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.

Development and Characterization of Polylactide Blends with Improved Toughness by Reactive Extrusion with Lactic Acid Oligomers.

In this work, we report the development and characterization of polylactide (PLA) blends with improved toughness by the addition of 10 wt.% lactic acid oligomers (OLA) and assess the feasibility of reactive extrusion (REX) and injection moulding to obtain high impact resistant injection moulded parts. To improve PLA/OLA interactions, two approaches are carried out. On the one hand, reactive extrusion of PLA/OLA with different dicumyl peroxide (DCP) concentrations is evaluated and, on the other hand, the effect of maleinized linseed oil (MLO) is studied. The effect of DCP and MLO content used in the reactive extrusion process is evaluated in terms of mechanical, thermal, dynamic mechanical, wetting and colour properties, as well as the morphology of the obtained materials. The impact strength of neat PLA (39.3 kJ/m2) was slightly improved up to 42.4 kJ/m2 with 10 wt.% OLA. Nevertheless, reactive extrusion with 0.3 phr DCP (parts by weight of DCP per 100 parts by weight of PLA-OLA base blend 90:10) led to a noticeable higher impact strength of 51.7 kJ/m2, while the reactive extrusion with 6 phr MLO gave an even higher impact strength of 59.5 kJ/m2, thus giving evidence of the feasibility of these two approaches to overcome the intrinsic brittleness of PLA. Therefore, despite MLO being able to provide the highest impact strength, reactive extrusion with DCP led to high transparency, which could be an interesting feature in food packaging, for example. In any case, these two approaches represent environmentally friendly strategies to improve PLA toughness.

Green Composites from Partially Bio-Based Poly(butylene succinate-co-adipate)-PBSA and Short Hemp Fibers with Itaconic Acid-Derived Compatibilizers and Plasticizers.

In this work, green composites have been developed and characterized using a bio-based polymeric matrix such as BioPBSA and the introduction of 30 wt.% short hemp fibers as a natural reinforcement to obtain materials with maximum environmental efficiency. In order to increase the interfacial adhesion between the matrix and the fiber to obtain better properties in the composites, a reactive extrusion process has been carried out. On the one hand, different additives derived from bio-based itaconic acid have been added to the BioPBSA/HEMP composite, such as dibutyl itaconate (DBI) and a copolymer of PBSA grafted with itaconic acid (PBSA-g-IA). On the other hand, a different copolymer of PBSA grafted with maleic anhydride (PBSA-g-MA) was also tested. The resulting composites have been processed by injection-molding to obtain different samples which were evaluated in terms of mechanical, thermal, chemical, dynamic-mechanical, morphological and wettability and color properties. In relation to the mechanical properties, the incorporation of hemp fibers resulted in an increase in the stiffness of the base polymer. The tensile modulus of pure BioPBSA increased from 281 MPa to 3482 MPa with 30% fiber. The addition of DBI shows a remarkable improvement in the ductility of the composites, while copolymers with IA and MA, generate mechanically balanced composites. In terms of thermal properties, the incorporation of hemp fiber and compatibilizing agents led to a reduction in thermal stability. However, from the point of view of thermomechanical properties, a clear increase in rigidity is achieved throughout the temperature range studied. As far as the color of the samples is concerned, the incorporation of hemp generates a typical color, while the incorporation of the compatibilizing agents does not modify this color excessively. Finally, the introduction of lignocellulosic fibers greatly affects water absorption and contact angle, although the use of additives helped to mitigate this effect.

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 and Characterization of Environmentally Friendly Wood Plastic Composites from Biobased Polyethylene and Short Natural Fibers Processed by Injection Moulding.

Environmentally friendly wood plastic composites (WPC) with biobased high density polyethylene (BioHDPE) as the polymer matrix and hemp, flax and jute short fibers as natural reinforcements, were melt-compounded using twin-screw extrusion and shaped into pieces by injection molding. Polyethylene-graft-maleic anhydride (PE-g-MA) was added at two parts per hundred resin to the WPC during the extrusion process in order to reduce the lack in compatibility between the lignocellulosic fibers and the non-polar polymer matrix. The results revealed a remarkable improvement of the mechanical properties with the combination of natural fibers, along with PE-g-MA, highly improved stiffness and mechanical properties of neat BioHDPE. Particularly, hemp fiber drastically increased the Young's modulus and impact strength of BioHDPE. Thermal analysis revealed a slight improvement in thermal stability with the addition of the three lignocellulosic fibers, increasing both melting and degradation temperatures. The incorporation of the fibers also increased water absorption due to their lignocellulosic nature, which drastically improved the polarity of the composite. Finally, fire behavior properties were also improved in terms of flame duration, thanks to the ability of the fibers to form char protective barriers that isolate the material from oxygen and volatiles.

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.

Kinetic Analysis of the Curing Process of Biobased Epoxy Resin from Epoxidized Linseed Oil by Dynamic Differential Scanning Calorimetry.

