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This work is devoted to the investigation of dielectric permittivity which is influenced by electronic, ionic, and dipolar polarization mechanisms, contributing to the material's capacity to store electrical energy. In this study, an extended dataset of 86 polymers was analyzed, and two quantitative structure-property relationship (QSPR) models were developed to predict dielectric permittivity. From an initial set of 1273 descriptors, the most relevant ones were selected using a genetic algorithm, and machine learning models were built using the Gradient Boosting Regressor (GBR). In contrast to Multiple Linear Regression (MLR)- and Partial Least Squares (PLS)-based models, the gradient boosting models excel in handling nonlinear relationships and multicollinearity, iteratively optimizing decision trees to improve accuracy without overfitting. The developed GBR models showed high R 2 coefficients of 0.938 and 0.822, for the training and test sets, respectively. An Accumulated Local Effect (ALE) technique was applied to assess the relationship between the selected descriptors-eight for the GB_A model and six for the GB_B model, and their impact on target property. ALE analysis revealed that descriptors such as TDB09m had a strong positive effect on permittivity, while MLOGP2 showed a negative effect. These results highlight the effectiveness of the GBR approach in predicting the dielectric properties of polymers, offering improved accuracy and interpretability.

This article provides insights into hydrogels of the most promising biodegradable natural polymers and their mechanisms of degradation, highlighting the different possibilities of controlling hydrogel degradation rates. Since biodegradable hydrogels can be designed as scaffolding materials to mimic the physical and biochemical properties of natural tissues, these hydrogels have found widespread application in the field of tissue engineering and controlled release. In the same manner, their potential as water reservoirs, macro- and microelement carriers, or matrixes for the selective adsorption of pollutants make them excellent candidates for sustainable soil amendment solutions. Accordingly, this article summarizes the recent advances in natural biodegradable hydrogels in the fields of tissue engineering, controlled release, and soil remediation, emphasizing the new opportunities that degradability and its tunability offer for the design and applicability of hydrogels.

The current paradigm of polymer flow assumes that (i) the effect of the molecular weight of the macromolecules, M, and of the temperature, T, on the expression of the viscosity of polymer melts separate; (ii) the molecular weight for entanglement, M c , is independent of T; and (iii) the determination of M c by the break in the log viscosity curve against log M unequivocally differentiates un-entangled melts from entangled melts. We use reliable rheological data on monodispersed polystyrene samples from very low molecular weight (M/M c = 0.015) to relatively high molecular weight (M/M c = 34) to test the separation of M and T in the expression of the viscosity; we reveal that an overall illusion of the validity of the separation of T and M is mathematically comprehensible, especially at high temperature and for M > 2M c , but that, strictly speaking, the separation of M and T is not valid, except for certain periodic values of M equal to M c , 2M c , 4M c , 8M c , 16M c , etc. (period doubling) organized around a "pole reference" value M R = 4M c . We also reveal, for M < M c , the existence of a lower molecular weight limit, M' c = M c /8 for the onset of the macromolecular behavior (macro-coil). The discrete and periodic values of M that validate the separation of the effect of M and T on the viscosity generate the fragmentation of the molecular range into three rheological ranges. Likewise, we show that the effect of temperature is also fragmented into three rheological ranges for T > T g : T g < T< (T g + 23°), (T g + 23°) < T < T LL and T > T LL' where T LL is the liquid-liquid temperature. Our conclusion is that the classical formulation of the viscosity of polymer melts is so overly simplified that it is missing important experimental facts, such as period doubling for the separation of T and M, T LL , M' c , and M c , resulting in its inability to understand the true nature of entanglements. We present in the discussion of the paper the alternative approach to the viscoelastic behavior, "the duality and cross-duality" of the Dual-conformers, showing how this model formalism was used to test mathematically and invalidate the separation of T and M in the classical formulation of viscosity.

The steep increase in carbon dioxide (CO 2 ) emissions has created great concern due to its role in the greenhouse effect and global warming. One approach to mitigate CO 2 levels involves its application in specific technologies. In this context, CO 2 can be used for a more sustainable synthesis of polycarbonates (CO 2 -PCs). In this research, CO 2 -PC films and composites with multiwalled carbon nanotubes (MWCNTs, ranging from 0.2 to 7.0 wt.%) have been prepared to achieve more sustainable multifunctional sensing devices. The inclusion of the carbonaceous fillers allows for the electrical conductivity to be enhanced, reaching the percolation threshold (P c ) at 0.1 wt.% MWCNTs and a maximum electrical conductivity of 0.107 S·m -1 for the composite containing 1.5 wt.% MWCNTs. The composite containing 3.0 wt.% MWCNTs was also studied, showing a stable and linear response under temperature variations from 40 to 100 °C and from 30 to 45 °C, with a sensitivity of 1.3 × 10 -4 °C -1 . Thus, this investigation demonstrates the possibility of employing CO 2 -derived PC/MWCNT composites as thermoresistive sensing materials, allowing for the transition towards sustainable polymer-based electronics.

Low-density green polyethylene (LDGPE) composites reinforced with 5 wt% of bamboo fiber and 3 wt% of a compatibilizing agent (polyethylene grafted with maleic anhydride and tannin) were processed through extrusion and injection molding. Bamboo fiber, Bambusa Vulgaris, was characterized using Fourier-transform infrared spectroscopy (FTIR). The molded specimens were analyzed for their thermal, mechanical, and morphological properties. The estimated concentration was chosen to provide the best mechanical strength to the material studied. FTIR analysis of the fibers revealed the presence of groups characteristic of bamboo fiber and tannin. Differential scanning calorimetry revealed that both compatibilizing agents increased the matrix's degree of crystallinity. However, scanning electron microscopy (SEM) showed that, despite the presence of compatibilizing agents, there was no significant improvement in adhesion between the bamboo fibers and LDGPE.

