The Influence of Different Sustainable Silk-Based Fillers on the Thermal and Mechanical Properties of Polylactic Acid Composites.

In this work, different silk fillers combined with maleinized corn oil (MCO), as environmentally friendly plasticizers, were used to modify the mechanical and thermal properties of polylactic acid (PLA) composites. Melt extrusion and injection were used to obtain samples with a content of 10 wt.% of MCO and 0.5 phr of different silk fillers: crushed silk (CS), silk fibroin microparticles (SFM), and silk fibroin nanoparticles (SFN). PLA formulation with 10 wt.% of MCO and 0.5 g of CS per hundred grams of composite (phr) showed the highest increase in mechanical ductile properties with an increase in elongation at break of approximately 1400%, compared with PLA. Differential scanning calorimetry (DSC) showed a decrease of 2 °C in their glass transition temperature with the addition of different silk fillers. In addition, SFM and SFN increase the degree of crystallinity of PLA. This increment was also confirmed by infrared spectroscopy analysis. Field emission scanning electron microscopy (FESEM) images revealed a good dispersion of the different silk fillers. Among them, PLA formulation with 10 wt.% MCO and 0.5 phr of SFN, showed an optimal balance between maximum resistance and elongation at break, with 52.0 MPa and 10.8%, respectively, improving elongation at break by 635%. Furthermore, all samples were satisfactorily disintegrated under composting conditions.

Impact of Traces of Hydrogen Sulfide on the Efficiency of Ziegler-Natta Catalyst on the Final Properties of Polypropylene.

Sulfur compounds are removed from propylene through purification processes. However, these processes are not 100% effective, so low concentrations of compounds such as H2S may be present in polymer-grade propylene. This article studies the effects of H2S content on polypropylene polymerization through the controlled dosage of this compound with concentrations between 0.07 and 5 ppm and its monitoring during the process to determine possible reaction mechanisms and evaluate variations in properties of the material by TGA, FTIR, MFI, and XDR analysis. It was found that the fluidity index increases directly proportional to the concentration of H2S. In addition, the thermo-oxidative degradation is explained by means of the proposed reaction mechanisms of the active center of the Ziegler-Natta catalyst with the H2S molecule and the formation of substances with functional groups such as alcohol, ketones, aldehydes, CO, and CO2 by the oxidation of radical complexes. This study shows for the first time a reaction mechanism between the active center formed for polymerization and H2S, in addition to showing how trace impurities in the raw materials can affect the process, highlighting the importance of optimizing the processes of removal and purification of polymer-grade materials.

Mechanical, Dynamic-Mechanical, Thermal and Decomposition Behavior of 3D-Printed PLA Reinforced with CaCO3 Fillers from Natural Resources.

This study evaluates the effect of CaCO3 fillers extracted from waste eggshells on 3D-printed PLA performance. Samples of neat PLA and PLA reinforced with CaCO3 fillers embedded with different wt.% were prepared using an FDM (fused deposition modeling) technology. The samples were examined using mechanical, dynamic mechanical, thermal, and thermal decomposition analyses. The results revealed increasing elastic moduli, tensile strength, and flexure as the filler content increased. The rheological results from the MFR tests showed that the filler content did not influence the PLA-based samples' processability. Further, the thermal degradation of neat and various CaCO3-wt.%-reinforced PLA specimens revealed relatively small discrepancies in their exposure to the temperature increase, mainly concerning the eggshell organic components and volatile components, from their processability up to 300 °C. By contrast, the increased filler content positively shifted the peaks along the temperature scale at the maximum degradation rate. Additionally, the weight content of the natural reinforcement strongly influenced the surface wettability and appearance of the samples. Further, the SEM analysis featured both the presence of interlayer disturbances and the interfacial compatibility the PLA with the selected fillers.

Gum Rosin as a Size Control Agent of Poly(Butylene Adipate-Co-Terephthalate) (PBAT) Domains to Increase the Toughness of Packaging Formulations Based on Polylactic Acid (PLA).

