Biodegradable poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-PEG-PLLA) triblock copolymer could potentially be used in bioplastic applications because it is more flexible than PLLA. However, investigations into modifying PLLA-PEG-PLLA with effective fillers are still required. In this work, bamboo biochar (BC) was used as an eco-friendly and cost-effective filler for the flexible PLLA-PEG-PLLA. The influences of BC addition on crystallization properties, thermal stability, hydrophilicity, and mechanical properties of the PLLA-PEG-PLLA were explored and compared to those of the PLLA. The PLLA-PEG-PLLA matrix and BC filler were found to have strong interfacial adhesion and good phase compatibility, while the PLLA/BC composites displayed weak interfacial adhesion and poor phase compatibility. For the PLLA-PEG-PLLA, the addition of BC induced a nucleation effect that was characterized by a decrease in the cold crystallization temperature from 76 to 71-75 °C and an increase in the crystallinity from 18.6 to 21.8-24.0%; however, this effect was not observed for the PLLA. When compared to pure PLLA-PEG-PLLA, the PLLA-PEG-PLLA/BC composites displayed greater thermal stability, tensile stress, and Young\'s modulus. Temperature at maximum decomposition rate (Td,max) of PLLA end-blocks increased from 315 to 319-342 °C. Ultimate tensile stress of PLLA-PEG-PLLA matrix improved from 14.5 to 16.2-22.6 MPa and Young\'s modulus increased from 220 to 280-340 MPa. Based on the findings, the crystallizability, thermal stability, and mechanical properties of the flexible PLLA-PEG-PLLA bioplastic were all enhanced by the use of BC as a multi-functional filler.

Globally, the demand for single-use plastics has increased due to the rising demand for food delivery and household goods. This has led to environmental challenges caused by indiscriminate dumping and disposal. To address this issue, non-degradable plastics are being replaced with biodegradable alternatives. Polylactic acid (PLA) is a type of biodegradable plastic that has excellent mechanical properties. However, its applications are limited due to its low crystallinity and brittleness. Studies have been conducted to combat these limitations using carbon or inorganic nucleating agents. In this study, waste cement and PLA were mixed to investigate the effect of the hybrid inorganic nucleating agent on the crystallinity and mechanical properties of PLA. Waste cement accelerated the lamellar growth of PLA and improved its crystallinity. The results indicate that the flexural and impact strengths increased by approximately 3.63% and 76.18%, respectively.

Eco-friendly poly(L-lactic acid) (PLA) can be made more versatile, and its crystallization rate is accelerated by adding Zinc-based metal-organic framework (Zn-MOF) particles. Using differential scanning calorimetry (DSC), the non-isothermal melt crystallization behavior of biodegradable PLA nucleated by 0.3 to 3 wt% of Zn-MOF was examined. The non-isothermal melt crystallization kinetics parameters were determined using a modified Avrami model and Mo approach. Zn-MOF dramatically accelerated the crystallization process, as evidenced by several non-isothermal crystallization metrics, including the crystallization half-time and crystallization rate constant. The melt crystallization temperatures of the PLA-Zn-MOF composites, with contents of 0.7 and 1 wt%, were increased by 21 °C compared to the neat PLA. Using the Friedman isoconversional kinetic method, the neat PLA and PLA-Zn-MOF composites\' effective activation energy values, ∆E, were determined. The ∆E values of PLA-Zn-MOF from 0.3 to 1 wt% Zn-MOF composites were lower than that of neat PLA. Moreover, polarized optical microscopy revealed the formation of numerous small-sized PLA spherulites upon Zn-MOF addition. The results indicate that the Zn-MOF (at concentrations of 0.7 to 1.0 wt%) can be used as an efficient nucleating agent for PLA, where it increases the melt crystallization temperature, nucleation density, and crystallinity without changing the crystalline structure, while also significantly reduces the effective activation energy and the size of spherulites. Additionally, scanning electron microscopy confirms good dispersion of Zn-MOF (0.3 to 1 wt%) within the PLA matrix.

Current research on materials engineering focuses mainly on bio-based materials. One of the most frequently studied materials in this group is polylactide (PLA), which is a polymer derived from starch. PLA does not have a negative impact on the natural environment and additionally, it possesses properties comparable to those of industrial polymers. The aim of the work was to investigate the potential of organosilicon compounds as modifiers of the mechanical and rheological properties of PLA, as well as to develop a new method for conducting mechanical property tests through innovative high-throughput technologies. Precise dosing methods were utilized to create PLA/silicone polymer blends with varying mass contents, allowing for continuous characterization of the produced blends. To automate bending tests and achieve comprehensive characterization of the blends, a self-created workstation setup has been used. The tensile properties of selected blend compositions were tested, and their ability to withstand dynamic loads was studied. The blends were characterized through various methods, including rheological (MFI), X-ray (XRD), spectroscopic (FTIR), and thermal properties analysis (TG, DSC, HDT), and they were evaluated using microscopic methods (MO, SEM) to examine their structures.

