Polyhydroxy-3-Butyrate (PHB)-Based Composite Materials Reinforced with Cellulosic Fibers, Obtained from Barley Waste Straw, to Produce Pieces for Agriculture Applications: Production, Characterization and Scale-Up Analysis.

Cellulosic fibers obtained from Barley straw were utilized to reinforce PHB. Four different processed fibers were employed as reinforcing material: sawdust (SW), defibered (DFBF), delignified (DBF), and bleached (BBF) fibers. The composite was processed from two different perspectives: a discontinuous (bach) and an intensification process (extrusion). Once processed and transformed into final shape specimens, the materials were characterized by mechanical testing (tensile mode), scanning electron microscopy, and theoretical simulations by finite elements analysis (FEA). In terms of mechanical properties, only the elastic moduli (Et) exhibited results ranging from 37% to 170%, depending on the reinforcement composition. Conversely, strengths at break, under both tensile and bending tests, tended to decrease, indicating poor affinity between the components. Due to the mechanical treatment applied on the fiber, DFBF emerged as the most promising filler, with mechanical properties closest to those of neat PHB. DFBF-based composites were subsequently produced through process intensification using a twin-screw extruder, and molded into flowerpots. Mechanical results showed almost identical properties between the discontinuous and intensification processes. The suitability of the material for agriculture flowerpots was demonstrated through finite analysis simulation (FEA), which revealed that the maximum von Mises stresses (5.38 × 105 N/m2) and deformations (0.048 mm) were well below the limits of the composite materials.

A Comprehensive Study on the Effect of Plasticizers on the Characteristics of Polymer Inclusion Membranes (PIMs): Exploring Butyl Stearate as a Promising Alternative.

This study investigated the influence of various plasticizers commonly used in the manufacture of polymer inclusion membranes (PIMs), such as 2-nitrophenyl octyl ether (NPOE), phthalates, adipates, and sebacates on the mechanical, thermal, and transport properties of membranes. Additionally, butyl stearate (BTS), chosen for its non-toxic nature compared to phthalates and its cost-effectiveness relative to adipates and sebacates, was evaluated as a plasticizer in PIMs for the first time. All plasticizers were incorporated in PIMs made of either cellulose triacetate (CTA) or poly(vinyl chloride) (PVC) as the base polymers and the task-specific ionic liquid trioctylmethylammonium thiosalicylate (TOMATS) as the carrier. The plasticizers were found to significantly affect the characteristics of membrane hydrophilicity, mechanical flexibility, and thermal stability. Transport experiments using Hg(II) as a model target ion revealed that, for CTA-based PIMs, the plasticizer did not significantly affect transport efficiency. However, for PVC-based PIMs, BTS exhibited better efficiency when compared to NPOE. These findings highlight the potential of BTS as an attractive alternative to currently used plasticizers in PVC-based PIM formulations.

Effect of Extruder Type in the Interface of PLA Layers in FDM Printers: Filament Extruder Versus Direct Pellet Extruder.

FDM (Fused Deposition Modeling) is one of the most used and industrially applied additive manufacturing processes due to its fast prototyping and manufacturing, simplicity, and low cost of the equipment. However, the mechanical properties of the printed products have a large dependence on orientation and interface strength between layers which is mainly related to the thermal union obtained. This thermal union has a large dependence on the melting and cooling down process. Additionally, the materials used must be extruded in a continuous filament before their use, which limits the materials used. However, a pellet extruder could be used directly in the printing equipment, avoiding filament extrusion. In this work, specimens of PLA (Poly(lactic acid)) with different bead orientations have been produced via filament or pellet extrusion to compare the effect of the different melting processes in the manufacturing methodology. Pellet extruded specimens showed higher infill and mechanical properties. These results were related to better adhesion between layers due to the longer melting and cooling process. The result was confirmed using DSC and XRD techniques, where a higher crystallinity was observed. A bicomponent specimen (50% pellet-50% filament) was prepared and tested, showing higher mechanical results than expected, which was, again, due to the better thermal union obtained in the pellet extruder.

Simulated Environmental Conditioning of PHB Composites Reinforced with Barley Fibres to Determine the Viability of Their Use as Plastics for the Agriculture Sector.