Biodegradable blends based on plasticized poly(lactic acid) PLA and thermoplastic starch (TPS) have been obtained. The influence of the PLA plasticizer as a compatibility agent has been studied by using two different plasticizers such as neat oligomeric lactic acid (OLA) and functionalized with maleic acid (mOLA). In particular, the morphological, thermal, and mechanical properties have been studied as well as the shape memory ability of the melt-processed materials. Therefore, the influence of the interaction between different plasticizers and the PLA matrix as well as the compatibility between the two polymeric phases on the thermally-activated shape memory properties have been studied. It is very interesting to use the same additive able to act as both plasticizer and compatibilizer, decreasing the glass transition temperature of PLA to a temperature close to the physiological one, obtaining a material suitable for potential biomedical applications. In particular, we obtain that OLA-plasticized blend (oPLA/TPS) show very good thermally-activated capability at 45 °C and 50% deformation, while the blend obtained by using maleic OLA (moPLA/TPS) did not show shape memory behavior at 45 °C and 50% deformation. This fact is due to their morphological changes and the loss of two well-distinguished phases, one acting as fixed phase and the other one acting as switching phase to typically obtain shape memory response. Therefore, the thermally-activated shape memory results show that it is very important to make a balance between plasticizer and compatibilizer, considering the need of two well-established phases to obtain shape memory response.

The obtention of amorphous solid dispersions (ASDs) of mycophenolic acid (MPA) in poly(ε-caprolactone) (PCL) is reported in this paper. An improvement in the bioavailability of the drug is possible thanks to the favorable specific interactions occurring in this system. Differential scanning calorimetry (DSC) was used to investigate the miscibility of PCL/MPA blends, measuring glass transition temperature (T g ) and analyzing melting point depression to obtain a negative interaction parameter, which indicates the development of favorable inter-association interactions. Fourier transform infrared spectroscopy (FTIR) was used to analyze the specific interaction occurring in the blends. Drug release measurements showed that at least 70% of the drug was released by the third day in vitro in all compositions. Finally, preliminary in vitro cell culture experiments showed a decreased number of cancerous cells over the scaffolds containing MPA, presumably arising from the anti-cancer activity attributable to MPA.

Naturally derived biopolymers modifying or combining with other components are excellent candidates to promote the full potential of additive manufacturing in biomedicine, cosmetics, and the food industry. This work aims to develop new photo-cross-linkable alginate-based inks for extrusion 3D printing. Specifically, this work is focused on the effect of the addition of cross-linkers with different chemical structures (polyethylene glycol diacrylate (PEGDA), N,N' -methylenebisacrylamide (NMBA), and acrylic acid (AA)) in the potential printability and physical properties of methacrylated alginate (AlgMe) hydrogels. Although all inks showed maximum photo-curing conversions and gelation times less than 2 min, only those structures printed with the inks incorporating cross-linking agents with flexible and long chain structure (PEGDA and AA) displayed acceptable size accuracy (~0.4-0.5) and printing index (Pr ~1.00). The addition of these cross-linking agents leads to higher Young's moduli (from 1.6 to 2.0-2.6 KPa) in the hydrogels, and their different chemical structures results in variations in their mechanical and rheological properties. However, similar swelling ability (~15 swelling factor), degradability (~45 days 100% weight loss), and cytocompatibility (~100%) were assessed in all the systems, which is of great importance for the final applicability of these hydrogels.

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.

Waste carbon fibre-reinforced plastics were recycled by pyrolysis followed by a thermo-catalytic treatment in order to achieve both fibre and resin recovery. The conventional pyrolysis of this waste produced unusable gas and hazardous liquid streams, which made necessary the treatment of the pyrolysis vapours. In this work, the vapours generated from pyrolysis were valorised thermochemically. The thermal treatment of the pyrolysis vapours was performed at 700 °C, 800 °C and 900 °C, and the catalytic treatment was tested at 700 °C and 800 °C with two Ni-based catalysts, one commercial and one homemade over a non-conventional olivine support. The catalysts were deeply characterised, and both had low surface area (99 m 2 /g and 4 m 2 /g, respectively) with low metal dispersion. The thermal treatment of the pyrolysis vapours at 900 °C produced high gas quantity (6.8 wt%) and quality (95.5 vol% syngas) along with lower liquid quantity (13.3 wt%) and low hazardous liquid (92.1 area% water). The Ni-olivine catalyst at the lowest temperature, 700 °C, allowed us to obtain good gas results (100% syngas), but the liquid was not as good (only 58.4 area% was water). On the other hand, the Ni commercial catalyst at 800 °C improved both the gas and liquid phases, producing 6.4 wt% of gas with 93 vol% of syngas and 13.6 wt% of liquid phase with a 97.5 area% of water. The main reaction mechanisms observed in the treatment of pyrolysis vapours were cracking, dry and wet reforming and the Boudouard reaction.

Metalloenzymes are able to catalyze complex biochemical reactions in cellular (aqueous) media with high efficiency. In recent years, a variety of metal-containing single-chain nanoparticles (SCNPs) have been synthesized as simplified metalloenzyme-mimetic nano-objects. However, most of the metal-containing SCNPs reported so far contained complexed metal ions but not metal nanoclusters (NCs) with diameter <5 nm, which could be used as powerful, emerging catalysts. Herein, we report the synthesis of gold nanoclusters (Au-NCs) within SCNPs and the further use of Au-NCs/SCNPs as catalytic nanoreactors in water. We demonstrate that a common motif contained in several drugs (i.e., the aminophenyl-oxazolidinone fragment present in Rivaroxaban, Sutezolid, and Linezolid) can be efficiently prepared in water from a hydrophobic precursor compound by using the Au-NCs/SCNPs as efficient catalytic nanoreactors. In summary, this work paves the way forthe synthesis of metal-NCs/SCNPs for advanced catalysis in aqueous media.