Gum rosin (GR) was used as a natural additive to improve the compatibility between polylactic acid, PLA, and poly(butylene adipate-co-terephthalate, PBAT, blended with 20 wt.% of PBAT (PLA/PBAT). The PBAT was used as a soft component to increase the ductility of PLA and its fracture toughness. The coalescence of the PBAT domains was possible due to the plasticization effect of the GR component. These domains contributed to increasing the toughness of the final material due to the variation and control of the PBAT domains' size and consequently, reducing the stress concentration points. The GR was used in contents of 5, 10, 15, and 20 phr. Consequently, the flexural properties were improved and the impact resistance increased up to 80% in PLA/PBAT_15GR with respect to the PLA/PBAT formulation. Field emission scanning electron microscope (FESEM) images allowed observing that the size of PBAT domains of 2-3 µm was optimal to reduce the impact stress. Differential scanning calorimetry (DSC) analysis showed a reduction of up to 8 °C on the PLA melting temperature and up to 5.3 °C of the PLA glass transition temperature in the PLA/PBAT_20GR formulation, which indicates an improvement in the processability of PLA. Finally, transparent films with improved oxygen barrier performance and increased hydrophobicity were obtained suggesting the potential interest of these blends for the food packaging industry.

Films Based on Mater-Bi® Compatibilized with Pine Resin Derivatives: Optical, Barrier, and Disintegration Properties.

Mater-Bi® NF866 (MB) was blended with gum rosin and two pentaerythritol esters of gum rosin (labeled as LF and UT), as additives, to produce biobased and compostable films for food packaging or agricultural mulch films. The films were prepared by blending MB with 5, 10, and 15 wt.% of each additive. The obtained films were characterized by optical, colorimetric, wettability, and oxygen barrier properties. Moreover, the additives and the MB-based films were disintegrated under composting conditions and the effect of each additive on the biodegradation rate was studied. All films were homogeneous and optically transparent. The color of the films tended to yellow tones due to the addition of pine resin derivatives. All the formulated films presented a complete UV-transmittance blocking effect in the UVA and UVB region, and those with 5 wt.% of pine resin derivatives increased the MB hydrophobicity. Low amounts of resins tend to maintain the oxygen transmission rate (OTR) values of the neat MB, due to its good solubilizing and compatibilizing effects. The disintegration under composting conditions test revealed that gum rosin completely disintegrates in about 90 days, while UT degrades 80% and LF degrades 5%, over 180 days of incubation. As expected, the same tendency was obtained for the disintegration of the studied films, although Mater-Bi® reach 28% of disintegrability over the 180 days of the composting test.

Films Based on Thermoplastic Starch Blended with Pine Resin Derivatives for Food Packaging.

Completely biobased and biodegradable thermoplastic starch (TPS) based materials with a tunable performance were prepared for food packaging applications. Five blends were prepared by blending TPS with 10 wt%. of different pine resins derivatives: gum rosin (GR), disproportionated gum rosin (RD), maleic anhydride-modified gum rosin (CM), pentaerythritol ester of gum rosin (LF), and glycerol ester of gum rosin (UG). The materials were characterized in terms of thermo-mechanical behavior, surface wettability, color performance, water absorption, X-ray diffraction pattern, and disintegration under composting conditions. It was determined that pine resin derivatives increase the hydrophobicity of TPS and also increase the elastic component of TPS which stiffen the TPS structure. The water uptake study revealed that GR and LF were able to decrease the water absorption of TPS, while the rest of the resins kept the water uptake ability. X-ray diffraction analyses revealed that GR, CM, and RD restrain the aging of TPS after 24 months of aging. Finally, all TPS-resin blends were disintegrated under composting conditions during the thermophilic incubation period (90 days). Because of the TPS-resin blend's performance, the prepared materials are suitable for biodegradable rigid food packaging applications.

Study of the Properties of a Biodegradable Polymer Filled with Different Wood Flour Particles.

Lignocellulosic wood flour particles with three different sizes were used to reinforce Solanyl® type bioplastic in three compositions (10, 20, and 30 wt.%) and further processed by melt-extrusion and injection molding to simulate industrial conditions. The wood flour particles were morphologically and granulometric analyzed to evaluate their use as reinforcing filler. The Fuller method on wood flour particles was successfully applied and the obtained results were subsequently corroborated by the mechanical characterization. The rheological studies allowed observing how the viscosity was affected by the addition of wood flour and to recover information about the processing conditions of the biocomposites. Results suggest that all particles can be employed in extrusion processes (shear rate less than 1000 s-1). However, under injection molding conditions, biocomposites with high percentages of wood flour or excessively large particles may cause an increase in defective injected-parts due to obstruction of the gate in the mold. From a processing point of view and based on the biocomposites performance, the best combination resulted in Solanyl® type biopolymer reinforced with wood flour particles loaded up to 20 wt.% of small and medium particles size. The obtained biocomposites are of interest for injected molding parts for several industrial applications.