Nowadays, the search for new materials with a sustainable character to reduce the production of residues is under continuous research. In this sense, fully biodegradable composites based on polyhydroxybutyrate and different pretreated fibres coming from barley straw have been fabricated, and their resistance to environmental controlled conditions have been characterized. The materials were already compounded in a kinetic mixer and injection-moulded as specimens for tensile assay to be aged in a Xenotest chamber so as to simulate environmental conditioning. The samples, after accelerated aging, were characterized thus: mechanical characterization (tensile assay), water uptake (immersion and contact angle), and surface observation (optical and SEM microscopy). The incorporation of the fibres helps the composite to keep its structure for a longer time. On the other hand, the presence of the fibres increases the water uptake capacity to allow water permeation in the composite, which allows final degradation, characterised by a significant drop in properties after one month of exposure to simulated environmental conditions.

Maleic Anhydride Polylactic Acid Coupling Agent Prepared from Solvent Reaction: Synthesis, Characterization and Composite Performance.

In the present work, a functionalization of polylactic acid (PLA) has been carried out to anchor maleic anhydride onto the main polymer chain to promote improvement in the compatibility of this polymer matrix with cellulose fibres. Low-molecular-weight PLA has been reacted with maleic anhydride following different procedures: a bulk reaction in an internal mixer and a solution reaction. The presence of oxygen during bulk processing did not allow for functionalization, guiding the reaction towards a decrease in the molecular weight of the material. On the contrary, a controlled reaction under an inert atmosphere in the presence of dioxane as the solvent, at reflux temperature, led to the functionalization of the polymer reaching different yields depending on the percentage of radical initiator and maleic anhydride added and reaction time. The yield of functionalization has been monitored by acid number titration as well as 1H NMR, with optimal yield values of functionalization being up to 3.5%. The PLA-functionalized formula has been used to make commercial PLA compatible with cellulose fibres derived from a thermomechanical treatment. The addition of 10% w/w of fibres to PLA increases the ultimate tensile strength (UTS) of PLA by up to 15%. The incorporation of 4 w/w of the already-functionalized coupling agent to the composite produces improvements in UTS of up to 24% regarding PLA, which confirms the functionalization from a performance point of view.

Multicolor PEGDA/LCNF Hydrogel in the Presence of Red Cabbage Anthocyanin Extract.

Colorimetric indicator gels were developed by incorporating anthocyanin (AC) obtained from red cabbage into poly (ethylene glycol) diacrylate (PEGDA)-based hydrogel containing lignocellulose nanofiber (LCNF). The PEGDA-based hydrogel was prepared by mixing all of the mentioned components at the specific composition, and the hydrogels were cured under UV light (245 nm) for 1 min. The pH-response, UV absorption, swelling ratio, and mechanical properties of PEGDA/LCNF were determined. It was further found that PEGDA and LCNF mount play an important role in adjusting the mechanical properties of PEGDA/LCNF. In general, the presence of LCNF improved the mechanical properties and swelling ratio of PEGDA. The incorporation of red cabbage anthocyanin into the PEGDA/LCNF film showed multicolor response when specific pH buffers were introduced. Based on the multicolor response of PEGDA/LCNF/CA, this gel film indicator can be developed as a food freshness indicator that focuses on the detection of ammonia and amine compound.

Nanoclay Effect into the Biodegradation and Processability of Poly(lactic acid) Nanocomposites for Food Packaging.

One of the most promising expectations in the design of new materials for food packaging is focused on the development of biodegradable systems with improved barrier character. In this sense PLA reinforced with nanoclay is a potential alternative to the use of conventional oil-derivative polymers due to the synergetic effect of the biodegradable character of PLA and the barrier-induced effect derived from the dispersion of nanoparticles. In this work, composite materials based on PLA and reinforced with bentonite nanoparticles (up to 4% w/w) (NC) have been prepared to produce films with improved barrier character against water vapor transportation. Additionally, the biodegradable character of the composites depending on the crystallinity of the polymer and percentage of NC have been evaluated in the presence of an enzymatic active medium (proteinase K). Finally, a study of the capacity to film production of the composites has been performed to determine the viability of the proposals. The dispersion of the nanoparticles induced a tortuous pathway of water vapor crossing, reducing this diffusion by more than 22%. Moreover, the nanoclays materials were in all the cases acceptable for food packing in terms of migration. A migration lower than 1 mg/m2 was obtained in all the materials. Nonetheless, the presence of the nanoclays in decreased biodegradable capacity was observed. The time was enlarged to more than 15 days for the maximum content (4% w/w). On the other hand, the incorporation of NC does not avoid the processability of the material to obtain film-shaped processed materials.

