Peroxide-Induced Synthesis of Maleic Anhydride-Grafted Poly(butylene succinate) and Its Compatibilizing Effect on Poly(butylene succinate)/Pistachio Shell Flour Composites.

Framing the Circular Bioeconomy, the use of reactive compatibilizers was applied in order to increase the interfacial adhesion and, hence, the physical properties and applications of green composites based on biopolymers and food waste derived lignocellulosic fillers. In this study, poly(butylene succinate) grafted with maleic anhydride (PBS-g-MAH) was successfully synthetized by a reactive melt-mixing process using poly(butylene succinate) (PBS) and maleic anhydride (MAH) that was induced with dicumyl peroxide (DCP) as a radical initiator and based on the formation of macroradicals derived from the hydrogen abstraction of the biopolymer backbone. Then, PBS-g-MAH was used as reactive compatibilizer for PBS filled with different contents of pistachio shell flour (PSF) during melt extrusion. As confirmed by Fourier transform infrared (FTIR), PBS-g-MAH acted as a bridge between the two composite phases since it was readily soluble in PBS and could successfully form new esters by reaction of its multiple MAH groups with the hydroxyl (-OH) groups present in cellulose or lignin of PSF and the end ones in PBS. The resultant compatibilized green composites were, thereafter, shaped by injection molding into 4-mm thick pieces with a wood-like color. Results showed significant increases in the mechanical and thermomechanical rigidity and hardness, meanwhile variations on the thermal stability were negligible. The enhancement observed was related to the good dispersion and the improved filler-matrix interfacial interactions achieved by PBS-g-MAH and also to the PSF nucleating effect that increased the PBS's crystallinity. Furthermore, water uptake of the pieces progressively increased as a function of the filler content, whereas the disintegration in controlled compost soil was limited due to their large thickness.

Tailoring the Properties of Thermo-Compressed Polylactide Films for Food Packaging Applications by Individual and Combined Additions of Lactic Acid Oligomer and Halloysite Nanotubes.

In this work, films of polylactide (PLA) prepared by extrusion and thermo-compression were plasticized with oligomer of lactic acid (OLA) at contents of 5, 10, and 20 wt%. The PLA sample containing 20 wt% of OLA was also reinforced with 3, 6, and 9 parts per hundred resin (phr) of halloysite nanotubes (HNTs) to increase the mechanical strength and thermal stability of the films. Prior to melt mixing, ultrasound-assisted dispersion of the nanoclays in OLA was carried out at 100 °C to promote the HNTs dispersion in PLA and the resultant films were characterized with the aim to ascertain their potential in food packaging. It was observed that either the individual addition of OLA or combined with 3 phr of HNTs did not significantly affect the optical properties of the PLA films, whereas higher nanoclay contents reduced lightness and induced certain green and blue tonalities. The addition of 20 wt% of OLA increased ductility of the PLA film by nearly 75% and also decreased the glass transition temperature (Tg) by over 18 °C. The incorporation of 3 phr of HNTs into the OLA-containing PLA films delayed thermal degradation by 7 °C and additionally reduced the permeabilities to water and limonene vapors by approximately 8% and 47%, respectively. Interestingly, the highest barrier performance was attained for the unfilled PLA film plasticized with 10 wt% of OLA, which was attributed to a crystallinity increase and an effect of "antiplasticization". However, loadings of 6 and 9 phr of HNTs resulted in the formation of small aggregates that impaired the performance of the blend films. The here-attained results demonstrates that the properties of ternary systems of PLA/OLA/HNTs can be tuned when the plasticizer and nanofiller contents are carefully chosen and the resultant nanocomposite films can be proposed as a bio-sourced alternative for compostable packaging applications.

Bio-Polyethylene-Based Composites Reinforced with Alkali and Palmitoyl Chloride-Treated Coffee Silverskin.

