Analysis of the Effect of Network Structure and Disulfide Concentration on Vitrimer Properties.

A set of five vitrimers with glass transition temperatures in the range of 80-90 °C were designed to assess the effect of the network structure and disulfide concentration on their dynamic and mechanical properties, and to find the best performing system overall compared to the commercial Araldite LY1564/Aradur 3486 commercial thermoset system. Vitrimer networks were prepared by incorporating mono- and bifunctional epoxy reactive diluents and an amine chain extender into the Araldite LY1564/4-aminophenyldisulfide system.

Enhanced Biodegradability in Soil of Chicken Feather by Steam Explosion for Potential Application in Agricultural Biodegradable Plastics.

Feather waste is a major issue from an economic and environmental point of view. Even though there are already routes for the valorisation of feathers into fertilisers and feather meal, these are considered to have low added value. For more attractive applications, for example in agricultural biodegradable plastics, higher and faster degradability in soil is required. To face this challenge alternative approaches to accelerate biodegradation and disintegration processes are needed. In this context, steam explosion appears as an effective technology to modify the structure of feather and improve its soil degradability. In this work, chicken feathers were treated by steam explosion and the effect of treatment on their structure and physico-chemical and thermal properties were evaluated. Finally, the effect of the process conditions on the disintegration and biodegradation in soil of feathers was also investigated, finding an increased degradation in soil of steam explosion treated feathers. These results open up the possibilities of using feather waste as a component for environmentally friendly agricultural bioplastics that can be degraded in-situ in soil.

Aero Grade Epoxy Vitrimer towards Commercialization.

Traditional crosslinked aero grade epoxy resins have excellent thermal-mechanical properties and solvent resistance, but they cannot be remolded, recycled, or repaired. Vitrimers can be topologically rearranged via an associative exchange mechanism, endowing them with thermoplasticity. Introducing dynamic bonds into crosslinked networks to obtain more sustainable thermosets is currently an interesting research topic. While recent research into vitrimers has indicated many advantages over traditional thermosets, an important shortcoming has been identified: susceptibility to creep at service temperature due to the dynamic bonds present in the network. In addition, designing aero grade epoxy vitrimers (similar to RTM6 resin) still remains a challenge. Herein, low creep aero grade epoxy vitrimer with thermal and mechanical properties similar to those of aero grade epoxy resins and with the ability to be recyclable, repairable, and reprocessable, has been prepared. In this manuscript, we demonstrate that aero grade epoxy vitrimer with reduced creep can be easily designed by the introduction of a certain fraction of permanent crosslinks, without having a negative effect on the stress relaxation of the material. Subsequently, the mechanical and relaxation properties were investigated and compared with those of classical aero grade epoxy resin. A high Tg (175 °C) epoxy vitrimer was obtained which fulfilled all mechanical and thermal specifications of the aero sector. This work provides a simple network design to obtain aero grade epoxy resins with excellent creep resistance at elevated temperatures while being sustainable.

3D Printable Dynamic Hydrogel: As Simple as it Gets!

3D printing technology offers a vast range of applications for tissue engineering applications. Over the past decade a vast range of new equipment has been developed; while, 3D printable biomaterials, especially hydrogels, are investigated to fit the printability requirements. The current candidates for bioprinting often require post-printing cross-linking to maintain their shape. On the other hand, dynamic hydrogels are considered as the most promising candidate for this application with their extrudability and self-healing properties. However, it proves to be very difficult to match the required rheological in a simple material. Here, this study presents for the first time the simplest formulation of a dynamic hydrogel based on thiol-functionalized hyaluronic acid formulated with gold ions that fulfill all the requirements to be printed without the use of external stimuli, as judged by the rheological studies. The printability is also demonstrated with a 3D printer allowing for the printing of the dynamic hydrogel as it is, achieving 3D construct with a relatively good precision and up to 24 layers, corresponding to 10 mm high. This material is the simplest 3D printable hydrogel and its mixture with cells and biological compounds is expected to open a new era in 3D bioprinting.

Assessing the Effect of CeO2 Nanoparticles as Corrosion Inhibitor in Hybrid Biobased Waterborne Acrylic Direct to Metal Coating Binders.

