Implications of the Circular Economy in the Context of Plastic Recycling: The Case Study of Opaque PET.

The use of recycled opaque PET (r-O-PET, with TiO2) as a reinforcement for the recycled polypropylene matrix (r-PP) was evaluated through the life cycle assessment according to different scenarios corresponding to two different recycled blends and considered two virgin raw plastic material as reference materials when comparing the environmental performance of the proposed treatments. The results indicate that the environmental performance was quite different for each blend, since the additional extrusion process required in scenario 2 (blend with TiO2) causes all impact categories analysed to report higher values when compared with scenario 1 (blend without TiO2). The stage that contributes the most corresponds to the different extrusion processes included in both recycling blends, representing at least 80% of the total for global warming. Compared with virgin raw materials, the blend with TiO2 showed better performance in all the impact categories analysed in comparison with virgin PA66, while the blend without TiO2 showed the opposite trend when compared to PP. Furthermore, the fact that the upcycling treatment was carried out on a pilot scale provides room for improvement when implemented on a full scale. It is worth noting the high energy consumption of the treatment processes and their associated cost, in addition to the market cost of virgin raw materials, however, when considering the environmental cost of raw materials, it is observed that when substituting virgin materials PP and PA66 for the blends evaluated in this study results in a reduction of the environmental price of up to 2.5 times.

Improvement of the Thermal Stability of Polymer Bioblends by Means of Reactive Extrusion.

Poly(lactic acid) (PLA) and biosourced polyamide (PA) bioblends, with a variable PA weight content of 10-50%, were manufactured by melt blending in order to improve the behavior of PLA against thermal degradation. The effect of reactive extrusion on the thermal performance of PLA within bioblends was analyzed. The reactive extrusion was made by means of the addition of a styrene-acrylic multi-functional-epoxide oligomeric reactive agent (SAmfE), with the commercial name of Joncryl. Four parameters were considered in order to study the thermal behavior of bioblends against thermal decomposition: the onset decomposition temperature, the shape and temperature interval of the thermal decomposition patterns, the activation energy of the thermal decomposition, and the evidence leading to the most probable mechanism. The latter was determined by means of three evidence: standardized conversion functions, y(α) master plots, and integral mean error. It was shown that reactive extrusion of PLA as well as PA incorporation to the polymer matrix of PLA were responsible for an increase in the onset decomposition temperature of 10.4 °C. The general analytical equation (GAE) was used to evaluate the kinetic parameters of the thermal degradation of PLA within bioblends for various reaction mechanisms. It was shown that the random scission of macromolecular chains is the best mechanism for both untreated and treated PLA by means of reactive extrusion. It was shown that reactive extrusion together with higher content of PA resulted in an increased protective effect against the thermal degradation of PLA as demonstrated by an increase in activation energy of 60 kJ/mol. It was found that there is a relationship between the increase in activation energy and the increase in the onset decomposition temperature when using reactive extrusion. The improvement of the thermal stability of bioblends by means of reactive extrusion was explained by an increase in the complex viscosity from 980 to 2000 Pa·s at 0.06 rad/s and from 250 to 300 Pa·s at 630 rad/s for bioblend containing 30% of PLAREX and by a finer dispersion of PA within the PLAREX matrix. Results from DSC were not conclusive regarding the compatibility between both phases.

Kinetics of the Thermal Degradation of Poly(lactic acid) and Polyamide Bioblends.

Poly(lactic acid) (PLA) and biosourced polyamide (PA) bioblends, with a variable PA weight content of 10-50%, were prepared by melt blending in order to overcome the high brittleness of PLA. During processing, the properties of the melt were stabilized and enhanced by the addition of a styrene-acrylic multi-functional-epoxide oligomeric reactive agent (SAmfE). The general analytical equation (GAE) was used to evaluate the kinetic parameters of the thermal degradation of PLA within bioblends. Various empirical and theoretical solid-state mechanisms were tested to find the best kinetic model. In order to study the effect of PA on the PLA matrix, only the first stage of the thermal degradation was taken into consideration in the kinetic analysis (α < 0.4). On the other hand, standardized conversion functions were evaluated. Given that it is not easy to visualize the best accordance between experimental and theoretical values of standardized conversion functions, an index, based on the integral mean error, was evaluated to quantitatively support our findings relative to the best reaction mechanism. It was demonstrated that the most probable mechanism for the thermal degradation of PLA is the random scission of macromolecular chains. Moreover, y(α) master plots, which are independent of activation energy values, were used to confirm that the selected reaction mechanism was the most adequate. Activation energy values were calculated as a function of PA content. Moreover, the onset thermal stability of PLA was also determined.

Impact of Titanium Dioxide in the Mechanical Recycling of Post-Consumer Polyethylene Terephthalate Bottle Waste: Tensile and Fracture Behavior.

