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.

Incorporation of Argan Shell Flour in a Biobased Polypropylene Matrix for the Development of High Environmentally Friendly Composites by Injection Molding.

In this study, a new composite material is developed using a semi bio-based polypropylene (bioPP) and micronized argan shell (MAS) byproducts. To improve the interaction between the filler and the polymer matrix, a compatibilizer, PP-g-MA, is used. The samples are prepared using a co-rotating twin extruder followed by an injection molding process. The addition of the MAS filler improves the mechanical properties of the bioPP, as evidenced by an increase in tensile strength from 18.2 MPa to 20.8 MPa. The reinforcement is also observed in the thermomechanical properties, with an increased storage modulus. The thermal characterization and X-ray diffraction indicate that the addition of the filler leads to the formation of α structure crystals in the polymer matrix. However, the addition of a lignocellulosic filler also leads to an increased affinity for water. As a result, the water uptake of the composites increases, although it remains relatively low even after 14 weeks. The water contact angle is also reduced. The color of the composites changes to a color similar to wood. Overall, this study demonstrates the potential of using MAS byproducts to improve their mechanical properties. However, the increased affinity with water should be taken into account in potential applications.

Development and Characterization of High Environmentally Friendly Composites of Bio-Based Polyamide 1010 with Enhanced Fire Retardancy Properties by Expandable Graphite.

Bio-based polyamide 1010 was melt-compounded with different percentages (2.5 to 10.0 wt.%) of expandable graphite (EGr) as an environmentally friendly solution to improve the flame retardancy properties. The mechanical, morphological, thermal and fire retardancy properties (among others) are analysed. The novelty of the article lies in the use of fully removable polyamide. The effect of the incorporation of EGr in the properties of this polymer was analysed and characterised. The incorporation of EGr into the PA1010 matrix led to very promising results. Mechanically, the EGr provided increased stiffness and a tensile strength up to 7.5 wt.%, verifying good mechanical performance. The DMTA results also show how the incorporation of EGr in the PA1010 matrix clearly increases the stiffness of the composites over the entire temperature range analysed. In terms of physical properties, water absorption of PA1010 was reduced particularly in the 10% EGr, which reduces the water absorption of PA1010 by 20%. In terms of flame retardant properties, with the incorporation of EGr, a significant reduction in the heat release rate (HRR) values as the concentration of the additive increases and a reduction in the maximum peak heat release rate (pHRR) can be observed for all compounds. In particular, it goes from 934 kW/m2 for neat polyamide to a value of 374 kW/m2 with 10% EGr. Finally, an improvement in the UL-94 rating of the 7.5 and 10% EGr composites was also observed, going from V-2 in the PA to V-1 in these composites.

Upgrading Argan Shell Wastes in Wood Plastic Composites with Biobased Polyethylene Matrix and Different Compatibilizers.

The present study reports on the development of wood plastic composites (WPC) based on micronized argan shell (MAS) as a filler and high-density polyethylene obtained from sugarcane (Bio-HDPE), following the principles proposed by the circular economy in which the aim is to achieve zero waste by the introduction of residues of argan as a filler. The blends were prepared by extrusion and injection molding processes. In order to improve compatibility between the argan particles and the green polyolefin, different compatibilizers and additional filler were used, namely polyethylene grafted maleic anhydride (PE-g-MA 3 wt.-%), maleinized linseed oil (MLO 7.5 phr), halloysite nanotubes (HNTs 7.5 phr), and a combination of MLO and HNTs (3.75 phr each). The mechanical, morphological, thermal, thermomechanical, colorimetric, and wettability properties of each blend were analyzed. The results show that MAS acts as a reinforcing filler, increasing the stiffness of the Bio-HDPE, and that HNTs further increases this reinforcing effect. MLO and PE-g-MA, altogether with HNTs, improve the compatibility between MAS and Bio-HDPE, particularly due to bonds formed between oxygen-based groups present in each compound. Thermal stability was also improved provided by the addition of MAS and HNTs. All in all, reddish-like brown wood plastic composites with improved stiffness, good thermal stability, enhanced compatibility, and good wettability properties were obtained.

Upgrading Recycled Polypropylene from Textile Wastes in Wood Plastic Composites with Short Hemp Fiber.

