Search Results (11)

This paper presents a detailed analysis of the thermal and flammability properties of polylactide- (PLA) and poly(ethylene terephthalate)- (PET) based polymer blends with biofillers, such as calcium lignosulfonate (CLS), lignosulfonamide (SA) and lignosulfonate modified with tannic acid (BMT) and gallic acid (BMG). Calorimetric studies revealed the presence of two glass transitions, one cold crystallization temperature, and two melting points, confirming the partial immiscibility of the PLA and PET phases. The additives had different effects on the temperatures and ranges of phase transformations—BMT restricted PLA chain mobility, while CLS acted as a nucleating agent that promoted crystallization. Thermogravimetric analyses (TGA) analyses showed that the additives significantly affected the thermal stability under oxidizing conditions, some (e.g., BMG) lowered the onset degradation temperature, while the others (BMT, SA) increased the residual char content. The additives also altered combustion behavior; particularly BMG that most effectively reduced flammability, promoted char formation, and extended combustion time. CLS reduced PET flammability more effectively than PLA, especially at higher PET content (e.g., 65% reduction in PET for 2:1/CLS). SA inhibited only PLA combustion, with strong effects at higher PLA content (up to 76% reduction for 2:1/SA). BMT mainly reduced PET flammability (48% reduction in 1:1/BMT), while BMG inhibited PET more strongly at lower PET content (76% reduction for 2:1/BMG). The effect of each additive also depended on the PLA:PET ratio in the blend. FTIR analysis of the char residues revealed functional groups associated with decomposition products of carboxylic acids and aromatic esters. Ultimately, only blends containing BMT and BMG met the requirements for flammability class FV-1, while SA met FV-2 classification. BMG was the most effective additive, offering enhanced thermal stability, ignition delay, and durable char formation, making it a promising bio- based flame retardant for sustainable polyester materials. Full article

Polyphosphoric acid (PPA) and styrene–butadiene–styrene (SBS) were adopted to produce PPA-SBS-modified bio-blend bitumen, which achieved excellent mechanical performance. However, its long-range performance, such as the fatigue and thermal cracking behavior under long-term thermal oxidation, is not well understood. Therefore, a pressure aging vessel (PAV) system was applied to simulate the aging behavior of the bitumen under the action of thermal oxidation. Then, a linear amplitude sweep (LAS) test combined with a viscoelastic continuum damage (VECD) model was applied to investigate the fatigue properties of the bitumen. Moreover, a bending beam rheometer (BBR) test was conducted to evaluate the thermal cracking resistance of the bitumen before and after PAV aging. Meanwhile, an atomic force microscope (AFM) was applied to observe the microscopic topography. The results show that the original compound-modified bitumen can bear more fatigue damage than that of the control bitumen at the failure point, and it also has excellent fatigue resistance at 2.5%, 5%, 7.5%, and 10% applied strain. Moreover, the VECD model can accurately predict the fatigue life of the bitumen under different applied strains. The variation ratio of stiffness modulus for the compound-modified bitumen is below that of the control bitumen after PAV aging, so it shows a better anti-aging performance. Finally, the AFM test shows that PPA and bio-bitumen decrease the heterogeneity of the bitumen, reducing the difference between phases. Full article

The goal of this work was to investigate the morphological and chemical–physical changes induced by adding ZnO nanoparticles to bio-based polymeric materials based on polylactic acid (PLA) and polyamide 11 (PA11). Precisely, the photo- and water-degradation phenomena of nanocomposite materials were monitored. For this purpose, the formulation and characterization of novel bio-nanocomposite blends based on PLA and PA11 at a ratio of 70/30 wt.% filled with zinc oxide (ZnO) nanostructures at different percentages were performed. The effect of ZnO nanoparticles (≤2 wt.%) within the blends was thoroughly explored by employing thermogravimetry (TGA), size exclusion chromatography (SEC), matrix-assisted laser desorption ionization–time-of-flight mass spectrometry (MALDI-TOF MS) and scanning and transmission electron microscopy (SEM and TEM). Adding up to 1% wt. of ZnO resulted in a higher thermal stability of the PA11/PLA blends, with a decrement lower than 8% in terms of molar masses (MMs) values being obtained during blend processing at 200 °C. ZnO promoted trans-ester-amide reactions between the two polymers, leading to the formation of PLA/PA11 copolymers. These species could work as compatibilisers at the polymer interface, improving thermal and mechanical properties. However, the addition of higher quantities of ZnO affected such properties, influencing the photo-oxidative behaviour and thus thwarting the material’s application for packaging use. The PLA and blend formulations were subjected to natural aging in seawater for two weeks under natural light exposure. The 0.5% wt. ZnO sample induced polymer degradation with a decrease of 34% in the MMs compared to the neat samples. Full article

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 PLA_REX and by a finer dispersion of PA within the PLA_REX matrix. Results from DSC were not conclusive regarding the compatibility between both phases. Full article