In this work, biobased rigid polyurethane foams (PUFs) were developed with the aim of achieving thermal and fireproofing properties that can compete with those of the commercially available products. First, the synthesis of a biopolyol from a wood residue by means of a scaled-up process with suitable yield and reaction conditions was carried out. This biopolyol was able to substitute completely the synthetic polyols that are typically employed within a polyurethane formulation. Different formulations were developed to assess the effect of two flame retardants, namely, polyhedral oligomeric silsesquioxane (POSS) and amino polyphosphate (APP), in terms of their thermal properties and degradation and their fireproofing mechanism. The structure and the thermal degradation of the different formulations was evaluated via Fourier Transformed Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Likewise, the performance of the different PUF formulations was studied and compared to that of an industrial PUF. From these results, it can be highlighted that the addition of the flame retardants into the formulation showed an improvement in the results of the UL-94 vertical burning test and the LOI. Moreover, the fireproofing performance of the biobased formulations was comparable to that of the industrial one. In addition to that, it can be remarked that the biobased formulations displayed an excellent performance as thermal insulators (0.02371-0.02149 W·m -1 ·K -1 ), which was even slightly higher than that of the industrial one.

Surface modifications play a crucial role in enhancing the functionality of biomaterials. Different approaches can be followed in order to achieve the bioconjugation of drugs and biological compounds onto polymer surfaces. In this study, we focused on the immobilization of an amoxicillin antibiotic onto the surface of poly-L-lactic acid (PLLA) using a copper-free amino-yne click reaction. The utilization of this reaction allowed for a selective and efficient bioconjugation of the amoxicillin moiety onto the PLLA surface, avoiding copper-related concerns and ensuring biocompatibility. The process involved sequential steps that included surface activation via alkaline hydrolysis followed by an amidation reaction with ethylendiamine, functionalization with propiolic groups, and subsequent conjugation with amoxicillin via a click chemistry approach. Previous amoxicillin immobilization using tryptophan and fluorescent amino acid conjugation was carried out in order to determine the efficacy of the proposed methodology. Characterization techniques such as X-ray photoelectron spectroscopy (XPS), Attenuated Total Reflection (ATR)-Fourier Transform Infrared (FTIR) spectroscopy, surface imaging, water contact angle determination, and spectroscopic analysis confirmed the successful immobilization of both tryptophan and amoxicillin while maintaining the integrity of the PLLA surface. This tailored modification not only exhibited a novel method for surface functionalization but also opens avenues for developing antimicrobial biomaterials with improved drug-loading capacity.

Anthocyanins are a specific group of molecules found in nature that have recently received increasing attention due to their interesting biological and colorimetric properties that have been successfully applied in several fields such as food preservation and biomedicine. Consequently, reviews devoted to a general overview of these flavonoids have proliferated in recent years. Meanwhile, the incorporation of anthocyanins into polymeric systems has become an interesting strategy to widen the applicability of these molecules and develop new smart and functional polymers in the above cited areas. However, anthocyanin-based polymers have been scarcely reviewed in the literature. Accordingly, this review aims to be a systematic summary of the most recent approaches for the incorporation of anthocyanins into macro-, micro-, or nanostructured polymers. Moreover, this work describes the fundamentals of the applicability of smart anthocyanin-based polymers and offers an updated review of their most interesting applications as sensors, biological regulators, and active materials.

This work addresses a novel bio-solvolysis process for the treatment of complex poly(ethylene terephthalate) (PET) waste using a biobased monoethylene glycol (BioMEG) as a depolymerization agent in order to achieve a more sustainable chemical recycling process. Five difficult-to-recycle PET waste streams, including multilayer trays, coloured bottles and postconsumer textiles, were selected for the study. After characterization and conditioning of the samples, an evaluation of the proposed bio-solvolysis process was carried out by monitoring the reaction over time to determine the degree of PET conversion (91.3-97.1%) and bis(2-hydroxyethyl) terephthalate (BHET) monomer yield (71.5-76.3%). A monomer purification process, using activated carbon (AC), was also developed to remove the colour and to reduce the metal content of the solid. By applying this purification strategy, the whiteness (L*) of the BHET greatly increased from around 60 to over 95 (L* = 100 for pure white) and the Zn content was significantly reduced from around 200 to 2 mg/kg. The chemical structure of the purified monomers was analyzed via infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC), and the composition of the samples was measured by proton nuclear magnetic resonance ( 1 H-NMR), proving a high purity of the monomers with a BHET content up to 99.5% in mol.

Staudinger taught us that macromolecules were made up of covalently bonded monomer repeat units chaining up as polymer chains. This paradigm is not challenged in this paper. The main question raised in polymer physics remains: how do these long chains interact and move as a group when submitted to shear deformation at high temperature when they are viscous liquids? The current consensus is that we need to distinguish two cases: the deformation of "un-entangled chains" for macromolecules with molecular weight, M, smaller than M e , "the entanglement molecular weight", and the deformation of "entangled" chains for M > M e . The current paradigm stipulates that the properties of polymers derive from the statistical characteristics of the macromolecule itself, the designated statistical system that defines the thermodynamic state of the polymer. The current paradigm claims that the viscoelasticity of un-entangled melts is well described by the Rouse model and that the entanglement issues raised when M > Me, are well understood by the reptation model introduced by de Gennes and colleagues. Both models can be classified in the category of "chain dynamics statistics". In this paper, we examine in detail the failures and the current challenges facing the current paradigm of polymer rheology: the Rouse model for un-entangled melts, the reptation model for entangled melts, the time-temperature superposition principle, the strain-induced time dependence of viscosity, shear-refinement and sustained-orientation. The basic failure of the current paradigm and its inherent inability to fully describe the experimental reality is documented in this paper. In the discussion and conclusion sections of the paper, we suggest that a different solution to explain the viscoelasticity of polymer chains and of their "entanglement" is needed. This requires a change in paradigm to describe the dynamics of the interactions within the chains and across the chains. A brief description of our currently proposed open dissipative statistical approach, "the Grain-Field Statistics", is presented.