This work investigates the feasibility of using coffee silverskin (CSS) as a reinforcing agent in biobased polyethylene (BioPE) composites, by adding it in bulk and thin film samples. The effect of two different treatments, alkali bleaching (CSS_A) and esterification with palmitoyl chloride (CSS_P), on mechanical, thermal, morphological and water absorption behavior of produced materials at different CSS loading (10, 20 and 30 wt %) was investigated. A reactive graft copolymerization of BioPE with maleic anhydride was considered in the case of alkali treated CSS. It was found that, when introduced in bulk samples, improvement in the elastic modulus and a reduction in strain at maximum stress were observed with the increase in CSS fraction for the untreated and treated CSS composites, while the low aspect ratio of the CSS particles and their poor adhesion with the polymeric matrix were responsible for reduced ductility in films, decreasing crystallinity values and reduction of elastic moduli. When CSS_A and CSS_P are introduced in the matrix, a substantial reduction in the water uptake is also obtained in films, mainly due to presence of maleated PE, that builds up some interactions to eliminate the amounts of OH groups and hydrophobized CSS, due to the weakened absorption capacity of the functionalized CSS.

Development of starch-rich thermoplastic polymers based on mango kernel flour and different plasticizers.

This work reports on the development of starch-rich thermoplastic based formulations produced by using mango kernel flour, avoiding the extraction process of starch from mango kernel to produce these materials. Glycerol, sorbitol and urea at 15 wt% are used as plasticizers to obtain thermoplastic starch (TPS) formulations by extrusion and injection-moulding processes. Mechanical results show that sorbitol and urea allowed to obtain samples with tensile strength and elongation at break higher than the glycerol-plasticized sample, achieving values of 2.9 MPa of tensile strength and 42 % of elongation at break at 53 % RH. These results are supported by field emission scanning electron microscopy (FESEM) micrographs, where a limited concentration of voids was observed in the samples with sorbitol and urea, indicating a better interaction between starch and the plasticizers. Thermogravimetric analysis (TGA) shows that urea and sorbitol increase the thermal stability of TPS in comparison to the glycerol-plasticized sample. Differential scanning calorimetry (DSC) and dynamic-mechanical-thermal analysis (DMTA) verify the increase in stiffness of the sorbitol and urea plasticized TPS and also illustrate an increase in the glass transition temperature of both samples in comparison to the glycerol-plasticized sample. Glass transition temperatures of 45 °C were achieved for the sample with sorbitol.

Epoxidized and Maleinized Hemp Oil to Develop Fully Bio-Based Epoxy Resin Based on Anhydride Hardeners.

The present work aims to develop thermosetting resins using epoxidized hemp oil (EHO) as a bio-based epoxy matrix and a mixture of methyl nadic anhydride (MNA) and maleinized hemp oil (MHO) in different ratios as hardeners. The results show that the mixture with only MNA as a hardener is characterized by high stiffness and brittleness. In addition, this material is characterized by a high curing time of around 170 min. On the other hand, as the MHO content in the resin increases, the mechanical strength properties decrease and the ductile properties increase. Therefore, it can be stated that the presence of MHO confers flexible properties to the mixtures. In this case, it was determined that the thermosetting resin with balanced properties and high bio-based content contains 25% MHO and 75% MNA. Specifically, this mixture obtained a 180% higher impact energy absorption and a 195% lower Young's modulus than the sample with 100% MNA. Also, it has been observed that this mixture has significantly shorter times than the mixture containing 100% MNA (around 78 min), which is of great concern at an industrial level. Therefore, thermosetting resins with different mechanical and thermal properties can be obtained by varying the MHO and MNA content.

Activation Capacity of the Intrinsic Musculature of the Foot in Handball Athletes with Chronic Ankle Instability.