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. Full article

Motivated by environment preservation, the increased use of eco-friendly materials such as biodegradable polymers and biopolymers has raised the interest of researchers and the polymer industry. In this approach, this work aimed to produce bioblends using poly (lactic acid) (PLA) and high-density biopolyethylene (BioPE); due to the low compatibility between these polymers, this work evaluated the additional influence of the compatibilizing agents: poly (ethylene octene) and ethylene elastomer grafted with glycidyl methacrylate (POE-g-GMA and EE-g-GMA, respectively), polyethylene grafted with maleic anhydride (PE-g-MA), polyethylene grafted with acrylic acid (PE-g-AA) and the block copolymer styrene (ethylene-butylene)-styrene grafted with maleic anhydride (SEBS-g-MA) to the thermal, mechanical, thermomechanical, wettability and morphological properties of PLA/BioPE. Upon the compatibilizing agents’ addition, there was an increase in the degree of crystallinity observed by DSC (2.3–7.6% related to PLA), in the thermal stability as verified by TG (6–15 °C for T_D10%, 6–11 °C T_D50% and 112–121 °C for T_D99.9% compared to PLA) and in the mechanical properties such as elongation at break (with more expressive values for the addition of POE-g-GMA and SEBS-g-MA, 9 and 10%, respectively), tensile strength (6–19% increase compared to PLA/BioPE bioblend) and a significant increase in impact strength, with evidence of plastic deformation as observed through SEM, promoted by the PLA/ BioPE phases improvement. Based on the gathered data, the added compatibilizers provided higher performing PLA/BioPE. The POE-g-GMA compatibilizer was considered to provide the best properties in relation to the PLA/BioPE bioblend, as well as the PLA matrix, mainly in relation to impact strength, with an increase of approximately 133 and 100% in relation to PLA and PLA/BioPE bioblend, respectively. Therefore, new ecological materials can be manufactured, aiming at benefits for the environment and society, contributing to sustainable development and stimulating the consumption of eco-products. Full article

This work considers the application of eco-friendly, biodegradable materials based on polylactide (PLA) and polyhydroxybutyrate (PHB), instead of conventional polymeric materials, in order to prevent further environmental endangerment by accumulation of synthetic petro-materials. This new approach to the topic is focused on analyzing the processing properties of blends without incorporating any additives that could have a harmful impact on human organisms, including the endocrine system. The main aim of the research was to find the best PLA/PHB ratio to obtain materials with desirable mechanical, processing and application properties. Therefore, two-component polymer blends were prepared by mixing different mass ratios of PLA and PHB (100/0, 50/10, 50/20, 40/30, 50/50, 30/40, 20/50, 10/50 and 0/100 mass ratio) using an extrusion process. The prepared blends were analyzed in terms of thermal and mechanical properties as well as miscibility and surface characteristics. Taking into account the test results, the PLA/PHB blend with a 50/10 ratio turned out to be most suitable in terms of mechanical and processing properties. This blend has the potential to become a bio-based and simultaneously biodegradable material safe for human health dedicated for the packaging industry. Full article

Actually, in order to replace traditional fossil-based polymers, many efforts are devoted to the design and development of new and high-performance bioplastics materials. Poly(hydroxy alkanoates) (PHA_S) as well as polylactides are the main candidates as naturally derived polymers. The intention of the present study is to manufacture fully bio-based blends based on two polyesters: poly (3-hydroxybutyrate) (PHB) and polylactic acid (PLA) as real competitors that could be used to replace petrol polymers in packaging industry. Blends in the shape of films have been prepared by chloroform solvent cast solution methodology, at different PHB/PLA ratios: 1/0, 1/9, 3/7, 5/5, 0/1. A series of dynamic explorations have been performed in order to characterize them from a different point of view. Gas permeability to N₂, O₂, and CO₂ gases and probe (TEMPO) electron spin resonance (ESR) analyses were performed. Blend surface morphology has been evaluated by Scanning Electron Microscopy (SEM) while their thermal behavior was analyzed by Differential Scanning Calorimetry (DSC) technique. Special attention was devoted to color and transparency estimation. Both probe rotation mobility and N₂, O₂, and CO₂ permeation have monotonically decreased during the transition from PLA to PHB, for all contents of bio-blends, namely because of transferring from PLA with lower crystallinity to PHB with a higher one. Consequently, the role of the crystallinity was elucidated. The temperature dependences for CO₂ permeability and diffusivity as well as for probe correlation time allowed the authors to evaluate the activation energy of both processes. The values of gas transport energy activation and TEMPO rotation mobility are substantially close to each other, which should testify that polymer segmental mobility determines the gas permeability modality. Full article

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 (PLA_REx), with higher melt elasticity produced by reactive extrusion. To evaluate the ability of in situ micro-fibrillation (μf) 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-μf in both bio-blends was evaluated by the viscosity (p) and elasticity (k’) ratios determined from the rheological tests of pristine polymers. When PLA_REx was used, the requirements for PA-μf was fulfilled in the shear rate range observed at the extrusion die. Scanning electron microscopy (SEM) observations revealed that, unlike neat PLA, PLA_REx promoted PA-μf without hot stretching and the aspect ratio increased as DR increased. For neat PLA-based blends, PA-μf was promoted during the hot stretching stage. DMTA analysis revealed that the use of PLA_REx PLA_REx resulted in a better mechanical performance in the rubbery region (T > Tg _PLA-phase) due to the PA-μf morphology obtained. Full article

Dense CO₂ can be used as an environmentally-benign polymer processing medium because of its liquid-like densities and gas-like mass transfer properties.In this work, polymer bio-blends of polycarbonate (PC), a biocompatible polymer, and polycaprolactone (PCL), a biodegradable polymer were prepared. Dense CO₂ was used as a reaction medium for the melt-phase PC polymerization in the presence of dense CO₂-swollen PCL particles and this method was used to prepare porous PC/PCL blends. To extend the applicability of dense CO₂ to the biomedical industry and polymer blend processing, the impregnation of ibuprofen into the blend was conducted and subsequent dissolution characteristics were observed. Full article