The chemical recycling of poly(ethylene terephthalate) -PET- fractions, derived from actual household packaging waste streams, using solvolysis, was investigated. This recycling strategy was applied after a previous on-line automatic identification, by near-infrared spectroscopy -NIR-, and a subsequent selective sorting of the different PET materials that were present in the packaging wastes. Using this technology, it was possible to classify fractions exclusively including PET, virtually avoiding the presence of both other plastics and materials, such as paper, cardboard and wood, that are present in the packaging wastes, as they were efficiently recognised and differentiated. The simple PET fractions, including clear and monolayered materials, were adequate to be recycled by mechanical means meanwhile the complex PET fractions, containing highly coloured and multi-layered materials, were suitable candidates to be recycled by chemical routes. The depolymerisation capacity of the catalytic glycolysis, when applied to those complex PET wastes, was studied by evaluating the effect of the process parameters on the resulting formation and recovery of the monomer bis(2-hydroxyethyl) terephthalate -BHET- and the achieved quality of this reaction product. Comparable and reasonable results, in terms of monomer yield and its characteristics, were obtained independently of the type of complex PET waste that was chemically recycled.

Bio-based epoxy thermoset resins have been developed from epoxidized soybean oil (ESO) cured with tannic acid (TA). These two substances of vegetable origin have been gathering attention due to their accessibility, favorable economic conditions, and convenient chemical functionalization. TA's suitable high phenolic functionalization has been used to crosslink ESO by adjusting the -OH (from TA):epoxy (from ESO) molar ratio from 0.5:1 to 2.5:1. By means of Fourier-transform infrared spectroscopy, resulting in thermosets that evidenced optimal curing properties under moderate conditions (150-160 °C). The thermogravimetric analysis of the cured resins showed thermal stability up to 261 °C, with modulable mechanical and thermal properties determined by differential scanning calorimetry, dynamical mechanical thermal analysis, and tensile testing. Water contact angle measurements (83-87°) and water absorption tests (0.6-4.5 initial weight% intake) were performed to assess the suitability of the resins as waterproof coatings. Electrochemical impedance spectroscopy measurements were performed to characterize the anti-corrosive capability of these coatings on carbon steel substrates. Excellent barrier properties have been demonstrated due to the high electrical isolation and water impermeability of these oil-based coatings, without signs of deterioration over 6 months of immersion in a 3.5 wt.% NaCl solution. These results demonstrate the suitability of the developed materials as anti-corrosion coatings for specific applications.

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.

This work reports on the development of collagen films with graphene oxide nanoparticles (GO NPs), aiming toward the development of a new generation of functional sustainable sensors. For this purpose, different GO NP contents up to 3 wt % were incorporated into a collagen matrix, and morphological, thermal, mechanical and electrical properties were evaluated. Independently of the GO NP content, all films display an increase in thermal stability as a result of the increase in the structural order of collagen, as revealed by XRD analysis. Further, the inclusion of GO NPs into collagen promotes an increase in the intensity of oxygen characteristic absorption bands in FTIR spectra, due to the abundant oxygen-containing functional groups, which lead to an increase in the hydrophilic character of the surface. GO NPs also influence the mechanical properties of the composites, increasing the tensile strength from 33.2 ± 2.4 MPa (collagen) to 44.1 ± 1.0 MPa (collagen with 3 wt % GO NPs). Finally, the electrical conductivity also increases slightly with GO NP content, allowing the development of resistive bending sensors.

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.

Recent advancements in wood modification aim to enhance the inherent qualities of this versatile biological material, which includes renewability, ease of processing, and thermal insulation. This study focuses on evaluating the effectiveness of lignin as a protective agent for less durable wood species, namely, Pinus nigra and Fagus sylvatica L. The impregnation of wood with three various forms of lignin, such as kraft lignin, acetylated kraft lignin, and lignin nanoparticles, was carried out using the vacuum technique at room conditions. The results showed that the treatments significantly improve the hydrophobicity of wood surfaces, particularly in pine wood, and provide protection against UV ageing. Additionally, the treatments contributed to the stabilisation of moisture content at different humidity levels. Although slight colour variations were observed, their impact on the visual appearance was minimal, and the thermal analysis confirmed enhanced thermal properties. Additionally, plasma treatment further enhanced hydrophobicity after treatments, offering potential benefits in terms of moisture resistance and durability. The findings of this study highlight the promising effects of lignin-based treatments on wood properties, providing sustainable solutions for wood protection in various sectors. However, further optimisation is needed to fully explore the potential of lignin and lignin nanoparticles.

The substitution of fossil resources by alternatives derived from biomass is a reality that is taking on a growing relevance in the chemical and energy industries. In this sense, fats, oils, and their derived products have become indispensable inputs due to their broad functional attributes, stable price and sustainable character. Acrylated vegetable oils are considered to be very versatile materials for very broad applications (such as in adhesives, coatings or inks) since, in the presence of photoinitiators, they can be polymerized by means of UV-initiated free radical polymerizations. The usual process for the synthesis of acrylate vegetable oils consists in reacting epoxidized oils derivatives with acrylic acid. Here, the influence of different catalysts on the activity and selectivity of the process of acrylation of epoxidized soybean oil is studied. In addition, a novel one-step method for direct acrylation of vegetable oils is also explored. This new approach advantageously uses the original vegetable resource and eliminates intermediate reactions, thus being more environmentally efficient. This study offers a simple and low-cost option for synthesizing a biomass-derived monomer and studies the potential for the 3D printing of complex structures via digital light processing (DLP) 3D printing of the thus-obtained novel sustainable formulations.