Sorbitol derivatives and other additives are commonly used in various products, such as packaging or food packaging, to improve their mechanical, physical, and optical properties. To accurately and precisely evaluate the efficacy of adding sorbitol-type nucleating agents to these articles, their quantitative determination is essential. This study systematically investigated the quantification of sorbitol-type nucleating agents in food packaging made from impact copolymers of polypropylene (PP) and polyethylene (PE) using attenuated total reflectance infrared spectroscopy (ATR-FTIR) together with analysis of principal components (PCA) and machine learning algorithms. The absorption spectra revealed characteristic bands corresponding to the C-O-C bond and hydroxyl groups attached to the cyclohexane ring of the molecular structure of sorbitol, providing crucial information for identifying and quantifying sorbitol derivatives. PCA analysis showed that with the selected FTIR spectrum range and only the first two components, 99.5% of the variance could be explained. The resulting score plot showed a clear pattern distinguishing different concentrations of the nucleating agent, affirming the predictability of concentrations based on an impact copolymer. The study then employed machine learning algorithms (NN, SVR) to establish prediction models, evaluating their quality using metrics such as RMSE, R2, and RMSECV. Hyperparameter optimization was performed, and SVR showed superior performance, achieving near-perfect predictions (R2 = 0.9999) with an RMSE of 0.100 for both calibration and prediction. The chosen SVR model features two hidden layers with 15 neurons each and uses the Adam algorithm, balanced precision, and computational efficiency. The innovative ATR-FTIR coupled SVR model presented a novel and rapid approach to accurately quantify sorbitol-type nucleating agents in polymer production processes for polymer research and in the analysis of nucleating agent derivatives. The analytical performance of this method surpassed traditional methods (PCR, NN).

The EFSA Panel on Food Contact Materials, Enzymes and Processing Aids assessed the safety of calcium tert-butylphosphonate, which is intended to be used as a nucleating agent up to 0.15% w/w for the manufacture of polyolefin food contact materials (FCM) and articles for single and repeated use, in contact with all types of food, including infant formula and human milk. Specific migration was tested using polyethylene samples in 10% ethanol, 3% acetic acid and 95% ethanol for 2 h at 100°C, followed by 238 h at 40°C. Results for all three simulants were near or below the limit of detection of 10 μg/kg. As the solubility of the substance is far above the reported migration and above 60 mg/kg food, no assessment of the particle fraction was needed, and the conventional risk assessment was followed. The substance did not induce gene mutations in bacterial cells and structural chromosomal aberrations in mammalian cells, thus, did not raise concern for genotoxicity. The Panel considered that the use of the substance did not give rise to safety concern related to neurotoxicity for the general population, but this conclusion could not be applied to infants below 16 weeks of age, due to their specific sensitivity and the absence of dedicated data. The Panel concluded that calcium tert-butylphosphonate does not raise a safety concern for the consumer if it is used as a nucleating agent up to 0.15% w/w in the manufacture of polyolefin FCM that are intended to be in contact with all types of food for storage above 6 months at room temperature and below, including temperatures up to 100°C for maximum 2 h and up to 130°C for short durations. The Panel could not evaluate the safety of use to manufacture FCM for contact with infant formula and human milk.

Poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-PEG-PLLA) shows promise for use in bioplastic applications due to its greater flexibility over PLLA. However, further research is needed to improve PLLA-PEG-PLLA\'s properties with appropriate fillers. This study employed zinc phenylphosphate (PPZn) as a multi-functional filler for PLLA-PEG-PLLA. The effects of PPZn addition on PLLA-PEG-PLLA characteristics, such as crystallization and thermal and mechanical properties, were investigated. There was good phase compatibility between the PPZn and PLLA-PEG-PLLA. The addition of PPZn improved PLLA-PEG-PLLA\'s crystallization properties, as evidenced by the disappearance of the cold crystallization temperature, an increase in the crystallinity, an increase in the crystallization temperature, and a decrease in the crystallization half-time. The PLLA-PEG-PLLA\'s thermal stability and heat resistance were enhanced by the addition of PPZn. The PPZn addition also enhanced the mechanical properties of the PLLA-PEG-PLLA, as demonstrated by the rise in ultimate tensile stress and Young\'s modulus. We can conclude that the PPZn has potential for use as a multi-functional filler for the PLLA-PEG-PLLA composite due to its nucleating-enhancing, thermal-stabilizing, and reinforcing ability.

