Molecular Imprinting for High-Added Value Metals: An Overview of Recent Environmental Applications

One of the most hot topics of recent research is the reuse of some compounds existing as pollutants in environment. These compounds (molecules, ions, complexes, etc.) are of high-added value and it will be ideal to selectively bind them with any environmental application and reuse them in their initial or modified form. The latter can be achieved using molecular imprinting. In the present review article, an overview of the recent attempts for the selective binding of some precious metals (i.e., gold, silver, and platinum) of high-added value is done using molecular imprinted polymers (MIPs) as materials. The simplicity of their use, their relatively low cost, and the broad range of possible guest molecules (small organic molecules, ions, metals, and also biological macromolecules) have since led to the important development of molecular imprinting

Non-Isothermal Crystallization Kinetics of PBSu/Biochar Composites Studied by Isoconversional and Model Fitting Methods

Non-isothermal crystallization of Poly(butylene succinate) (PBSu)/biochar composites was studied at various constant cooling rates using differential scanning calorimetry. The analysis of the kinetics data revealed that the overall crystallization rate and activation energy of the PBSu polymer were significantly influenced by the addition of biochar. Specifically, the PBSu/5% biochar composite with a higher filler content was more effective as a nucleation agent in the polymer matrix, as indicated by the nucleation activity (ψ) value of 0.45. The activation energy of the PBSu/5% biochar composite was found to be higher than that of the other compositions, while the nucleation activity of the PBSu/biochar composites decreased as the biochar content increased. The Avrami equation, which is commonly used to describe the kinetics of crystallization, was found to be limited in accurately predicting the non-isothermal crystallization behavior of PBSu and PBSu/biochar composites. Although the Nakamura/Hoffman–Lauritzen model performed well overall, it may not have accurately predicted the crystallization rate at the end of the process due to the possibility of secondary crystallization. Finally, the combination of the Šesták–Berggren model with the Hoffman–Lauritzen theory was found to accurately predict the crystallization behavior of the PBSu/biochar composites, indicating a complex crystallization mechanism involving both nucleation and growth. The Kg parameter of neat PBSu was found to be 0.7099 K2, while the melting temperature and glass transition temperature of neat PBSu were found to be 114.91 °C and 35 °C, respectively, very close to the measured values. The Avrami nucleation dimension n was found to 2.65 for PBSu/5% biochar composite indicating that the crystallization process is complex in the composites

Kraft Lignin/Tannin as a Potential Accelerator of Antioxidant and Antibacterial Properties in an Active Thermoplastic Polyester-Based Multifunctional Material

This research focuses on key priorities in the field of sustainable plastic composites that will lead to a reduction in CO2 pollution and support the EU\u27s goal of becoming carbon neutral by 2050. The main challenge is to develop high-performance polyphenol-reinforced thermoplastic composites, where the use of natural fillers replaces the usual chemical additives with non-toxic ones, not only to improve the final performance but also to increase the desired multifunctionalities (structural, antioxidant, and antibacterial). Therefore, poly (lactic acid) (PLA) composites based on Kraft lignin (KL) and tannin (TANN) were investigated. Two series of PLA composites, PLA-KL and PLA-TANN, which contained natural fillers (0.5%, 1.0%, and 2.5% (w/w)) were prepared by hot melt extrusion. The effects of KL and TANN on the PLA matrices were investigated, especially the surface physicochemical properties, mechanical properties, and antioxidant/antimicrobial activity. The surface physicochemical properties were evaluated by measuring the contact angle (CA), roughness, zeta potential, and nanoindentation. The results of the water contact angle showed that neither KL nor TANN caused a significant change in the wettability, but only a slight increase in the hydrophilicity of the PLA composites. The filler loading, the size of the particles with their available functional groups on the surfaces of the PLA composites, and the interaction between the filler and the PLA polymer depend on the roughness and zeta potential behavior of the PLA-KL and PLA-TANN composites and ultimately improve the surface mechanical properties. The antioxidant properties of the PLA-KL and PLA-TANN composites were determined using the DPPH (2, 2\u27-diphenyl-1-picrylhydrazyl) test. The results show an efficient antioxidant behavior of all PLA-KL and PLA-TANN composites, which increases with the filler content. Finally, the KL- and PLA-based TANN have shown resistance to the Gram-negative bacteria, E. coli, but without a correlation trend between polyphenol filler content and structure

Influence of reactive diluent composition on properties and bio-based content of itaconic acid-based additive manufacturing materials