CeO2 nanoparticles were incorporated in waterborne binders containing high biobased content (up to 70%) in order to analyze the anticorrosion performance for direct to metal coatings. Biobased binders were synthesized by batch miniemulsion polymerization of 2-octyl acrylate and isobornyl methacrylate monomers using a phosphate polymerizable surfactant (Sipomer PAM200) that lead to the formation of phosphate functionalized latexes. Upon the direct application of such binders on steel, the functionalized polymer particles were able to interact with steel, creating a thin phosphatization layer between the metal and the polymer and avoiding flash rust. The in situ incorporation of the CeO2 nanoparticles during the polymerization process led to their homogeneous distribution in the final polymer film, which produced outstanding anticorrosion performance according to the Electrochemical Impedance Spectroscopy measurements. In fact, steel substrates coated with the hybrid polymer film (30-40 µm thick) showed high barrier corrosion resistance after 41 days (~1000 h) of immersion in NaCl water solution and active inhibition capabilities thanks to the presence of the CeO2 nanoparticles. This work opens the door to the fabrication of sustainable hybrid anticorrosion waterborne coatings.

Omniphobic Etched Aluminum Surfaces with Anti-Icing Ability.

In this work, omniphobic surfaces are developed by combining chemical etching and surface modification of aluminum. In the first step, hierarchical micro/nanostructuring is carried out by chemical etching. Thereafter, a perfluoropolyether is grafted onto the corrugated aluminum substrate, decreasing its surface free energy and turning the system omniphobic. The morphology and chemical composition of the developed surfaces are characterized. We observed a low affinity toward liquids, regardless of their chemical nature and surface tension. The surface shows superhydrophobic properties with a water contact angle of 160° and simultaneously strong oleophobic properties with a hexadecane contact angle of 141°. Furthermore, these omniphobic surfaces significantly delay the freezing time of water droplets to 5100 s, which is about 20-fold of the freezing time on pristine aluminum (260 s), and they even inhibit ice growth by repelling the incoming droplets prior to ice nucleation.

COSAN-stabilised omega-3 oil-in-water nanoemulsions to prolong lung residence time for poorly water soluble drugs.

Herein, we report on the capacity of the amphiphilic inorganic anion cobalt bis(dicarbollide) to stabilise oil-in-water nanoemulsions (NEs). The resulting NEs show long term stability in water and high drug-loading capacity, and can prolong the residence time of hydrophobic drugs in the lungs as determined by in vivo positron emission tomography imaging.

Improved Thermal Insulating Properties of Renewable Polyol Based Polyurethane Foams Reinforced with Chicken Feathers.

In the present work, sustainable rigid polyurethane foams (RPUF) reinforced with chicken feathers (CF) were prepared and characterized. The bio-based polyol used to formulate the foams was obtained from castor oil. This investigation reports the influence of the chicken feathers fibers as reinforcement of RPUF, on water absorption, thermal, mechanical and morphological properties (field-emission scanning electron microscope-FESEM) and thermal conductivity on water-blown biofoams. It was found that the biofoams improved thermal insulating properties when CF was added. The addition of CF to foams provided lower heat flux density to the biofoams obtaining bio-based materials with better insulation properties. The results obtained in this study proved that the incorporation of CF to RPUF modified the cell structure of the foams affecting their physical and mechanical properties, as well as functional properties such as the heat transmission factor. These biofoams containing up to 45% of bio-based materials have shown the potential to replace fully petroleum-based foams in thermal insulation applications.

Robust Aluminum Electrodeposition from Iionic Liquid Electrolytes Containing Light Aromatic Naphta as Additive.

Aluminum electrodeposition can be carried out from several ionic liquid electrolyte formulations. Nevertheless, this plating process has not been industrialized so far because of the durability of the electrolytes and because the Al coatings obtained are non-fully homogeneous in terms of coating morphology and thickness distribution. In this work we electrodeposited Al coatings from a 3-butyl-1-ethylimidazolium tetrachloroaluminate electrolyte additivated with increasing concentrations of a new cost-effective additive: light aromatic naphtha solvent. Firstly, electrolytes were characterized by cyclic voltammetry, where changes in the electrochemistry of the process were identified. Then, surface characterization showed that Al coatings morphology turned out to be smoother, more homogeneous and more compact with increasing additive concentration. Furthermore, the process was scaled up to flat plates of 18 cm2 area and also on 25 cm2 parts designed with straight corners to demonstrate both the optimization of the electrolytic bath performance and its throwing power enhancement.