This study experimentally investigates the effect of green polymeric nanoparticles on the interfacial tension (IFT) and wettability of carbonate reservoirs to effectively change the enhanced oil recovery (EOR) parameters. This experimental study compares the performance of xanthan/magnetite/SiO 2 nanocomposites (NC) and several green materials, i.e., eucalyptus plant nanocomposites (ENC) and walnut shell ones (WNC) on the oil recovery with performing series of spontaneous imbibition tests. Scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDAX), and BET (Brunauer, Emmett, and Teller) surface analysis tests are also applied to monitor the morphology and crystalline structure of NC, ENC, and WNC. Then, the IFT and contact angle (CA) were measured in the presence of these materials under various reservoir conditions and solvent salinities. It was found that both ENC and WNC nanocomposites decreased CA and IFT, but ENC performed better than WNC under different salinities, namely, seawater (SW), double diluted salted (2 SW), ten times diluted seawater (10 SW), formation water (FW), and distilled water (DIW), which were applied at 70 °C, 2000 psi, and 0.05 wt.% nanocomposites concentration. Based on better results, ENC nanofluid at salinity concentrations of 10 SW and 2 SW ENC were selected for the EOR of carbonate rocks under reservoir conditions. The contact angles of ENC nanocomposites at the salinities of 2 SW and 10 SW were 49 and 43.4°, respectively. Zeta potential values were -44.39 and -46.58 for 2 SW and 10 SW ENC nanofluids, which is evidence of the high stability of ENC nanocomposites. The imbibition results at 70 °C and 2000 psi with 0.05 wt.% ENC at 10 SW and 2 SW led to incremental oil recoveries of 64.13% and 60.12%, respectively, compared to NC, which was 46.16%.

Unsaturated polyester resin (UPR) is one of the first commercialized polymer matrices for composites reinforced with glass fibers, but has remained popular to this day. To reduce their environmental impact, natural fibers have been used as reinforcements. Researchers all over the world are still interested in these composites, and numerous papers have been published in the last four decades. Using bibliometric analysis, this work provides compiled, structured, and relevant information about the evolution and current state of these materials. This first study on UPR biocomposites based on bibliometric analysis examined 531 published papers identified in the Scopus database from 1982 to July 2022. An analysis of the most active states, leading institutions, and leading authors is followed by the identification of key areas such as the most common natural fibers used as reinforcements, fiber treatments, and composite design parameters such as processing techniques; recently, composite testing; and technological applications. The findings emphasize the importance of staying active in this global field and provide information on novel promising topics for future research.

The current concerns of both society and the materials industries about the environmental impact of thermoset composites, as well as new legislation, have led the scientific sector to search for more sustainable alternatives to reduce the environmental impact of thermoset composites. Until now, to a large extent, sustainable reinforcements have been used to manufacture more sustainable composites and thus contribute to the reduction of pollutants. However, in recent years, new alternatives have been developed, such as thermosetting resins with bio-based content and/or systems such as recyclable amines and vitrimers that enable recycling/reuse. Throughout this review, some new bio-based thermoset systems as well as new recyclable systems and sustainable reinforcements are described, and a brief overview of the biocomposites market and its impact is shown. By way of conclusion, it should be noted that although significant improvements have been achieved, other alternatives ought to be researched.

Polyhydroxyalkanoates are natural polyesters synthesized by microorganisms and bacteria. Due to their properties, they have been proposed as substitutes for petroleum derivatives. This work studies how the printing conditions employed in fuse filament fabrication (FFF) affect the properties of poly(hydroxybutyrate-co-hydroxy hexanoate) or PHBH. Firstly, rheological results predicted the printability of PHBH, which was successfully realized. Unlike what usually happens in FFF manufacturing or several semi-crystalline polymers, it was observed that the crystallization of PHBH occurs isothermally after deposition on the bed and not during the non-isothermal cooling stage, according to calorimetric measurements. A computational simulation of the temperature profile during the printing process was conducted to confirm this behavior, and the results support this hypothesis. Through the analysis of mechanical properties, it was shown that the nozzle and bed temperature increase improved the mechanical properties, reducing the void formation and improving interlayer adhesion, as shown by SEM. Intermediate printing velocities produced the best mechanical properties.

Electrically-conductive epoxy nanocomposites (NCs) with improved mechanical and adhesive properties were achieved through the combined addition of poly(ε-caprolactone) (PCL) and carbon nanotubes (CNTs). Three different ionic liquids (ILs) were used as dual role agents, i.e., as both curing and dispersing agents. Regardless of the IL used, the epoxy/PCL matrix of the NCs showed a single-phase behaviour and similar glass transition (T g ) and crosslinking density (ν e ) values to the unfilled epoxy/PCL/IL systems. Although the CNTs were more poorly dispersed in the epoxy/PCL/CNT/IL NCs than in the reference epoxy/CNT/IL NCs, which led to slightly lower electrical conductivity values, the epoxy/PCL/CNT/IL NCs were still semiconductive. Their low-strain mechanical properties (i.e., flexural modulus and flexural strength) were similar or better than those of the reference epoxy/IL systems and their high-strain mechanical properties (i.e., deformation at break and impact strength) were significantly better. In addition, the positive effects of the PCL and the CNTs on the adhesive properties of the epoxy/IL system were combined. The substitution of ILs for traditional amine-based curing agents and biodegradable PCL for part of the epoxy resin represents an important advance on the road towards greater sustainability., Competing Interests: The authors declare no conflict of interest.

Glucose is an analyte of great importance, both in the clinical and sports fields. Since blood is the gold standard biofluid used for the analytical determination of glucose, there is high interest in finding alternative non-invasive biofluids, such as sweat, for its determination. In this research, we present an alginate-based bead-like biosystem integrated with an enzymatic assay for the determination of glucose in sweat. The system was calibrated and verified in artificial sweat, and a linear calibration range was obtained for glucose of 10-1000 µM. The colorimetric determination was investigated, and the analysis was carried out both in the black and white and in the Red:Green:Blue color code. A limit of detection and quantification of 3.8 µM and 12.7 µM, respectively, were obtained for glucose determination. The biosystem was also applied with real sweat, using a prototype of a microfluidic device platform as a proof of concept. This research demonstrated the potential of alginate hydrogels as scaffolds for the fabrication of biosystems and their possible integration in microfluidic devices. These results are intended to bring awareness of sweat as a complementary tool for standard analytical diagnosis.