Manufacturing PLA/PCL Blends by Ultrasonic Molding Technology.

Ultrasonic molding (USM) is a good candidate for studying the plasticization of polymer mixtures or other composite materials due to either the little amount of material needed for processing, low waste or the needed low pressure and residence time of the mold. Thus, the novelty of this research is the capability of USM technology to process PLA/PCL blends and their corresponding neat materials, encompassing all the production stages, from raw material to the final specimen. The major findings of the work revealed that the thermal properties of the blends were not affected by the USM process, although the crystallinity degree experienced variations, decreasing for PLA and increasing for PCL, which was attributed to the crystallization rate of each polymer, the high process speed, the short cooling time and the small particle size. The employed ultrasonic energy increased the molecular weight with low variations through the specimen. However, the degradation results aligned with the expected trend of these material blends. Moreover, this study also showed the effect pellet shape and dimensions have over the process parameters, as well as the effect of the blend composition. It can be concluded that USM is a technology suitable to successfully process PLA/PCL blends with the correct determination of process parameter windows.

Nanocomposites Materials of PLA Reinforced with Nanoclays Using a Masterbatch Technology: A Study of the Mechanical Performance and Its Sustainability.

Packaging consumes around 40% of the total plastic production. One of the most important fields with high requirements is food packaging. Food packaging products have been commonly produced with petrol polymers, but due to environmental concerns, the market is being moved to biopolymers. Poly (lactic acid) (PLA) is the most promising biopolymer, as it is bio-based and biodegradable, and it is well established in the market. Nonetheless, its barrier properties need to be enhanced to be competitive with other polymers such as polyethylene terephthalate (PET). Nanoclays improve the barrier properties of polymeric materials if correct dispersion and exfoliation are obtained. Thus, it marks a milestone to obtain an appropriate dispersion. A predispersed methodology is proposed as a compounding process to improve the dispersion of these composites instead of common melt procedures. Afterwards, the effect of the polarity of the matrix was analyzing using polar and surface modified nanoclays with contents ranging from 2 to 8% w/w. The results showed the suitability of the predispersed and concentrated compound, technically named masterbatch, to obtain intercalated structures and the higher dispersion of polar nanoclays. Finally, the mechanical performance and sustainability of the prepared materials were simulated in a food tray, showing the best assessment of these materials and their lower fingerprint.

Impact Strength and Water Uptake Behavior of Bleached Kraft Softwood-Reinforced PLA Composites as Alternative to PP-Based Materials.

The research toward environmentally friendly materials has devoted a great effort on composites based on natural fiber-reinforced biopolymers. These materials have shown noticeable mechanical properties, mainly tensile and flexural strengths, as a consequence of increasingly strong interfaces. Previous studies have shown a good interface between natural fibers and poly (lactic acid) (PLA) when these fibers present a low lignin content in their surface chemical composition (bleached fibers). Nonetheless, one of the main drawbacks of these materials is the hydrophilicity of the reinforcements in front of the mineral ones like glass fiber. Meanwhile, the behavior of such materials under impact is also of importance to evaluate its usefulness. This research evaluates the water uptake behavior and the impact strength of bleached Kraft softwood-reinforced PLA composites that have been reported to show noticeable tensile and flexural properties. The paper explores the differences between these bio-based materials and commodity composites like glass fiber-reinforced polypropylene.

Effect of NaOH Treatment on the Flexural Modulus of Hemp Core Reinforced Composites and on the Intrinsic Flexural Moduli of the Fibers.