Sulfur Polymers Meet Poly(ionic liquid)s: Bringing New Properties to Both Polymer Families.

Sulfur-containing polymers and poly(ionic liquid)s are emerging macromolecules with unique properties and applications. This article shows the first integration of these two polymer families, leading to materials with a unique combination of properties. The synthetic strategy toward sulfur-containing poly(ionic liquid)s involves first the copolymerization of elemental sulfur with 4-vinylbenzyl chloride and subsequent quaternization of the alkyl chloride group using N-methyl imidazole. The synthetic pathway is completed by the anion exchange reaction of the poly(sulfur-co-4-vinylbenzyl imidazolium chloride) by a sulphonamide anion. The obtained polymers are fully characterized by NMR, FTIR, SEC, DSC, and TGA. The sulfur poly(ionic liquid)s combine some properties related to its poly(ionic liquid) nature, such as anion-dependent solubility (water vs organic solvents) and high ionic conductivity as well as properties related to its sulfur content, such as redox activity.

Flexible Biocomposites with Enhanced Interfacial Compatibility Based on Keratin Fibers and Sulfur-Containing Poly(urea-urethane)s.

Feathers are made of keratin, a fibrous protein with high content of disulfide-crosslinks and hydrogen-bonds. Feathers have been mainly used as reinforcing fiber in the preparation of biocomposites with a wide variety of polymers, also poly(urea-urethane)s. Surface compatibility between the keratin fiber and the matrix is crucial for having homogenous, high quality composites with superior mechanical properties. Poly(urea-urethane) type polymers are convenient for this purpose due to the presence of polar functionalities capable of forming hydrogen-bonds with keratin. Here, we demonstrate that the interfacial compatibility can be further enhanced by incorporating sulfur moieties in the polymer backbone that lead to new fiber-matrix interactions. We comparatively studied two analogous thermoplastic poly(urea-urethane) elastomers prepared starting from the same isocyanate-functionalized polyurethane prepolymer and two aromatic diamine chain extenders, bis(4-aminophenyl) disulfide (TPUU-SS) and the sulfur-free counterpart bis(4-aminophenyl) methane (TPUU). Then, biocomposites with high feather loadings (40, 50, 60 and 75 wt %) were prepared in a torque rheometer and hot-compressed into flexible sheets. Mechanical characterization showed that TPUU-SS based materials underwent higher improvement in mechanical properties than biocomposites made of the reference TPUU (up to 7.5-fold higher tensile strength compared to neat polymer versus 2.3-fold). Field Emission Scanning Electron Microscope (FESEM) images also provided evidence that fibers were completely embedded in the TPUU-SS matrix. Additionally, density, thermal stability, and water absorption of the biocomposites were thoroughly characterized.

Poly(anthraquinonyl sulfides): High Capacity Redox Polymers for Energy Storage.

Redox polymers with high energy storage capacity are searched in order to diminish the weight to the actual batteries. Poly(anthraquinonyl sulfide) PAQS is a popular redox polymer which has shown a high performance cathode for lithium, sodium and magnesium batteries. Although PAQS cathodes show high cycling stability it has a relatively low theoretical specific capacity of 225 mAh/g. In this paper we show the synthesis and characterization of new poly(anthraquinonyl sulfides) PAQxS in an attempt to improve the specific capacity of PAQS. Thus, a series of PAQxS polymers with different polysulfide segment lengths (x between 2 and 9 sulfur atoms) have been synthesized in high yields by reacting in situ formed sodium polysulfides with 1,5-dicholoroanthraquinone. The poly(anthraquinonyl sulfides) powders were characterized by ATR-FTIR, solid state 13C NMR for the organic part and Raman spectroscopy for the chalcogenide part. This characterization confirmed the chemical structure of the PAQxS based on an anthraquinone moiety bind together by polysulfide segments. The electrochemical characterization showed a dual reversible redox mechanism associated with both the anthraquinone and polysulfide electrochemistry. Finally, lithium coin cell battery test of the PAQxS redox polymers as cathodes indicated that the capacity of poly(anthraquinonyl sulfides) showed very high experimental initial capacity values above 600 mAh/g, less capacity loss than sulfur cathodes, and higher steady state capacity than PAQS.