Chronic ankle instability (CAI) is a common pathology in handball. The role of the intrinsic musculature of the foot in these players in relation to proprioception and stability has not been stablished. The objective of this study was to compare the ultrasound morphology of the heel fat pad of the foot in professional handball players to CAI in healthy players and establish relationships between CAI and physical and psychological variables. The study has been a descriptive observational case-control study in which 20 professional handball male players over 18 years of age were divided into 8 cases (CAI) and 12 controls (healthy). An ultrasound evaluation, the thickness and/or cross-sectional area at rest and the contraction measurement of the Abductor Digiti Minimi, Abductor Hallucis, Flexor Digitorum Brevis and Quadratus Plantae muscles were analyzed. Moreover, the compressibility index of the heel fat pad and the activation of the abdominal wall musculature (ultrasound), the flexion strength of the hallux and lesser toes (dynamometry), the foot functionality (Bristol Foot Score (BFS) questionnaire) and the psychological variables (self-reported questionnaires) were measured. There were no significant differences between the activation capacity values of the foot muscles of healthy and CAI athletes. Significant differences were found between groups regarding the BFS score (p = 0.007), d = 1.404), and significant correlations were also found between hallux flexion strength and lesser toes flexion strength in the total sample. Although there were no differences between the two groups, the identification of the activation pattern of these muscles in handball athletes is essential to the improvement of performance and preventing injuries such as CAI.

Intra- and inter-session reliability and repeatability of an infrared thermography device designed for materials to measure skin temperature of the triceps surae muscle tissue of athletes.

Background: Infrared thermography devices have been commonly applied to measure superficial temperature in structural composites and walls. These tools were cheaper than other thermographic devices used to measure superficial human muscle tissue temperature. In addition, infrared thermography has been previously used to assess skin temperature related to muscle tissue conditions in the triceps surae of athletes. Nevertheless, the reliability and repeatability of an infrared thermography device designed for materials, such as the Manual Infrared Camera PCE-TC 30, have yet to be determined to measure skin temperature of the triceps surae muscle tissue of athletes. Objective: The purpose was to determine the procedure's intra- and inter-session reliability and repeatability to determine skin temperature within the Manual Infrared Camera PCE-TC 30 thermography device in the triceps surae muscle tissue of athletes, which was initially designed to measure the superficial temperature of materials. Methods: A total of 34 triceps surae muscles were bilaterally assessed from 17 healthy athletes using the Manual Infrared Camera PCE-TC 30 thermography device to determine intra- (at the same day separated by 1 h) and inter-session (at alternate days separated by 48 h) reliability and repeatability of the skin temperature of the soleus, medial and lateral gastrocnemius muscles. The triceps surae complex weas measured by a region of interest of 1 cm2 through five infrared thermography images for each muscle. Statistical analyses comprised intraclass correlation coefficient (ICC), standard error of measurement (SEM), minimum detectable change (MCD), systematic error of measurement, correlation (r), and Bland-Altman plots completed with linear regression models (R 2). Results: Intra- and inter-session measurements of the proposed infrared thermography procedure showed excellent reliability (ICC(1,2) = 0.968-0.977), measurement errors (SEM = 0.186-0.232 °C; MDC = 0.515-0.643 °C), correlations (r = 0.885-0.953), and did not present significant systematic error of measurements (P > 0.05). Adequate agreement between each pair of measurement moments was presented by the Bland-Altman plots according to the limits of agreement and non-significant linear regression models (R 2 = 0.000-0.019; P > 0.05). Conclusions: The proposed procedure to determine skin temperature within the Manual Infrared Camera PCE-TC 30 thermography device presented excellent intra- and inter-session reliability and repeatability in athletes' triceps surae muscle tissue. Future studies should consider the SEM and MDC of this procedure to measure the skin temperature of soleus, medial, and lateral gastrocnemius muscles to promote triceps surae muscle prevention and recovery in athletes.

Dynamic-Mechanical and Decomposition Properties of Flax/Basalt Hybrid Laminates Based on an Epoxidized Linseed Oil Polymer.