The curing process of epoxy resin based on epoxidized linseed oil (ELO) is studied using dynamic differential scanning calorimetry (DSC) in order to determine the kinetic triplet (Ea, f(α) and A) at different heating rates. The apparent activation energy, Ea, has been calculated by several differential and integral isoconversional methods, namely Kissinger, Friedman, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Starink. All methods provide similar values of Ea (between 66 and 69 kJ/mol), and this shows independence versus the heating rate used. The epoxy resins crosslinking is characterized by a multi-step process. However, for the sake of the simplicity and to facilitate the understanding of the influence of the oxirane location on the curing kinetic, this can be assimilated to a single-step process. The reaction model has a high proportion of autocatalytic process, fulfilling that αM is between 0 and αp and αM < αp∞. Using as reference the model proposed by Sesták-Berggren, by obtaining two parameters (n and m) it is possible to obtain, on the one hand, the kinetic parameters and, on the other hand, a graphical comparison of the degree of conversion, α, versus temperature (T) at different heating rates with the average n and m values of this model. The good accuracy of the proposed model with regard to the actual values obtained by DSC gives consistency to the obtained parameters, thus suggesting the crosslinking of the ELO-based epoxy has apparent activation energies similar to other petroleum-derived epoxy resins.

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.

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 Varying the Amount of Short Hemp Fibers on Mechanical and Thermal Properties of Wood-Plastic Composites from Biobased Polyethylene Processed by Injection Molding.

Biobased HDPE (bioHDPE) was melt-compounded with different percentages (2.5 to 40.0 wt.%) of short hemp fibers (HF) as a natural reinforcement to obtain environmentally friendly wood plastic composites (WPC). These WPC were melt-compounded using a twin-screw extrusion and shaped into standard samples by injection molding. To improve the poor compatibility between the high non-polar BioHDPE matrix and the highly hydrophilic lignocellulosic fibers, a malleated copolymer, namely, polyethylene-graft-maleic anhydride (PE-g-MA), was used. The addition of short hemp fibers provided a remarkable increase in the stiffness that, in combination with PE-g-MA, led to good mechanical performance. In particular, 40 wt.% HF drastically increased the Young's modulus and impact strength of BioHDPE, reaching values of 5275 MPa and 3.6 kJ/m2, respectively, which are very interesting values compared to neat bioHDPE of 826 MPa and 2.0 kJ/m2. These results were corroborated by dynamic mechanical thermal analysis (DMTA) results, which revealed a clear increasing tendency on stiffness with increasing the fiber loading over the whole temperature range. The crystal structure was not altered by the introduction of the natural fibers as could be seen in the XRD patterns in which mainly the heights of the main peaks changed, and only small peaks associated with the presence of the fiber appeared. Analysis of the thermal properties of the composites showed that no differences in melting temperature occurred and the non-isothermal crystallization process was satisfactorily described from the combined Avrami and Ozawa model. As for the thermal degradation, the introduction of HF resulted in the polymer degradation taking place at a higher temperature. As for the change in color of the injected samples, it was observed that the increase in fiber generated a clear modification in the final shades of the pieces, reaching colors very similar to dark woods for percentages higher than 20% HF. Finally, the incorporation of an increasing percentage of fibers also increased water absorption due to its lignocellulosic nature in a linear way, which drastically improved the polarity of the composite.

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.

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.

Microencapsulation of Copper(II) Sulfate in Ionically Cross-Linked Chitosan by Spray Drying for the Development of Irreversible Moisture Indicators in Paper Packaging.

Copper(II) sulfate-loaded chitosan microparticles were herein prepared using ionic cross-linking with sodium tripolyphosphate (STPP) followed by spray drying. The microencapsulation process was optimal using an inlet temperature of 180 °C, a liquid flow-rate of 290 mL/h, an aspiration rate of 90%, and an atomizing gas flow-rate of 667 nL/h. Chitosan particles containing copper(II) sulfate of approximately 4 µm with a shrunken-type morphology were efficiently attained and, thereafter, fixated on a paper substrate either via cross-linking with STPP or using a chitosan hydrogel. The latter method led to the most promising system since it was performed at milder conditions and the original paper quality was preserved. The developed cellulose substrates were reduced and then exposed to different humidity conditions and characterized using colorimetric measurements in order to ascertain their potential as irreversible indicators for moisture detection. The results showed that the papers coated with the copper(II) sulfate-containing chitosan microparticles were successfully able to detect ambient moisture shown by the color changes of the coatings from dark brown to blue, which can be easily seen with the naked eye. Furthermore, the chitosan microparticles yielded no cytotoxicity in an in vitro cell culture experiment. Therefore, the cellulose substrates herein developed hold great promise in paper packaging as on-package colorimetric indicators for monitoring moisture in real time.

Injection-Molded Parts of Partially Biobased Polyamide 610 and Biobased Halloysite Nanotubes.

This works focuses on the development of environmentally friendly composites with a partially biobased polyamide 610 (PA610), containing 63% biobased content, and a natural inorganic filler at the nanoscale, namely, halloysite nanotubes (HNTs). PA610 composites containing 10, 20, and 30 wt% HNTs were obtained by melt extrusion in a twin screw co-rotating extruder. The resulting composites were injection-molded for further characterization. The obtained materials were characterized to obtain reliable data about their mechanical, thermal, and morphological properties. The effect of the HNTs wt% on these properties was evaluated. From a mechanical standpoint, the addition of 30 wt% HNTs gave an increase in tensile modulus of twice the initial value, thus verifying how this type of natural load provides increased stiffness on injection molded parts. The materials prepared with HNTs slightly improved the thermal stability, while a noticeable improvement on thermomechanical resistance over a wide temperature range was observed with increasing HNTs content. The obtained results indicate that high biobased content composites can be obtained with an engineering thermoplastic, i.e., PA610, and a natural inorganic nanotube-shaped filler, i.e., HNTs, with balanced mechanical properties and attractive behavior against high temperature.

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.

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.