As semi-crystalline polyester (lactic acid) (PLA) is combined with other reinforcing materials, challenges such as phase separation, environmental pollution, and manufacturing difficulties could hinder the benefits of PLA, including complete biodegradability and strong mechanical properties. In the present investigation, melt blending is utilized to establish a mixture of low- and high-molecular-weight polylactic acids (LPLA and HPLA). The crystallinity, rheology, and mechanical properties of the combination were analyzed using rotational rheometry, differential scanning calorimetry, X-ray diffraction, polarized optical microscopy, scanning electron microscopy, and universal testing equipment. The results demonstrate compatibility between LPLA and HPLA. Moreover, an increase in LPLA concentration leads to a decrease in the crystallization rate, spherulite size, fractional crystallinity, and XRD peak intensity during isothermal crystallization. LPLA acts as a diluent during isothermal crystallization, whereas HPLA functions as a nucleating agent in the non-isothermal crystallization process, promoting the growth of LPLA crystals and leading to co-crystallization. The blended system with a 5% LPLA mass fraction exhibits the highest tensile strength and enhances rheological characteristics. By effectively leveraging the relationship between various molecular weights of PLA\'s mechanical, rheological, and crystallization behavior, this scrutiny improves the physical and mechanical characteristics of the material, opening up new opportunities.

In this work, a novel α-nucleating agent (NA) for polypropylene (PP) termed APAl-3C-12Li was prepared and evaluated compared with the commercially available type NA-21. For the synthesis of the organophosphate-type NA (APAl-3C), the -OH group of the acid part of NA-21 was substituted by the isopropoxy group. The structure of APAl-3C was analyzed by spectroscopy and element analysis, the results of which were consistent with the theoretical molecular formula. APAl-3C\'s thermal stability was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG), which showed only weak mass loss below 230 °C, meaning that it would not decompose during the processing of PP. The APAl-3C-12Li was used as a novel nucleating agent, studying its effects on crystallization, microstructure, mechanical and optical properties. Tests were performed in a PP random copolymer at different contents, in comparison to the commercial NA-21. The composite with 0.5 wt% APAl-3C-12Li has a similar crystallization temperature of 118.8 °C as with the addition of 0.5 wt% NA-21. An advantage is that the composite with the APAl-3C-12Li has a lower haze value of 9.3% than the counterpart with NA-21. This is due to the weaker polarity of APAl-3C-12Li after the introduction of methyl and better uniform dispersion in the PP matrix, resulting in stronger improvement of optical and mechanical properties.

A notable application of polymeric nanocomposites is the design of water vapor permeable (WVP) membranes. \"Breathable\" membranes can be created by the incorporation of micro/nanofillers, such as CaCO3, that interrupt the continuity of the polymeric phase and when subjected to additional uniaxial or biaxial stretching this process leads to the formation of micro/nanoporous structures. Among the candidate nanofillers, carbon nanotubes (CNTs) have demonstrated excellent intrinsic WVP properties. In this study, chemically modified MWCNTs with oligo olefin-type groups (MWCNT-g-PP) are incorporated by melt processes into a PP matrix; a β-nucleating agent (β-ΝA) is also added. The crystallization behavior of the nanocomposite films is evaluated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The WVP performance of the films is assessed via the \"wet\" cup method. The nanohybrid systems, incorporating both MWCNT-g-PP and β-NA, exhibit enhanced WVP compared to films containing only MWCNT-g-PP or β-NA. This improvement can be attributed to the significant increase in the growth of α-type crystals taking place at the edges of the CNTs. This increased crystal growth exerts a form of stress on the metastable β-phase, thereby expanding the initial microporosity. In parallel, the coexistence of the inherently water vapor-permeable CNTs, further enhances the water vapor permeability reaching a specific water vapor transmission rate (Sp.WVTR) of 5500 μm.g/m2.day in the hybrid composite compared to 1000 μm.g/m2.day in neat PP. Notably, the functionalized MWCNT-g-PP used as nanofiller in the preparation of the \"breathable\" PP films demonstrated no noteworthy cytotoxicity levels within the low concentration range used, an important factor in terms of sustainability.