This contribution focuses on the development of flax and flax/basalt hybrid reinforced composites based on epoxidized linseed oil (ELO) resin, exploiting the feasibility of different ratios of glutaric anhydride (GA) to maleinized linseed oil (MLO) in the hardener system (50:0, 40:10 and 30:20 wt.%) to provide crosslinked thermosets with balanced properties. The hybrid laminates have been manufactured by resin transfer molding (RTM) and subjected to dynamic-mechanical (DMA) and thermal gravimetry (TGA) analysis. The presence of glutaric anhydride (GA) resulted in hard and relatively brittle flax and flax/basalt laminates, whose loss moduli decreased as the number of basalt plies diminished. Furthermore, the increase in MLO content in the GA:MLO hardener system shifted the glass transition temperatures (Tg) from 70 °C to 59 and 56 °C, which is representative of a decrease in brittleness of the crosslinked resin. All samples exhibited two stages of their decomposition process irrespective of the MLO content. The latter influenced the residual mass content that increased with the increase of the MLO wt.% from 10 to 30 wt.%, with shifts of the final degradation temperatures from 410 °C to 425 °C and 445 °C, respectively.

Manufacturing and Characterization of Environmentally Friendly Wood Plastic Composites Using Pinecone as a Filler into a Bio-Based High-Density Polyethylene Matrix.

The use of wood plastic composites (WPC) is growing very rapidly in recent years, in addition, the use of plastics of renewable origin is increasingly implemented because it allows to reduce the carbon footprint. In this context, this work reports on the development of composites of bio-based high density polyethylene (BioHDPE) with different contents of pinecone (5, 10, and 30 wt.%). The blends were produced by extrusion and injection-molded processes. With the objective of improving the properties of the materials, a compatibilizer has been used, namely polyethylene grafted with maleic anhydride (PE-g-MA 2 phr). The effect of the compatibilizer in the blend with 5 wt.% has been compared with the same blend without compatibilization. Mechanical, thermal, morphological, colorimetric, and wettability properties have been analyzed for each blend. The results showed that the compatibilizer improved the filler-matrix interaction, increasing the ductile mechanical properties in terms of elongation and tensile strength. Regarding thermal properties, the compatibilizer increased thermal stability and improved the behavior of the materials against moisture. In general, the pinecone materials obtained exhibited reddish-brown colors, allowing their use as wood plastic composites with a wide range of properties depending on the filler content in the blend.

Biopolymers from Natural Resources.

During the last decades, the increasing ecology in the reduction of environmental impact caused by traditional plastics is contributing to the growth of more sustainable plastics with the aim to reduce the consumption of non-renewable resources for their production [...].

Development of Polylactic Acid Thermoplastic Starch Formulations Using Maleinized Hemp Oil as Biobased Plasticizer.

In this study, hemp seed oil was reacted with maleic anhydride in an ene reaction to obtain maleinized hemp seed oil (MHO). The use of MHO as a plasticizer and compatibilizer has been studied for polylactic acid (PLA) and thermoplastic starch (TPS) blends (80/20, respectively). By mechanical, thermal and morphological characterizations, the addition of MHO provides a dual effect, acting as plasticizer and compatibilizer between these two partially miscible biopolymers. The addition of MHO up to 7.5 phr (parts by weight of MHO per hundred parts of PLA and TPS) revealed a noticeable increase in the ductile properties, reaching an elongation at break 155% higher than the PLA/TPS blend. Furthermore, contrary to what has been observed with maleinized oils such as linseed oil, the thermal properties do not decrease significantly as a result of the plasticizing effect, due to the compatibilizing behavior of the MHO and the natural antioxidants present in the oil. Finally, a disintegration test was carried out in aerobic conditions at 58 °C, for 24 days, to demonstrate that the incorporation of the MHO, although causing a slight delay, does not impair the biodegradability of the blend, obtaining total degradation in 24 days.

Contribution to a Circular Economy Model: From Lignocellulosic Wastes from the Extraction of Vegetable Oils to the Development of a New Composite.