This research reports the manufacturing and characterization of green composites made from recycled polypropylene obtained from the remnants of polypropylene non-woven fabrics used in the textile industry and further reinforced with short hemp fibers (SHFs). To improve the interaction of the reinforcing fibers with the recycled polymeric matrix, two types of compatibilizing agents (maleic anhydride grafted, PP-g-MA, and maleinized linseed oil, MLO) were added during melt-processing, the percentage of which had to remain constant concerning the amount of fiber loading to ensure complete reactivity. Standardized test specimens were obtained by injection molding. The composites were characterized by mechanical (tensile, impact, and hardness), thermal (DSC, TGA), thermomechanical, FTIR, and FESEM microscopy tests. In addition, color and water uptake properties were also analyzed. The results show that the addition of PP-g-MA to rPP was satisfactory, thus improving the fiber-matrix interaction, resulting in a marked reinforcing effect of the hemp fibers in the recycled PP matrix, which can be reflected in the increased stiffness of the samples. In parallel to the compatibilizing effect, a plasticizing effect was obtained by incorporating MLO, causing a decrease in the glass transition temperature of the composites by approximately 6 °C and an increase in ductility compared to the unfilled recycled polypropylene samples.

Development and Characterization of Weft-Knitted Fabrics of Naturally Occurring Polymer Fibers for Sustainable and Functional Textiles.

This study focuses on the potential uses in textiles of fibers of soy protein (SP) and chitin, which are naturally occurring polymers that can be obtained from agricultural and food processing by-products and wastes. The as-received natural fibers were first subjected to a three-step manufacturing process to develop yarns that were, thereafter, converted into fabrics by weft knitting. Different characterizations in terms of physical properties and comfort parameters were carried out on the natural fibers and compared to waste derived fibers of coir and also conventional cotton and cotton-based fibers, which are widely used in the textile industry. The evaluation of the geometry and mechanical properties revealed that both SP and chitin fibers showed similar fineness and tenacity values than cotton, whereas coir did not achieve the expected properties to develop fabrics. In relation to the moisture content, it was found that the SP fibers outperformed the other natural fibers, which could successfully avoid variations in the mechanical performance of their fabrics as well as impair the growth of microorganisms. In addition, the antimicrobial activity of the natural fibers was assessed against different bacteria and fungi that are typically found on the skin. The obtained results indicated that the fibers of chitin and also SP, being the latter functionalized with biocides during the fiber-formation process, showed a high antimicrobial activity. In particular, reductions of up to 100% and 60% were attained for the bacteria and fungi strains, respectively. Finally, textile comfort was evaluated on the weft-knitted fabrics of the chitin and SP fibers by means of thermal and tactile tests. The comfort analysis indicated that the thermal resistance of both fabrics was similar to that of cotton, whereas their air permeability was higher, particularly for chitin due to its higher fineness, which makes these natural fibers very promising for summer clothes. Both the SP and chitin fabrics also presented relatively similar values of fullness and softness than the pure cotton fabric in terms of body feeling and richness. However, the cotton/polyester fabric was the only one that achieved a good range for uses in winter-autumn cloths. Therefore, the results of this work demonstrate that non-conventional chitin and SP fibers can be considered as potential candidates to replace cotton fibers in fabrics for the textile industry due to their high comfort and improved sustainability. Furthermore, these natural fibers can also serve to develop novel functional textiles with antimicrobial properties.

Manufacturing and Characterization of Highly Environmentally Friendly Sandwich Composites from Polylactide Cores and Flax-Polylactide Faces.