This paper describes the potential of using hemp core waste in the composite industry. These lignocellulosic residues can be used to produce environmentally friendly and economically viable composites and improve the overall value chain of hemp production. To this purpose, hemp core residues were alkaline treated at different NaOH concentrations and then mechanically defibrated. Hemp core fibers were mixed with polypropylene and injection molded to obtain testing specimens. The effect of sodium hydroxide on the flexural modulus of composites was studied from macro and micro mechanical viewpoints. Results showed remarkable improvements in the flexural modulus due to the presence of hemp core fibers in the composites. At a 50 wt % of reinforcement content, increments around 239%, 250% and 257% were obtained for composites containing fibers treated at a 5, 7.5 and 10 wt % of NaOH, respectively. These results were comparable to those of wood composites, displaying the potential of hemp core residues. The intrinsic flexural modulus of the hemp core fibers was computed by means of micromechanical analysis and was calculated using the ratios between a fiber flexural modulus factor and a fiber tensile modulus factor. The results agreed with those obtained by using models such as Hirsch and Tsai-Pagano. Other micromechanical parameters were studied to fully understand the contribution of the phases. The relationship between the fibers' intrinsic flexural and Young's moduli was studied, and the differences between properties were attributed to stress distribution and materials' anisotropy.

Improved Process to Obtain Nanofibrillated Cellulose (CNF) Reinforced Starch Films with Upgraded Mechanical Properties and Barrier Character.

Nowadays, the interest on nanofibrillated cellulose (CNF) has increased owing to its sustainability and its capacity to improve mechanical and barrier properties of polymeric films. Moreover, this filler shows some drawbacks related with its high capacity to form aggregates, hindering its dispersion in the matrix. In this work, an improved procedure to optimize the dispersability of CNF in a thermoplastic starch was put forward. On the one hand, CNF needs a hydrophilic dispersant to be included in the matrix, and on the other, starch needs a hydrophilic plasticizer to obtain a thermoformable material. Glycerol was used to fulfil both targets at once. CNF was predispersed in the plasticizer before nanofibrillation and later on was included into starch, obtaining thin films. The tensile strength of these CNF-starch composite films was 60% higher than the plain thermoplastic starch at a very low 0.36% w/w percentage of CNF. The films showed a noticeable correlation between water uptake, and temperature and humidity. Regarding permeability, a ca. 55% oxygen and water vapor permeability drop was found by nanofiller loading. The hydrolytic susceptibility of the composite was confirmed, being similar to that of the thermoplastic starch.

Towards More Sustainable Material Formulations: A Comparative Assessment of PA11-SGW Flexural Performance versus Oil-Based Composites.

The replacement of commodity polyolefin, reinforced with glass fiber (GF), by greener alternatives has been a topic of research in recent years. Cellulose fibers have shown, under certain conditions, enough tensile capacities to replace GF, achieving competitive mechanical properties. However, if the objective is the production of environmentally friendlier composites, it is necessary to replace oil-derived polymer matrices by bio-based or biodegradable ones, depending on the application. Polyamide 11 (PA11) is a totally bio-based polyamide that can be reinforced with cellulosic fibers. Composites based on this polymer have demonstrated enough tensile strength, as well as stiffness, to replace GF-reinforced polypropylene (PP). However, flexural properties are of high interest for engineering applications. Due to the specific character of short-fiber-reinforced composites, significant differences are expected between the tensile and flexural properties. These differences encourage the study of the flexural properties of a material prior to the design or development of a new product. Despite the importance of the flexural strength, there are few works devoted to its study in the case of PA11-based composites. In this work, an in-depth study of the flexural strength of PA11 composites, reinforced with Stoneground wood (SGW) from softwood, is presented. Additionally, the results are compared with those of PP-based composites. The results showed that the SGW fibers had lower strengthening capacity reinforcing PA11 than PP. Moreover, the flexural strength of PA11-SGW composites was similar to that of PP-GF composites.

Impact Strength and Water Uptake Behaviors of Fully Bio-Based PA11-SGW Composites.