The present works focuses on the development of a novel fully bio-based composite using a bio-based high-density polyethylene (Bio-HDPE) obtained from sugar cane as matrix and a by-product of extraction of chia seed oil (CO) as filler, with the objective of achieving a circular economy model. The research aims to revalorize an ever-increasing waste stream produced by the growing interest in vegetable oils. From the technical point of view, the chia seed flour (CSF) was chemically modified using a silane treatment. This treatment provides a better interfacial adhesion as was evidenced by the mechanical and thermal properties as well as field emission scanning electron microscopy (FESEM). The effect of silane treatment on water uptake and disintegration rate was also studied. On the other hand, in a second stage, an optimization of the percentage of treated CSF used as filler was carried out by a complete series of mechanical, thermal, morphological, colour, water absorption and disintegration tests with the aim to evaluate the new composite developed using chia by-products. It is noteworthy as the disintegration rate increased with the addition of CSF filler, which leads to obtain a partially biodegradable wood plastic composite (WPC) and therefore, becoming more environmentally friendly.

Comparative Study of the Properties of Plasticized Polylactic Acid with Maleinized Hemp Seed Oil and a Novel Maleinized Brazil Nut Seed Oil.

In this study, for the first time, Brazil nut seed oil was chemically modified with maleic anhydride to obtain maleinized Brazil nut seed oil (MBNO). The same process was developed to obtain maleinized hemp seed oil (MHO). The use of MBNO and MHO was studied as bio-based plasticizers by incorporating them with different contents ranging from 0 to 10 phr in a polylactic acid (PLA) matrix. By means of mechanical, thermal and thermomechanical characterization techniques, the properties of the different formulations were studied to evaluate the plasticizing effect of the MBNO and MHO. With the addition of both plasticizers, a significant increase in ductile properties was observed, reaching an increase in elongation at break of 643% with 7.5 phr MBNO and 771% with 10 phr MHO compared to neat PLA. In addition, it has been observed that the mechanical resistant properties do not decrease, since the oils enhance the crystallization of PLA by increasing the free volume between its chains and counteracting the effect. Finally, a disintegration test was carried out under thermophilic conditions at 58 °C for 27 days, demonstrating that the incorporation of MHO and MBNO does not significantly affect the biodegradability of neat PLA.

Influence of Ultraviolet Radiation Exposure Time on Styrene-Ethylene-Butadiene-Styrene (SEBS) Copolymer.

The effect of ultraviolet radiation on styrene-ethylene-butadiene-styrene (SEBS) has been studied at different exposures times in order to obtain a better understanding of the mechanism of ageing. The polymer materials were mechanically tested and then their surfaces were analyzed using a scanning electron microscope (SEM) and atomic force microscopy (AFM). Moreover, the optical analysis of contact angle (OCA) was used to evaluate the surface energy (γs) and the yellowing index (YI) and attenuated total reflectance infrared spectroscopy (ATR-FTIR) were used to observe structural and physical changes in aging SEBS. The results obtained for the SEBS, in relation to the duration of exposure, showed superficial changes that cause a decrease in the surface energy (γs) and, therefore, a decrease in surface roughness. This led to a reduction in mechanical performance, decreasing the tensile strength by about 50% for exposure times of around 200 h.

Compatibilization and Characterization of Polylactide and Biopolyethylene Binary Blends by Non-Reactive and Reactive Compatibilization Approaches.