This work focuses on the manufacturing and characterization of highly environmentally friendly lightweight sandwich structures based on polylactide (PLA) honeycomb cores and PLA-flax fabric laminate skins or facings. PLA honeycombs were manufactured using PLA sheets with different thicknesses ranging from 50 to 500 µm. The PLA sheets were shaped into semi-hexagonal profiles by hot-compression molding. After this stage, the different semi-hexagonal sheets were bonded together to give hexagonal panels. The skins were manufactured by hot-compression molding by stacking two Biotex flax/PLA fabrics with 40 wt% PLA fibers. The combined use of temperature (200 °C), pressure, and time (2 min) allowed PLA fibers to melt, flow, and fully embed the flax fabrics, thus leading to thin composite laminates to be used as skins. Sandwich structures were finally obtained by bonding the PLA honeycomb core with the PLA-flax skins using an epoxy adhesive. A thin PLA nonwoven was previously attached to the external hexagonal PLA core, to promote mechanical interlock between the core and the skins. The influence of the honeycomb core thickness on the final flexural and compression properties was analyzed. The obtained results indicate that the core thickness has a great influence on the flexural properties, which increases with core thickness; nevertheless, as expected, the bonding between the PLA honeycomb core and the skins is critical. Excellent results have been obtained with 10 and 20 mm thickness honeycombs with a core shear of about 0.60 and facing bending stresses of 31-33 MPa, which can be considered as candidates for technical applications. The ultimate load to the sample weight ratio reached values of 141.5 N·g-1 for composites with 20 mm thick PLA honeycombs, which is comparable to other technical composite sandwich structures. The bonding between the core and the skins is critical as poor adhesion does not allow load transfer and, while the procedure showed in this research gives interesting results, new developments are necessary to obtain standard properties on sandwich structures.

Improvement of Impact Strength of Polylactide Blends with a Thermoplastic Elastomer Compatibilized with Biobased Maleinized Linseed Oil for Applications in Rigid Packaging.

This research work reports the potential of maleinized linseed oil (MLO) as biobased compatibilizer in polylactide (PLA) and a thermoplastic elastomer, namely, polystyrene-b-(ethylene-ran-butylene)-b-styrene (SEBS) blends (PLA/SEBS), with improved impact strength for the packaging industry. The effects of MLO are compared with a conventional polystyrene-b-poly(ethylene-ran-butylene)-b-polystyrene-graft-maleic anhydride terpolymer (SEBS-g-MA) since it is widely used in these blends. Uncompatibilized and compatibilized PLA/SEBS blends can be manufactured by extrusion and then shaped into standard samples for further characterization by mechanical, thermal, morphological, dynamical-mechanical, wetting and colour standard tests. The obtained results indicate that the uncompatibilized PLA/SEBS blend containing 20 wt.% SEBS gives improved toughness (4.8 kJ/m2) compared to neat PLA (1.3 kJ/m2). Nevertheless, the same blend compatibilized with MLO leads to an increase in impact strength up to 6.1 kJ/m2, thus giving evidence of the potential of MLO to compete with other petroleum-derived compatibilizers to obtain tough PLA formulations. MLO also provides increased ductile properties, since neat PLA is a brittle polymer with an elongation at break of 7.4%, while its blend with 20 wt.% SEBS and MLO as compatibilizer offers an elongation at break of 50.2%, much higher than that provided by typical SEBS-g-MA compatibilizer (10.1%). MLO provides a slight decrease (about 3 °C lower) in the glass transition temperature (Tg) of the PLA-rich phase, thus showing some plasticization effects. Although MLO addition leads to some yellowing due to its intrinsic yellow colour, this can contribute to serving as a UV light barrier with interesting applications in the packaging industry. Therefore, MLO represents a cost-effective and sustainable solution to the use of conventional petroleum-derived compatibilizers.

The Effect of Halloysite Nanotubes on the Fire Retardancy Properties of Partially Biobased Polyamide 610.

The main objective of the work reported here was the analysis and evaluation of halloysite nanotubes (HNTs) as natural flame retardancy filler in partially biobased polyamide 610 (PA610), with 63% of carbon from natural sources. HNTs are naturally occurring clays with a nanotube-like shape. PA610 compounds containing 10%, 20%, and 30% HNT were obtained in a twin-screw co-rotating extruder. The resulting blends were injection molded to create standard samples for fire testing. The incorporation of the HNTs in the PA610 matrix leads to a reduction both in the optical density and a significant reduction in the number of toxic gases emitted during combustion. This improvement in fire properties is relevant in applications where fire safety is required. With regard to calorimetric cone results, the incorporation of 30% HNTs achieved a significant reduction in terms of the peak values obtained of the heat released rate (HRR), changing from 743 kW/m2 to about 580 kW/m2 and directly modifying the shape of the characteristic curve. This improvement in the heat released has produced a delay in the mass transfer of the volatile decomposition products, which are entrapped inside the HNTs' lumen, making it difficult for the sample to burn. However, in relation to the ignition time of the samples (TTI), the incorporation of HNTs reduces the ignition start time about 20 s. The results indicate that it is possible to obtain polymer formulations with a high renewable content such as PA610, and a natural occurring inorganic filler in the form of a nanotube, i.e., HNTs, with good flame retardancy properties in terms of toxicity, optical density and UL94 test.