Self-Healing Dynamic Hydrogel as Injectable Shock-Absorbing Artificial Nucleus Pulposus.

The intervertebral discs (IVDs) provide unique flexibility to the spine and exceptional shock absorbing properties under impact. The inner core of the IVD, the nucleus pulposus (NP) is responsible for this adaptive behavior. Herein, we evaluate an injectable, self-healing dynamic hydrogel (DH) based on gold(I)-thiolate/disulfide (Au-S/SS) exchange as NP replacement in a spine motion segment model. For the first time, we report the application of dynamic covalent hydrogels inside biological tissues. The dynamic exchange between Au-S species and disulfide bonds (SS) resulted in self-healing ability and frequency-dependent stiffness of the hydrogel, which was also confirmed in spine motion segments. Injection of preformed DH into nucleotomized IVDs restored the full biomechanical properties of intact IVDs, including the stiffening effect observed at increasing frequencies, which cannot be achieved with conventional covalent hydrogel. DH has the potential to counteract IVD degeneration associated with high frequency vibrations. Self-healing properties, confirmed by rheology studies and macroscopic observation after injection, were required to inject preformed DH, which recovered its mechanical integrity and microstructure to act as an artificial NP. On the other hand, covalent hydrogel did not show any restoration of NP properties as this conventional material suffered irreversible damages after injection, which demonstrates that the dynamic properties are crucial for this application. The persistence of DH in the IVD space following cyclic high-frequency loading, confirmed by tomography after mechanical testing, suggests that this material would have long life span as an injectable NP replacement material.

Electrochemical Reduction of Oxygen in Aprotic Ionic Liquids Containing Metal Cations: A Case Study on the Na-O2 system.

Metal-air batteries are intensively studied because of their high theoretical energy-storage capability. However, the fundamental science of electrodes, electrolytes, and reaction products still needs to be better understood. In this work, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) was chosen to study the influence of a wide range of metal cations (Mn+ ) on the electrochemical behavior of oxygen. The relevance of the theory of Lewis hard and soft acids and bases to predict satisfactorily the reduction potential of oxygen in electrolytes containing metal cations is demonstrated. Systems with soft and intermediate Mn+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium and lithium. Furthermore, DFT calculations on the energy of formation of the resulting metal oxides rationalize the effect of Mn+ on oxygen reduction. A case study on the Na-O2 system is described in detail. Among other things, the Na+ concentration of the electrolyte is shown to control the electrochemical pathway (solution precipitation vs. surface deposition) by which the discharge product grows. All in all, fundamental insights for the design of advanced electrolytes for metal-air batteries, and Na-air batteries in particular, are provided.

Fully Biodegradable Biocomposites with High Chicken Feather Content.

The aim of this work was to develop new biodegradable polymeric materials with high loadings of chicken feather (CF). In this study, the effect of CF concentration and the type of biodegradable matrix on the physical, mechanical and thermal properties of the biocomposites was investigated. The selected biopolymers were polylactic acid (PLA), polybutyrate adipate terephthalate (PBAT) and a PLA/thermoplastic copolyester blend. The studied biocomposites were manufactured with a torque rheometer having a CF content of 50 and 60 wt %. Due to the low tensile strength of CFs, the resulting materials were penalized in terms of mechanical properties. However, high-loading CF biocomposites resulted in lightweight and thermal-insulating materials when compared with neat bioplastics. Additionally, the adhesion between CFs and the PLA matrix was also investigated and a significant improvement of the wettability of the feathers was obtained with the alkali treatment of the CFs and the addition of a plasticizer like polyethylene glycol (PEG). Considering all the properties, these 100% fully biodegradable biocomposites could be adequate for panel components, flooring or building materials as an alternative to wood⁻plastic composites, contributing to the valorisation of chicken feather waste as a renewable material.

Functional Single-Chain Polymer Nanoparticles: Targeting and Imaging Pancreatic Tumors in Vivo.