A biobased diglycidyl ether of vanillin (DGEVA) epoxy resin was nanostructured by poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-PPO-PEO) triblock copolymer. Due to the miscibility/immiscibility properties of the triblock copolymer in DGEVA resin, different morphologies were obtained depending on the triblock copolymer amount. A hexagonally packed cylinder morphology was kept until reaching 30 wt% of PEO-PPO-PEO content, while a more complex three-phase morphology was obtained for 50 wt%, in which large worm-like PPO domains appear surrounded by two different phases, one of them rich in PEO and another phase rich in cured DGEVA. UV-vis measurements show that the transmittance is reduced with the increase in triblock copolymer content, especially at 50 wt%, probably due to the presence of PEO crystals detected by calorimetry.

A new phosphate-containing bio-polyester based on glycerol and citric acid was synthesized and evaluated as fire-retardant (FR) in wooden particleboards. Phosphorus pentoxide was used to first introduce phosphate esters in the glycerol followed by esterification with citric acid to produce the bio-polyester. The phosphorylated products were characterized by ATR-FTIR, 1 H-NMR and TGA-FTIR. After polyester curing, they were grinded and incorporated in laboratory produced particleboards. The fire reaction performance of the boards was evaluated by cone calorimeter. An increased char residue was produced depending on the phosphorus content and the THR (Total Heat Release), PHRR (Peak of Heat Release Rate) and MAHRE (Maximum Average of the Rate of Heat Emission) were considerably reduced in presence of the FRs. Highlights: Phosphate containing bio-polyester as fire retardant in wooden particle board; Fire performance is improved; Bio-polyester acts in the condensed and gas phases; Additive effectiveness similar to ammonium polyphosphate.

There is an actual need for developing materials for wound healing applications with anti-inflammatory, antioxidant, or antibacterial properties in order to improve the healing performance. In this work, we report the preparation and characterization of soft and bioactive iongel materials for patches, based on polymeric poly(vinyl alcohol) (PVA) and four ionic liquids containing the cholinium cation and different phenolic acid anions, namely cholinium salicylate ([Ch][Sal]), cholinium gallate ([Ch][Ga]), cholinium vanillate ([Ch][Van]), and cholinium caffeate ([Ch][Caff]). Within the iongels, the phenolic motif in the ionic liquids plays a dual role, acting as a PVA crosslinker and a bioactive compound. The obtained iongels are flexible, elastic, ionic conducting, and thermoreversible materials. Moreover, the iongels demonstrated high biocompatibility, non-hemolytic activity, and non-agglutination in mice blood, which are key-sought material specifications in wound healing applications. All the iongels have shown antibacterial properties, being PVA-[Ch][Sal], the one with higher inhibition halo for Escherichia Coli . The iongels also revealed high values of antioxidant activity due to the presence of the polyphenol, with the PVA-[Ch][Van] iongel having the highest activity. Finally, the iongels show a decrease in NO production in LPS-stimulated macrophages, with the PVA-[Ch][Sal] iongel displaying the best anti-inflammatory activity (>63% at 200 µg/mL).

Hydrogels have become one of the potential polymers used with great performance for many issues and can be promoted as biomaterials with highly innovative characteristics and different uses. Gelatin is obtained from collagen, a co-product of the meat industry. Thus, converting wastes such as cartilage, bones, and skins into gelatin would give them added value. Furthermore, biodegradability, non-toxicity, and easy cross-linking with other substances can promote polymers with high performance and low cost for many applications, turning them into sustainable products with high acceptance in society. Gelatin-based hydrogels have been shown to be useful for different applications with important and innovative characteristics. For instance, these hydrogels have been used for biomedical applications such as bone reconstruction or drug delivery. Furthermore, they have also shown substantial performance and important characteristics for remediation for removing pollutants from water, watercourse, and effluents. After its uses, gelatin-based hydrogels can easily biodegrade and, thus, can be sustainably used in the environment. In this study, gelatin was shown to be a potential polymer for hydrogel synthesis with highly renewable and sustainable characteristics and multiple uses.

Material extrusion (MEX), more commonly known as fused deposition modelling (FDM/FFF), is one of the most widely used techniques in polymeric Additive Manufacturing (AM). This technology is increasingly present in fields such as engineering and medicine with polymeric materials, including additives of many types. Polylactic acid polymer (PLA) is one of the most widely used materials currently on the market for MEX technology. In addition to its ease of printing, it is a plastic of natural origin, biodegradable and supplants petroleum derivatives in many applications. However, the effect of ageing on the mechanical properties of PLA are still to be evaluated and understood. The main objective of this work is to investigate the effects of ageing of PLA samples on the tensile properties. To investigate the effect of ageing, the samples were tested periodically after exposure to fertilized soil for a period up to 6 months. In addition, some of the samples were chemically pre-treated to improve the surface quality, and the effect of ageing on the treated and untreated samples was also evaluated. This study showed that ultimate strength decreased with ageing from 46 to 36 MPa (22%), and it increased with treatment time in high percentages (even 40%) depending on the time of immersion in the solvent. However, this effect of the chemical treatment gradually disappeared, with the exception of the surface improvement obtained.

In the last few years, the polymerization of monomers within the nanocavities of porous materials has been thoroughly studied and developed, allowing for the synthesis of polymers with tailored morphologies, chemical architectures and functionalities. This is thus a subject of paramount scientific and technological relevance, which, however, has not previously been analyzed from a general perspective. The present overview reports the state of the art on polymerization reactions in spatial confinement within porous materials, focusing on the use of anodized aluminum oxide (AAO) templates. It includes the description of the AAO templates used as nanoreactors. The polymerization reactions are categorized based on the polymerization mechanism. Amongst others, this includes electrochemical polymerization, free radical polymerization, step polymerization and atom transfer radical polymerization (ATRP). For each polymerization mechanism, a further subdivision is made based on the nature of the monomer used. Other aspects of "in situ" polymerization reactions in restricted AAO geometries include: conversion monitoring, kinetic studies, modeling and polymer characterization. In addition to the description of the polymerization process itself, the use of polymer materials derived from polymerization in AAO templates in nanotechnology applications, is also highlighted. Finally, the review is concluded with a general discussion outlining the challenges that remain in the field.