Assessment of the Mechanical and Thermal Properties of Injection-Molded Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/Hydroxyapatite Nanoparticles Parts for Use in Bone Tissue Engineering.

In the present study, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HHx)] was reinforced with hydroxyapatite nanoparticles (nHA) to produce novel nanocomposites for potential uses in bone reconstruction. Contents of nHA in the 2.5-20 wt % range were incorporated into P(3HB-co-3HHx) by melt compounding and the resulting pellets were shaped into parts by injection molding. The addition of nHA improved the mechanical strength and the thermomechanical resistance of the microbial copolyester parts. In particular, the addition of 20 wt % of nHA increased the tensile (Et) and flexural (Ef) moduli by approximately 64% and 61%, respectively. At the highest contents, however, the nanoparticles tended to agglomerate, and the ductility, toughness, and thermal stability of the parts also declined. The P(3HB-co-3HHx) parts filled with nHA contents of up to 10 wt % matched more closely the mechanical properties of the native bone in terms of strength and ductility when compared with metal alloys and other biopolymers used in bone tissue engineering. This fact, in combination with their biocompatibility, enables the development of nanocomposite parts to be applied as low-stress implantable devices that can promote bone reconstruction and be reabsorbed into the human body.

Development and Characterization of Sustainable Composites from Bacterial Polyester Poly(3-Hydroxybutyrate-co-3-hydroxyhexanoate) and Almond Shell Flour by Reactive Extrusion with Oligomers of Lactic Acid.

Eco-efficient Wood Plastic Composites (WPCs) have been obtained using poly(hydroxybutyrate-co-hexanoate) (PHBH) as the polymer matrix, and almond shell flour (ASF), a by-product from the agro-food industry, as filler/reinforcement. These WPCs were prepared with different amounts of lignocellulosic fillers (wt %), namely 10, 20 and 30. The mechanical characterization of these WPCs showed an important increase in their stiffness with increasing the wt % ASF content. In addition, lower tensile strength and impact strength were obtained. The field emission scanning electron microscopy (FESEM) study revealed the lack of continuity and poor adhesion among the PHBH-ASF interface. Even with the only addition of 10 wt % ASF, these green composites become highly brittle. Nevertheless, for real applications, the WPC with 30 wt % ASF is the most attracting material since it contributes to lowering the overall cost of the WPC and can be manufactured by injection moulding, but its properties are really compromised due to the lack of compatibility between the hydrophobic PHBH matrix and the hydrophilic lignocellulosic filler. To minimize this phenomenon, 10 and 20 phr (weight parts of OLA-Oligomeric Lactic Acid per one hundred weight parts of PHBH) were added to PHBH/ASF (30 wt % ASF) composites. Differential scanning calorimetry (DSC) suggested poor plasticization effect of OLA on PHBH-ASF composites. Nevertheless, the most important property OLA can provide to PHBH/ASF composites is somewhat compatibilization since some mechanical ductile properties are improved with OLA addition. The study by thermomechanical analysis (TMA), confirmed the increase of the coefficient of linear thermal expansion (CLTE) with increasing OLA content. The dynamic mechanical characterization (DTMA), revealed higher storage modulus, E', with increasing ASF. Moreover, DTMA results confirmed poor plasticization of OLA on PHBH-ASF (30 wt % ASF) composites, but interesting compatibilization effects.

Manufacturing and Properties of Binary Blend from Bacterial Polyester Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and Poly(caprolactone) with Improved Toughness.