The development of tools for the early diagnosis of pancreatic adenocarcinoma is an urgent need in order to increase treatment success rate and reduce patient mortality. Here, we present a modular nanosystem platform integrating soft nanoparticles with a targeting peptide and an active imaging agent for diagnostics. Biocompatible single-chain polymer nanoparticles (SCPNs) based on poly(methacrylic acid) were prepared and functionalized with the somatostatin analogue PTR86 as the targeting moiety, since somatostatin receptors are overexpressed in pancreatic cancer. The gamma emitter 67Ga was incorporated by chelation and allowed in vivo investigation of the pharmacokinetic properties of the nanoparticles using single photon emission computerized tomography (SPECT). The resulting engineered nanosystem was tested in a xenograph mouse model of human pancreatic adenocarcinoma. Imaging results demonstrate that accumulation of targeted SCPNs in the tumor is higher than that observed for nontargeted nanoparticles due to improved retention in this tissue.

Electron Transport Layer-Free Solar Cells Based on Perovskite-Fullerene Blend Films with Enhanced Performance and Stability.

The solution processing of pinhole-free methylammonium lead triiodide perovskite-C70 fullerene (MAPbI3 :C70 ) blend films on fluorine-doped tin oxide (FTO)-coated glass substrates is presented. Based on this approach, a simplified and robust protocol for the preparation of efficient electron-transport layer (ETL)-free perovskite solar cells is described. Power conversion efficiency (PCE) of 13.6 % under AM 1.5 G simulated sunlight is demonstrated for these devices. Comparative impedance spectroscopy and photostability analysis of the MAPbI3 :C70 and single MAPbI3 films compared with conventional compact TiO2 ETL-based devices are shown. The beneficial impact of using MAPbI3 :C70 blend films is emphasized.

Efficient Regular Perovskite Solar Cells Based on Pristine [70]Fullerene as Electron-Selective Contact.

[70]Fullerene is presented as an efficient alternative electron-selective contact (ESC) for regular-architecture perovskite solar cells (PSCs). A smart and simple, well-described solution processing protocol for the preparation of [70]- and [60]fullerene-based solar cells, namely the fullerene saturation approach (FSA), allowed us to obtain similar power conversion efficiencies for both fullerene materials (i.e., 10.4 and 11.4 % for [70]- and [60]fullerene-based devices, respectively). Importantly, despite the low electron mobility and significant visible-light absorption of [70]fullerene, the presented protocol allows the employment of [70]fullerene as an efficient ESC. The [70]fullerene film thickness and its solubility in the perovskite processing solutions are crucial parameters, which can be controlled by the use of this simple solution processing protocol. The damage to the [70]fullerene film through dissolution during the perovskite deposition is avoided through the saturation of the perovskite processing solution with [70]fullerene. Additionally, this fullerene-saturation strategy improves the performance of the perovskite film significantly and enhances the power conversion efficiency of solar cells based on different ESCs (i.e., [60]fullerene, [70]fullerene, and TiO2 ). Therefore, this universal solution processing protocol widens the opportunities for the further development of PSCs.

Functionalization of Cellulose Nanocrystals in Choline Lactate Ionic Liquid.

Cellulose nanocrystals (CNCs) are valuable nanomaterials obtained from renewable resources. Their properties make them suitable for a wide range of applications, including polymer reinforcement. However, due to their highly hydrophilic character, it is necessary to modify their surface with non-polar functional groups before their incorporation into a hydrophobic polymer matrix. In this work, cellulose nanocrystals were modified using a silane coupling agent and choline lactate, an ionic liquid derived from renewable resources, as a reaction medium. Modified cellulose nanocrystals were characterized by infrared spectroscopy, showing new peaks associated to the modification performed. X-ray diffraction was used to analyze the crystalline structure of functionalized cellulose nanocrystals and to optimize the amount of silane for functionalization. Poly(lactic acid) (PLA) nanocomposites containing 1 wt % of functionalized cellulose nanocrystals were prepared. They were characterized by field-emission scanning electron microscopy (FE-SEM) and mechanical tests. The use of choline lactate as reaction media has been shown to be an alternative method for the dispersion and silanization of the cellulose nanocrystals without the addition of an external catalyst.