Kraft lignin, a side-stream from the pulp and paper industry, can be modified by laccases for the synthesis of high added-value products. This work aims to study different laccase sources, including a bacterial laccase from Streptomyces ipomoeae (SiLA) and a fungal laccase from Myceliophthora thermophila (MtL), for kraft lignin polymerization. To study the influence of some variables in these processes, a central composite design (CCD) with two continuous variables (enzyme concentration and reaction time) and three levels for each variable was used. The prediction of the behavior of the output variables (phenolic content and molecular weight of lignins) were modelled by means of response surface methodology (RSM). Moreover, characterization of lignins was performed by Fourier-transform infrared (FTIR) spectroscopy and different nuclear magnetic resonance (NMR) spectroscopy techniques. In addition, antioxidant activity was also analyzed. Results showed that lignin polymerization (referring to polymerization as lower phenolic content and higher molecular weight) occurred by the action of both laccases. The enzyme concentration was the most influential variable in the lignin polymerization reaction within the range studied for SiLA laccase, while the most influential variable for MtL laccase was the reaction time. FTIR and NMR characterization analysis corroborated lignin polymerization results obtained from the RSM.

The management of food waste and by-products has become a challenge for the agri-food sector and an example are whey by-products produced in dairy industries. Seeking other whey valorisation alternatives and applications, whey protein films for food packaging applications were developed in this study. Films containing different amounts (0, 5, 10, and 15 wt%) of ascorbic acid were manufactured via compression-moulding and their physicochemical, thermal, barrier, optical, and mechanical properties were analysed and related to the film structure. Additionally, the environmental assessment of the films was carried out to analyse the impact of film manufacture. Regarding physicochemical properties, both FTIR and water uptake analyses showed the presence of non-covalent interactions, such as hydrogen bonding, between whey protein and ascorbic acid as band shifts at the 1500-1700 cm -1 region as well as a water absorption decrease from 380% down to 240% were observed. The addition of ascorbic acid notably improved the UV-Vis light absorbance capacity of whey protein films up to 500 nm, a relevant enhancement for protecting foods susceptible to UV-Vis light-induced lipid oxidation. In relation to the environmental assessment, it was concluded that scaling up film manufacture could lead to a reduction in the environmental impacts, mainly electricity consumption.

3D printing is a manufacturing technique in constant evolution. Day by day, new materials and methods are discovered, making 3D printing continually develop. 3D printers are also evolving, giving us objects with better resolution, faster, and in mass production. One of the areas in 3D printing that has excellent potential is 4D printing. It is a technique involving materials that can react to an environmental stimulus (pH, heat, magnetism, humidity, electricity, and light), causing an alteration in their physical or chemical state and performing another function. Lately, 3D/4D printing has been increasingly used for fabricating materials aiming at drug delivery, scaffolds, bioinks, tissue engineering (soft and hard), synthetic organs, and even printed cells. The majority of the materials used in 3D printing are polymeric. These materials can be of natural origin or synthetic ones of different architectures and combinations. The use of block copolymers can combine the exemplary properties of both blocks to have better mechanics, processability, biocompatibility, and possible stimulus behavior via tunable structures. This review has gathered fundamental aspects of 3D/4D printing for biomaterials, and it shows the advances and applications of block copolymers in the field of biomaterials over the last years.

The use of lignocellulosic fillers in rigid polyurethane foams (RPUFs) has been receiving great attention due to their good mechanical and insulation properties and the high sustainable appeal of the obtained cellular polymers, although high water uptakes are found in most of these systems. To mitigate this detrimental effect, RPUFs filled with wood flour (2.5% wt) were fabricated with the addition of furfuryl alcohol (FA) to create a polymer grafted with the wood filler. Two concentrations of FA (10 wt% and 15 wt%) were investigated in relation to the wood flour, and the RPUFs were characterized for cell morphology, density, compressive properties, thermal stability, and water uptake. The introduction of wood flour as a filler decreased the cell size and increased the anisotropy index of the RPUFs and, in addition to that, the FA grafting increased these effects even more. In general, there were no significant changes in both mechanical and thermal properties ascribed to the incorporation of the fillers. On the other hand, a reduction of up to 200% in water uptake was ascribed to the FA-treated fillers.

The wool fibers of the Latxa sheep breed were combined with a soy protein isolate (SPI) matrix to develop sustainable biocomposites with acoustic properties, adding value to Latxa sheep wool, which is currently considered a residue. Samples with 7, 10, 15, and 20 wt % wool were prepared by freeze drying in order to develop porous structures, as shown by SEM analysis. Additionally, XRD analysis provided the evidence of a change toward a more amorphous structure with the incorporation of wool fibers due to the interactions between the soy protein and keratin present in wool fibers, as shown by the relative intensity changes in the FTIR bands. The biocomposites were analyzed in a Kundt's tube to obtain their sound absorption coefficient at normal incidence. The results showed an acoustic absorption coefficient that well-surpassed 0.9 for frequencies above 1000 Hz. This performance is comparable to that of the conventional synthetic materials present in the market and, thus, sheep wool/SPI biocomposites are suitable to be used as acoustic absorbers in the building industry, highlighting the potential of replacing not only synthetic fibers but also synthetic polymers, with natural materials to enhance the sustainability of the building sector.

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) is a bio-based polyester with the potential to replace some common polymers of fossil origin. However, PHBH presents serious limitations, such as low stiffness, tendency to undergo crystallization over long time periods and low resistance to thermal degradation during processing. In this work, we studied the use of alumina nanowires to generate PHBH-alumina nanocomposites, modifying the properties of PHBH to improve its usability. Solvent casting and melt blending were used to produce the nanocomposites. Then, their physicochemical properties and aquatic toxicity were measured. Finally, LCA was used to evaluate and compare the environmental impacts of several scenarios relevant to the processing and end of life (EoL) conditions of PHBHs. It was observed that, at low concentrations (3 wt.%), the alumina nanowires have a small positive impact on the stiffness and thermal degradation for the samples. However, for higher concentrations, the observed effects differed for each of the applied processing techniques (solvent casting or melt blending). The toxicity measurements showed that PHBH alone and in combination with alumina nanowires (10 wt.%) did not produce any impact on the survival of brine shrimp larvae after 24 and 48 h of exposure. The 18 impact categories evaluated by LCA allowed defining the most environmentally friendly conditions for the processing and EoL of PHBHs, and comparing the PHBH-related impacts to those of some of the most common fossil-based plastics. It was concluded that the preferable processing technique for PHBH is melt blending and that PHBH is unquestionably more environmentally friendly than every other analyzed plastic.