Improvement of PBAT Processability and Mechanical Performance by Blending with Pine Resin Derivatives for Injection Moulding Rigid Packaging with Enhanced Hydrophobicity.

Polybutylene adipate-co-terephthalate (PBAT) is a biodegradable polymer with good features for packaging applications. However, the mechanical performance and high prices of PBAT limit its current usage at the commercial level. To improve the properties and reduce the cost of PBAT, pine resin derivatives, gum rosin (GR) and pentaerythritol ester of GR (UT), were proposed as sustainable additives. For this purpose, PBAT was blended with 5, 10, and 15 wt.% of additives by melt-extrusion followed by injection moulding. The overall performance of the formulations was assessed by tensile test, microstructural, thermal, and dynamic mechanical thermal analysis. The results showed that although good miscibility of both resins with PBAT matrix was achieved, GR in 10 wt.% showed better interfacial adhesion with the PBAT matrix than UT. The thermal characterization suggested that GR and UT reduce PBAT melting enthalpy and enhance its thermal stability, improving PBAT processability. A 10 wt.% of GR significantly increased the tensile properties of PBAT, while a 15 wt.% of UT maintained PBAT tensile performance. The obtained materials showed higher hydrophobicity than neat PBAT. Thus, GR and UT demonstrated that they are advantageous additives for PBAT-resin compounding for rigid food packaging which are easy to process and adequate for industrial scalability. At the same time, they enhance its mechanical and hydrophobic performance.

Silane-Functionalized Sheep Wool Fibers from Dairy Industry Waste for the Development of Plasticized PLA Composites with Maleinized Linseed Oil for Injection-Molded Parts.

Poly(lactic acid) (PLA) was plasticized with maleinized linseed oil (MLO) and further reinforced with sheep wool fibers recovered from the dairy industry. The wool fibers were firstly functionalized with 1 and 2.5 phr of tris(2-methoxyethoxy)(vinyl) (TVS) silane coupling agent and were further used in 1, 5, and 10 phr to reinforce the PLA/MLO matrix. Then, the composite materials were processed by extrusion, followed by injection-molding processes. The mechanical, thermal, microstructural, and surface properties were assessed. While the addition of untreated wool fibers to the plasticized PLA/MLO matrix caused a general decrease in the mechanical properties, the TVS treatment was able to slightly compensate for such mechanical losses. Additionally, a shift in cold crystallization and a decrease in the degree of crystallization were observed due to the fiber silane modification. The microstructural analysis confirmed enhanced interaction between silane-modified fibers and the polymeric matrix. The inclusion of the fiber into the PLA/MLO matrix made the obtained material more hydrophobic, while the yellowish color of the material increased with the fiber content.

New Materials for 3D-Printing Based on Polycaprolactone with Gum Rosin and Beeswax as Additives.

In this work, different materials for three-dimensional (3D)-printing were studied, which based on polycaprolactone with two natural additives, gum rosin, and beeswax. During the 3D-printing process, the bed and extrusion temperatures of each formulation were established. After, the obtained materials were characterized by mechanical, thermal, and structural properties. The results showed that the formulation with containing polycaprolactone with a mixture of gum rosin and beeswax as additive behaved better during the 3D-printing process. Moreover, the miscibility and compatibility between the additives and the matrix were concluded through the thermal assessment. The mechanical characterization established that the addition of the mixture of gum rosin and beeswax provides greater tensile strength than those additives separately, facilitating 3D-printing. In contrast, the addition of beeswax increased the ductility of the material, which makes the 3D-printing processing difficult. Despite the fact that both natural additives had a plasticizing effect, the formulations containing gum rosin showed greater elongation at break. Finally, Fourier-Transform Infrared Spectroscopy assessment deduced that polycaprolactone interacts with the functional groups of the additives.