In this study, different compatibilizing agents were used to analyze their influence on immiscible blends of polylactide (PLA) and biobased high-density polyethylene (bioPE) 80/20 (wt/wt). The compatibilizing agents used were polyethylene vinyl acetate (EVA) with a content of 33% of vinyl acetate, polyvinyl alcohol (PVA), and dicumyl peroxide (DPC). The influence of each compatibilizing agent on the mechanical, thermal, and microstructural properties of the PLA-bioPE blend was studied using different microscopic techniques (i.e., field emission electron microscopy (FESEM), transmission electron microscopy (TEM), and atomic force microscopy with PeakForce quantitative nanomechanical mapping (AFM-QNM)). Compatibilized PLA-bioPE blends showed an improvement in the ductile properties, with EVA being the compatibilizer that provided the highest elongation at break and the highest impact-absorbed energy (Charpy test). In addition, it was observed by means of the different microscopic techniques that the typical droplet-like structure is maintained, but the use of compatibilizers decreases the dimensions of the dispersed droplets, leading to improved interfacial adhesion, being more pronounced in the case of the EVA compatibilizer. Furthermore, the incorporation of the compatibilizers caused a very marked decrease in the crystallinity of the immiscible PLA-bioPE blend.

On the Use of Phenolic Compounds Present in Citrus Fruits and Grapes as Natural Antioxidants for Thermo-Compressed Bio-Based High-Density Polyethylene Films.

This study originally explores the use of naringin (NAR), gallic acid (GA), caffeic acid (CA), and quercetin (QUER) as natural antioxidants for bio-based high-density polyethylene (bio-HDPE). These phenolic compounds are present in various citrus fruits and grapes and can remain in their leaves, peels, pulp, and seeds as by-products or wastes after juice processing. Each natural additive was first melt-mixed at 0.8 parts per hundred resin (phr) of bio-HDPE by extrusion and the resultant pellets were shaped into films by thermo-compression. Although all the phenolic compounds colored the bio-HDPE films, their contact transparency was still preserved. The chemical analyses confirmed the successful inclusion of the phenolic compounds in bio-HDPE, though their interaction with the green polyolefin matrix was low. The mechanical performance of the bio-HDPE films was nearly unaffected by the natural compounds, presenting in all cases a ductile behavior. Interestingly, the phenolic compounds successfully increased the thermo-oxidative stability of bio-HDPE, yielding GA and QUER the highest performance. In particular, using these phenolic compounds, the onset oxidation temperature (OOT) value was improved by 43 and 41.5 °C, respectively. Similarly, the oxidation induction time (OIT) value, determined in isothermal conditions at 210 °C, increased from 4.5 min to approximately 109 and 138 min. Furthermore, the onset degradation temperature in air of bio-HDPE, measured for the 5% of mass loss (T5%), was improved by up to 21 °C after the addition of NAR. Moreover, the GA- and CA-containing bio-HDPE films showed a high antioxidant activity in alcoholic solution due to their favored release capacity, which opens up novel opportunities in active food packaging. The improved antioxidant performance of these phenolic compounds was ascribed to the multiple presence of hydroxyl groups and aromatic heterocyclic rings that provide these molecules with the features to permit the delocalization and the scavenging of free radicals. Therefore, the here-tested phenolic compounds, in particular QUER, can represent a sustainable and cost-effective alternative of synthetic antioxidants in polymer and biopolymer formulations, for which safety and environmental issues have been raised over time.

Manufacturing and Characterization of Composite Fibreboards with Posidonia oceanica Wastes with an Environmentally-Friendly Binder from Epoxy Resin.

Highly environmentally-friendly fibreboards were manufactured by hot-press moulding using Posidonia ocaeanica wastes and a partially biobased epoxy resin as binder. Fibreboards with a constant fibre content of 70 wt % were successfully manufactured by thermo-compression. The effects of a conventional alkali treatment were compared to the synergistic effects that additional silanization with two silanes (amino and glycidyl) can exert on the mechanical and thermo-mechanical properties of fibreboards. The results revealed a remarkable improvement of the mechanical properties with the combination of the alkali treatment followed by the silanization. Scanning electron microscopy also revealed increased resin-fibre interactions due to the synergistic effect of both amino- and glycidyl-silanes. These fibreboards represent a formaldehyde-free solution and can positively contribute to sustainable development as the lignocellulosic component is a waste and the binder resin is partially biobased.