In this work, shape-customized scaffolds based on waterborne polyurethane-urea (WBPUU) were prepared via the combination of direct ink writing 3D-printing and freeze-drying techniques. To improve the printing performance of the ink and guarantee a good shape fidelity of the scaffold, cellulose nanocrystals (CNC) were added during the synthesis of the WBPUU and some of the printed constructs were immersed in CaCl 2 prior to the freeze-drying process to promote ionic crosslinking between calcium ions and the polyurethane. The results showed that apart from allowing the ink to be successfully printed, obtaining scaffolds with good shape fidelity, the addition of the CNC resulted in a greater homogeneity of the porous structure as well as an increase of the swelling capacity of the scaffolds. Additionally, the CNC has a reinforcement effect in the printed systems, presenting a higher compression modulus as the CNC content increases. In the case of samples crosslinked by calcium ions, a rigid shell was observed by scanning electron microscopy, which resulted in stiffer scaffolds that presented a lower water absorption capacity as well as an enhancement of the thermal stability. These results showed the potential of this type of post-printing process to tune the mechanical properties of the scaffold, thus widening the potential of this type of material.

Polylactide (PLA) is among the most commonly used polymers for biomedical applications thanks to its biodegradability and cytocompatibility. However, its inherent stiffness and brittleness are clearly inappropriate for the regeneration of soft tissues (e.g., neural tissue), which demands biomaterials with soft and elastomeric behavior capable of resembling the mechanical properties of the native tissue. In this work, both L- and D,L-lactide were copolymerized with ethylene brassylate, a macrolactone that represents a promising alternative to previously studied comonomers (e.g., caprolactone) due to its natural origin. The resulting copolymers showed an elastomeric behavior characterized by relatively low Young's modulus, high elongation at break and high strain recovery capacity. The thermoplastic nature of the resulting copolymers allows the incorporation of nanofillers (i.e., carbon nanotubes) that further enable the modulation of their mechanical properties. Additionally, nanostructured scaffolds were easily fabricated through a thermo-pressing process with the aid of a commercially available silicon stamp, providing geometrical cues for the adhesion and elongation of cells representative of the nervous system (i.e., astrocytes). Accordingly, the lactide and ethylene brassylate-based copolymers synthesized herein represent an interesting formulation for the development of polymeric scaffolds intended to be used in the regeneration of soft tissues, thanks to their adjustable mechanical properties, thermoplastic nature and observed cytocompatibility.

Polyurethanes are gaining increasing interest for their use as structural components subjected to cyclic loads, such as leaf springs. Thermoset polyurethane (PUR) based technology offers some advantages, such as fatigue resistance, low viscosity, and fast curing. However, current PUR formulations present two major drawbacks: their petrochemical origin and high reactivity. The aim of this work was to develop a novel biobased PUR (BIO-PUR) with the required mechanical properties and processability for manufacturing structural composites by resin transfer moulding (RTM). For this purpose, a high functionality and high hydroxyl index castor-oil-based polyol was used combined with a biobased glycerol (BIO-Gly) to increase the crosslinking density and improve the final properties of the BIO-PUR. The viscosity and reactivity of the different systems were studied by means of rheology tests and differential scanning calorimetry (DSC). Thermal and mechanical properties were studied by dynamic mechanical analysis (DMA) and flexural tests. Furthermore, the RTM process of a representative part was simulated and validated through the manufacturing and testing of plates. The properties of the BIO-PUR resin systems were strongly influenced by the addition of biobased glycerol and its effect on the crosslinking density. The combination of a high functionality and hydroxyl index biobased polyol with the biobased glycerol resulted in a high-performance BIO-PUR with the required reactivity and final properties for structural applications.

There is an increasing medical need for the development of new materials that could replace damaged organs, improve healing of critical wounds or provide the environment required for the formation of a new healthy tissue. The three-dimensional (3D) printing approach has emerged to overcome several of the major deficiencies of tissue engineering. The use of Cannabis sativa as a therapy for some diseases has spread throughout the world thanks to its benefits for patients. In this work, we developed a bioink made with gelatin and alginate that was able to be printed using an extrusion 3D bioprinter. The scaffolds obtained were lyophilized, characterized and the swelling was assessed. In addition, the scaffolds were loaded with Cannabis sativa oil extract. The presence of the extract provided antimicrobial and antioxidant activity to the 3D scaffolds. Altogether, our results suggest that the new biocompatible material printed with 3D technology and with the addition of Cannabis sativa oil could become an attractive alternative to common treatments of soft-tissue infections and wound repair.

In order to continue the development of inks valid for cold extrusion 3D printing, waterborne, polyurethane-urea (WBPUU) based inks with cellulose nanofibers (CNF), as a rheological modulator, were prepared by two incorporation methods, ex situ and in situ , in which the CNF were added after and during the synthesis process, respectively. Moreover, in order to improve the affinity of the reinforcement with the matrix, modified CNF was also employed. In the ex situ preparation, interactions between CNFs and water prevail over interactions between CNFs and WBPUU nanoparticles, resulting in strong gel-like structures. On the other hand, in situ addition allows the proximity of WBPUU particles and CNF, favoring interactions between both components and allowing the formation of chemical bonds. The fewer amount of CNF/water interactions present in the in situ formulations translates into weaker gel-like structures, with poorer rheological behavior for inks for 3D printing. Stronger gel-like behavior translated into 3D-printed parts with higher precision. However, the direct interactions present between the cellulose and the polyurethane-urea molecules in the in situ preparations, and more so in materials reinforced with carboxylated CNF, result in stronger mechanical properties of the final 3D parts.