A Deeper Microscopic Study of the Interaction between Gum Rosin Derivatives and a Mater-Bi Type Bioplastic.

The interaction between gum rosin and gum rosin derivatives with Mater-Bi type bioplastic, a biodegradable and compostable commercial bioplastic, were studied. Gum rosin and two pentaerythritol esters of gum rosin (Lurefor 125 resin and Unik Tack P100 resin) were assessed as sustainable compatibilizers for the components of Mater-Bi® NF 866 polymeric matrix. To study the influence of each additive in the polymeric matrix, each gum rosin-based additive was compounded in 15 wt % by melt-extrusion and further injection molding process. Then, the mechanical properties were assessed, and the tensile properties and impact resistance were determined. Microscopic analyses were carried out by field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and atomic force microscopy with nanomechanical assessment (AFM-QNM). The oxygen barrier and wettability properties were also assayed. The study revealed that the commercial thermoplastic starch is mainly composed of three phases: A polybutylene adipate-co-terephthalate (PBAT) phase, an amorphous phase of thermoplastic starch (TPSa), and a semi-crystalline phase of thermoplastic starch (TPSc). The poor miscibility among the components of the Mater-Bi type bioplastic was confirmed. Finally, the formulations with the gum rosin and its derivatives showed an improvement of the miscibility and the solubility of the components depending on the additive used.

Effect of Different Compatibilizers on Injection-Molded Green Fiber-Reinforced Polymers Based on Poly(lactic acid)-Maleinized Linseed Oil System and Sheep Wool.

A method to modify polymers is that of introducing fibers in a matrix to produce a fiber-reinforced polymer (FRP). Consequently, the aim of this work was to study the compatibility effect of four coupling agents on wool FRP properties, using poly(lactic acid) plasticized with maleinized linseed oil as polymer matrix. The content of wool assessed was 1 phr. The compatibilizers were (3-(2-aminoethylamino)propyl)-trimethoxysilane, trimethoxy (2-(7-oxabicyclo (4.1.0)hept-3-yl) ethyl) silane, tris(2-methoxyethoxy)(vinyl) silane and titanium (IV) (triethanolaminate)isopropoxide. Initially, wool was modified with coupling agents in an acetone/water (50/50) solution. Mechanical properties were evaluated by tensile and flexural properties, hardness by Shore D measurement and impact resistance by Charpy's energy. Differential scanning calorimetry, dynamic thermo-mechanical analysis, and thermogravimetric analysis were conducted to evaluate the interaction among components and the effect of the coupling agents on the thermal properties of the original material. Color, wettability and scanning electron microscopy were used to describe physical and microstructural properties. Modification of fibers allows achieving improved mechanical properties and changes the thermal properties of the FRPs slightly. Coupling agent treatment helps to formulate PLA-MLO and sheep wool materials and to improve their performance, thereby creating a broader spectrum of applications for PLA maintaining the bio-based character of the material.

On the Use of PLA-PHB Blends for Sustainable Food Packaging Applications.

Poly(lactic acid) (PLA) is the most used biopolymer for food packaging applications. Several strategies have been made to improve PLA properties for extending its applications in the packaging field. Melt blending approaches are gaining considerable interest since they are easy, cost-effective and readily available processing technologies at the industrial level. With a similar melting temperature and high crystallinity, poly(hydroxybutyrate) (PHB) represents a good candidate to blend with PLA. The ability of PHB to act as a nucleating agent for PLA improves its mechanical resistance and barrier performance. With the dual objective to improve PLAPHB processing performance and to obtain stretchable materials, plasticizers are frequently added. Current trends to enhance PLA-PHB miscibility are focused on the development of composite and nanocomposites. PLA-PHB blends are also interesting for the controlled release of active compounds in the development of active packaging systems. This review explains the most relevant processing aspects of PLA-PHB based blends such as the influence of polymers molecular weight, the PLA-PHB composition as well as the thermal stability. It also summarizes the recent developments in PLA-PHB formulations with an emphasis on their performance with interest in the sustainable food packaging field. PLA-PHB blends shows highly promising perspectives for the replacement of traditional petrochemical based polymers currently used for food packaging.