Polyhydroxyalkanoates (PHAs) represent a promising group of bacterial polyesters for new applications. Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) is a very promising bacterial polyester with potential uses in the packaging industry; nevertheless, as with many (almost all) bacterial polyesters, PHBH undergoes secondary crystallization (aging) which leads to an embrittlement. To overcome or minimize this, in the present work a flexible petroleum-derived polyester, namely poly(ε-caprolactone), was used to obtain PHBH/PCL blends with different compositions (from 0 to 40 PCL wt %) using extrusion followed by injection moulding. The thermal analysis of the binary blends was studied by means of differential scanning calorimetry (DSC) and thermogravimetry (TGA). Both TGA and DSC revealed immiscibility between PHBH and PCL. Mechanical dynamic thermal analysis (DMTA) allowed a precise determination of the glass transition temperatures (Tg) as a function of the blend composition. By means of field emission scanning electron microscopy (FESEM), an internal structure formed by two phases was observed, with a PHBH-rich matrix phase and a finely dispersed PCL-rich phase. These results confirmed the immiscibility between these two biopolymers. However, the mechanical properties obtained through tensile and Charpy tests, indicated that the addition of PCL to PHBH considerably improved toughness. PHBH/PCL blends containing 40 PCL wt % offered an impact resistance double that of neat PHBH. PCL addition also contributed to a decrease in brittleness and an improvement in toughness and some other ductile properties. As expected, an increase in ductile properties resulted in a decrease in some mechanical resistant properties, e.g., the modulus and the strength (in tensile and flexural conditions) decreased with increasing wt % PCL in PHBH/PCL blends.

Evaluation of Different Compatibilization Strategies to Improve the Performance of Injection-Molded Green Composite Pieces Made of Polylactide Reinforced with Short Flaxseed Fibers.

Green composites made of polylactide (PLA) and short flaxseed fibers (FFs) at 20 wt % were successfully compounded by twin-screw extrusion (TSE) and subsequently shaped into pieces by injection molding. The linen waste derived FFs were subjected to an alkalization pretreatment to remove impurities, improve the fiber surface quality, and make the fibers more hydrophobic. The alkali-pretreated FFs successfully reinforced PLA, leading to green composite pieces with higher mechanical strength. However, the pieces also showed lower ductility and toughness and the lignocellulosic fibers easily detached during fracture due to the absence or low interfacial adhesion with the biopolyester matrix. Therefore, four different compatibilization strategies were carried out to enhance the fiber-matrix interfacial adhesion. These routes consisted on the silanization of the alkalized FFs with a glycidyl silane, namely (3-glycidyloxypropyl) trimethoxysilane (GPTMS), and the reactive extrusion (REX) with three compatibilizers, namely a multi-functional epoxy-based styrene-acrylic oligomer (ESAO), a random copolymer of poly(styrene-co-glycidyl methacrylate) (PS-co-GMA), and maleinized linseed oil (MLO). The results showed that all the here-tested compatibilizers improved mechanical strength, ductility, and toughness as well as the thermal stability and thermomechanical properties of the green composite pieces. The highest interfacial adhesion was observed in the green composite pieces containing the silanized fibers. Interestingly, PS-co-GMA and, more intensely, ESAO yielded the pieces with the highest mechanical performance due to the higher reactivity of these additives with both composite components and their chain-extension action, whereas MLO led to the most ductile pieces due to its secondary role as plasticizer for PLA.

Development of Injection-Molded Polylactide Pieces with High Toughness by the Addition of Lactic Acid Oligomer and Characterization of Their Shape Memory Behavior.

This work reports the effect of the addition of an oligomer of lactic acid (OLA), in the 5-20 wt% range, on the processing and properties of polylactide (PLA) pieces prepared by injection molding. The obtained results suggested that the here-tested OLA mainly performs as an impact modifier for PLA, showing a percentage increase in the impact strength of approximately 171% for the injection-molded pieces containing 15 wt% OLA. A slight plasticization was observed by the decrease of the glass transition temperature (Tg) of PLA of up to 12.5 °C. The OLA addition also promoted a reduction of the cold crystallization temperature (Tcc) of more than 10 °C due to an increased motion of the biopolymer chains and the potential nucleating effect of the short oligomer chains. Moreover, the shape memory behavior of the PLA samples was characterized by flexural tests with different deformation angles, that is, 15°, 30°, 60°, and 90°. The obtained results confirmed the extraordinary effect of OLA on the shape memory recovery (Rr) of PLA, which increased linearly as the OLA loading increased. In particular, the OLA-containing PLA samples were able to successfully recover over 95% of their original shape for low deformation angles, while they still reached nearly 70% of recovery for the highest angles. Therefore, the present OLA can be successfully used as a novel additive to improve the toughness and shape memory behavior of compostable packaging articles based on PLA in the new frame of the Circular Economy.