This work provides an experimental analysis regarding the fracture behavior of recycled opaque PET (rPET-O) containing titanium dioxide (TiO2) under plane stress conditions. For this purpose, a commercially post-consumer transparent colored/opaque PET flakes mix was processed using a semi-industrial extrusion calendering process. The manufactured rPET-O sheets had a TiO2 content of 1.45 wt.%. The mechanical and fracture properties of unaged and physically aged (1 year) samples were determined through uniaxial tensile experiments and the Essential Work of Fracture (EWF) methodology, respectively, and were compared to those of recycled transparent PET (rPET-T). Under tensile loading, independently of the aging time, rPET-O samples exhibited similar mechanical behavior as rPET-T up to the yield point. The main differences remained in the post-yielding region. The presence of TiO2 particles allowed reducing the strain energy density up to neck formation in aged samples. Regarding the EWF analysis, it is argued that the energy consumed up to the onset of crack propagation (we) for rPET-T was mainly dependent of the molecular mobility. That is, the we value decreased by 26% when rPET-T was physically aged. Interestingly, we values remained independent of the aging time for rPET-O. In fact, it was highlighted that before crack propagation, the EWF response was principally governed by matrix cavitation ahead of the crack tip, which allowed a significant release of the triaxial stress state independently of the molecular mobility. This property enabled rPET-O to exhibit a resistance to crack initiation 17% higher as compared to rPET-T when the material was physically aged. Finally, independently of the aging time, rPET-O exhibited a resistance to crack growth approximately 21% larger than rPET-T due to matrix fibrillation in large scale deformation.

Innovative One-Shot Paradigm to Tune Filler-Polymer Matrix Interface Properties by Plasma Polymer Coating in Osteosynthesis Applications.

The present study aims to improve the interfacial bonding between hydroxyapatite particles (HAs) and polylactide (PLA) to enhance the mechanical performance and biocompatibility of bone implants based on HA/PLA. For this, one-shot surface functionalization of HA via plasma polymerization is developed. Taking advantage of acetylene plasma chemistry, the hydrophobicity of HA particles was finely tuned prior to their introduction into a PLA matrix via an extrusion process. The effect of the plasma power (20 or 100 W) on the composition of the plasma polymer film (PPF) formed on the HA surface was studied via Fourier transform infrared (FTIR) spectroscopy, time-of-flight secondary-ion mass spectrometry (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). The amount of PPF formed was evaluated via thermogravimetric analyses (TGA). Cytotoxicity of the modified HA particles was monitored by the WST-1 proliferation assay and lactate dehydrogenase (LDH) release and showed that independent on the studied conditions, cell viability remained above the 70% threshold and LDH accumulation changes were insignificant, suggesting good biocompatibility. Contact angle measurements and morphological and rheological analyses showed that the low working power promoted more hydrophobic surfaces and a better HA/PLA interface. Dynamic mechanical analyses revealed that the storage modulus at 37 °C increased for the composite containing functionalized particles by 1.5 times compared to the neat particle's composites. This work opens a route toward further one-shot development of improved scaffolds for bone tissue engineering.

PLA/PA Bio-Blends: Induced Morphology by Extrusion.

The effect of processing conditions on the final morphology of Poly(Lactic Acid) (PLA) with bio-based Polyamide 10.10 (PA) 70/30 blends is analyzed in this paper. Two types of PLA were used: Commercial (neat PLA) and a rheologically modified PLA (PLAREx), with higher melt elasticity produced by reactive extrusion. To evaluate the ability of in situ micro-fibrillation (f) of PA phase during blend compounding by twin-screw extrusion, two processing parameters were varied: i) Screw speed rotation (rpm); and ii) take-up velocity, to induce a hot stretching with different Draw Ratios (DR). The potential ability of PA-f in both bio-blends was evaluated by the viscosity (p) and elasticity (k') ratios determined from the rheological tests of pristine polymers. When PLAREx was used, the requirements for PA-f was fulfilled in the shear rate range observed at the extrusion die. Scanning electron microscopy (SEM) observations revealed that, unlike neat PLA, PLAREx promoted PA-f without hot stretching and the aspect ratio increased as DR increased. For neat PLA-based blends, PA-f was promoted during the hot stretching stage. DMTA analysis revealed that the use of PLAREx PLAREx resulted in a better mechanical performance in the rubbery region (T > Tg PLA-phase) due to the PA-f morphology obtained.

Multifunctional Enzymatically Generated Hydrogels for Chronic Wound Application.

The healing of chronic wounds requires intensive medical intervention at huge healthcare costs. Dressing materials should consider the multifactorial nature of these wounds comprising deleterious proteolytic and oxidative enzymes and high bacterial load. In this work, multifunctional hydrogels for chronic wound application were produced by enzymatic cross-linking of thiolated chitosan and gallic acid. The hydrogels combine several beneficial to wound healing properties, controlling the matrix metalloproteinases (MMPs) and myeloperoxidase (MPO) activities, oxidative stress, and bacterial contamination. In vitro studies revealed above 90% antioxidant activity, and MPO and collagenase inhibition by up to 98 and 23%, respectively. Ex vivo studies with venous leg ulcer exudates confirmed the inhibitory capacity of the dressings against MPO and MMPs. Additionally, the hydrogels reduced the population of the most frequently encountered in nonhealing wounds bacterial strains. The stable at physiological conditions and resistant to lysozyme degradation hydrogels showed high biocompatibility with human skin fibroblasts.