach for skeletal muscle tissue engineering applications.

Multicatalysis Combining 3D-Printed Devices and Magnetic Nanoparticles in One-Pot Reactions: Steps Forward in Compartmentation and Recyclability of Catalysts.

A tricatalytic compartmentalized system that immobilizes metallic species to perform one-pot sequential functionalization is described: a three-dimensional (3D)-printed palladium monolith, ferritic copper(I) magnetic nanoparticles, and a 3D-printed polypropylene capsule-containing copper(II) loaded onto polystyrene-supported 1,5,7-triazabicyclo[4.4.0]dec-5-ene (PS-TBD) allowed the rapid synthesis of diverse substituted 1-([1,1'-biphenyl]-4-yl)-1H-1,2,3-triazoles. The procedure is based on the Chan-Lam azidation/copper alkyne-azide cycloaddition/Suzuki reaction strategy in the solution phase. This catalytic system enabled the efficient assembly of the final compounds in high yields without the need for special additives or intermediate isolation. The monolithic catalyst-containing immobilized palladium species was synthesized by surface chemical modification of a 3D-printed silica monolith using a soluble polyimide resin as a key reagent, thus creating an extremely robust composite. All three immobilized catalysts described here were easily recovered and reused in numerous cycles. This work exemplifies the role of 3D printing in the design and manufacture of devices for compartmented multicatalytic systems to carry out complex one-pot transformations.