Composite materials have attracted the attention of some industrial fields due to their lightness and relatively good mechanical properties. One of these properties is impact strength, essential to ensure the processability and application of these materials under impact conditions. In addition, it is known that water absorption has a plasticizing effect in polymers and polymer composites which can change the properties of such materials and limit their use. Moreover, this effect worsens when hydrophilic reinforcement is used. In this work, the impact and water uptake behavior of totally bio-based composites from polyamide 11 (PA11) and lignocellulosic pine fibers mechanically processed as stone groundwood (SGW) were studied. The impact resistance of PA11 and its composites was higher than expected, obtaining better results than those of polyolefin-based materials. The evaluated mechanical properties and the micrographs showed an adequate interface. The water uptake test showed that PA11 and its composites had non-Fickian and Fickian case I behaviours, respectively. It was found that the maximum water absorbance was similar to that of SGW reinforced polypropylene.

Evaluation of Thermal and Thermomechanical Behaviour of Bio-Based Polyamide 11 Based Composites Reinforced with Lignocellulosic Fibres.

In this work, polyamide 11 (PA11) and stone ground wood fibres (SGW) were used, as an alternative to non-bio-based polymer matrices and reinforcements, to obtain short fibre reinforced composites. The impact of the reinforcement on the thermal degradation, thermal transitions and microstructure of PA11-based composites were studied. Natural fibres have lower degradation temperatures than PA11, thus, composites showed lower onset degradation temperatures than PA11, as well. The thermal transition and the semi-crystalline structure of the composites were similar to PA11. On the other hand, when SGW was submitted to an annealing treatment, the composites prepared with these fibres increased its crystallinity, with increasing fibre contents, compared to PA11. The differences between the glass transition temperatures of annealed and untreated composites decreased with the fibre contents. Thus, the fibres had a higher impact in the composites mechanical behaviour than on the mobility of the amorphous phase. The crystalline structure of PA11 and PA11-SGW composites, after annealing, was transformed to α' more stable phase, without any negative impact on the properties of the fibres.

Oxidized dextrins as alternative crosslinking agents for polysaccharides: application to hydrogels of agarose-chitosan.

Hydrogel networks that combine suitable physical and biomechanical characteristics for tissue engineering scaffolds are in demand. The aim of this work was the development of hydrogel networks based on agarose and chitosan using oxidized dextrins as low cytotoxicity crosslinking agents, paying special attention to the study of the influence of the polysaccharide composition and oxidation degree of the dextrins in the final characteristics of the network. The results show that the formation of an interpenetrating or a semi-interpenetrating polymer network was mainly dependent on a minimum agarose content and degree of oxidation of dextrin. Spectroscopic, thermal and swelling analysis revealed good compatibility with an absence of phase separation of polysaccharides at agarose:chitosan proportions of 50:50 and 25:75. The analysis of atomic force microscopy images showed the formation of a fibrillar microstructure whose distribution within the crosslinked chitosan depended mainly on the crosslinker. All materials exhibited the viscoelastic behaviour typical of gels, with a constant storage modulus independent of frequency for all compositions. The stiffness was strongly influenced by the degree of oxidation of the crosslinker. Cellular response to the hydrogels was studied with cells of different strains, and cell adhesion and proliferation was correlated with the homogeneity of the samples and their elastic properties. Some hydrogel formulations seemed to be candidates for tissue engineering applications such as wound healing or soft tissue regeneration.

Bioresorbable and nonresorbable polymers for bone tissue engineering.

In recent years, bone tissue engineering has emerged as one of the main research areas in the field of regenerative biomedicine. Frequency and relevance age-related diseases, such as healing and regeneration of bone tissues, are rising due to increasing life expectancy. Even though bone tissue has excellent self-regeneration ability, when bone defects exceed a critical size, impaired bone formation can occur and surgical intervention becomes mandatory. Bone tissue engineering represents an alternative approach to conventional bone transplants. The main aim of tissue engineering is to repair, regenerate or reconstruct damaged or degenerative tissue. This review presents an overview on the main materials, techniques and strategies in the field of bone tissue engineering. Whilst presenting some reviews recently published that deepen on each of the sections of the paper, this review article aims to present some of the most relevant advances, both in terms of new materials and strategies, currently being developed for bone repair and regeneration.