Among the additive manufacturing techniques, UV-curing processes are of special interest, as they allow for the fabrication of thermosetting materials with high resolutions and optical clarity. Traditionally, these processes require the use of formulations, consisting of polyester or polyurethane oligomers, combined with photoinitiators and reactive diluents. The latter are usually vinyl monomers such as acrylates or acrylamides, used to reduce the viscosity of the formulation and render it processable by additive manufacturing machines. In this work, we investigate whether a combination of diluents can be used to tune the thermomechanical properties of the printed materials, and if it can be exploited to increase their overall bio-based content without compromising their performance. To do so, a series of itaconic acidbased polyesters with diferent chemical structures (aliphatic–aromatic) were synthesized and formulated with reactive diluents acryloyl morpholine (ACMO) and isobornyl acrylate (IBOA). The physicochemical properties of the prepared formulations, together with their reactivity towards UV-light were assessed via photo diferential scanning calorimetry (photo-DSC) and photo-rheology measurements. The same formulations were then used to fabricate test specimen via digital light processing (DLP) 3D printing, which were characterized on their thermomechanical properties by means of dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) measurements. The glass transition temperature of the printed samples reached a maximum of 98 °C, while the diluent ratio could be used to manipulate the Tg in a linear trend. All materials of this study exhibited Td,5% above 250 °C, suggesting good thermal stability. These results show that materials with a very high bio-based content (up to 85%) and very promising thermomechanical properties could be obtained by employing a diluent mixture during the formulation phase

Biobased poly(ethylene furanoate-:Co -ethylene succinate) copolyesters: Solid state structure, melting point depression and biodegradability

Novel, biobased poly(ethylene furanoate-co-ethylene succinate) copolyesters were successfully prepared by melt polycondensation and their solid state structure, melting point depression and biodegradability were evaluated in detail.</p

The Effect of Biochar Addition on Thermal Stability and Decomposition Mechanism of Poly(butylene succinate) Bionanocomposites

In the present study, poly(butylene succinate) (PBSu) and its bionanocomposites containing 1, 2.5, and 5 wt.% biochar (MSP700) were prepared via in situ melt polycondensation in order to investigate the thermal stability and decomposition mechanism of the materials. X-ray photoelectron spectroscopy (XPS) measurements were carried out to analyze the surface area of a biochar sample and PBSu/biochar nanocomposites. From XPS, it was found that only physical interactions were taking place between PBSu matrix and biochar nanoadditive. Thermal stability, decomposition kinetics, and the decomposition mechanism of the pristine PBSu and PBSu/biochar nanocomposites were thoroughly studied by thermogravimetric analysis (TGA) and pyrolysis–gas chromatography/mass spectrometry (Py−GC/MS). TGA thermograms depicted that all materials had high thermal stability, since their decomposition started at around 300 °C. However, results indicated a slight reduction in the thermal stability of the PBSu biochar nanocomposites because of the potential catalytic impact of biochar. Py−GC/MS analysis was employed to examine, in more detail, the thermal degradation mechanism of PBSu nanocomposites filled with biochar. From the decomposition products identified by Py−GC/MS after pyrolysis at 450 °C, it was found that the decomposition pathway of the PBSu/biochar nanocomposites took place mainly via β-hydrogen bond scission, which is similar to that which took place for neat PBSu. However, at higher biochar content (5 wt.%), some localized differences in the intensity of the peaks of some specific thermal degradation products could be recognized, indicating that α-hydrogen bond scission was also taking place. A study of the thermal stability and decomposition pathway of PBSu/biochar bionanocomposites is crucial to examine if the new materials fulfill the requirements for further investigation for mulch films in agriculture or in electronics as possible applications

A New Era in Engineering Plastics: Compatibility and Perspectives of Sustainable Alipharomatic Poly(ethylene terephthalate)/Poly(ethylene 2,5-furandicarboxylate) Blends

The industrialisation of poly(ethylene 2,5-furandicarboxylate) for total replacement of poly(ethylene terephthalate) in the polyester market is under question. Preparation of high-performing polymer blends is a well-established strategy for tuning the properties of certain homopolymers and create tailor-made materials to meet the demands for a number of applications. In this work, the structure, thermal properties and the miscibility of a series of poly(ethylene terephthalate)/poly(ethylene 2,5-furandicarboxylate) (PET/PEF) blends have been studied. A number of thermal treatments were followed in order to examine the thermal transitions, their dynamic state and the miscibility characteristics for each blend composition. Based on their glass transition temperatures and melting behaviour the PET/PEF blends are miscible at high and low poly(ethylene terephthalate) (PET) contents, while partial miscibility was observed at intermediate compositions. The multiple melting was studied and their melting point depression was analysed with the Flory-Huggins theory. In an attempt to further improve miscibility, reactive blending was also investigated

Synthesis and Study of Fully Biodegradable Composites Based on Poly(butylene succinate) and Biochar

Biodegradable polymers offer a promising alternative to the global plastic problems and especially in the last decade, to the microplastics problems. For the first time, samples of poly(butylene succinate) (PBSu) biocomposites containing 1, 2.5, and 5 wt% biochar (BC) were prepared by in situ polymerization via the two-stage melt polycondensation procedure. BC was used as a filler for the PBSu to improve its mechanical properties, thermal transitions, and biodegradability. The structure of the synthesized polymers was examined by 1H and 13C nuclear magnetic resonance (NMR) and X-Ray diffraction (XRD) along with an estimation of the molecular weights, while differential scanning calorimetry (DSC) and light flash analysis (LFA) were also employed to record the thermal transitions and evaluate the thermal conductivity, respectively. It was found that the amount of BC does not affect the molecular weight of PBSu biocomposites. The fine dispersion of BC, as well as the increase in BC content in the polymeric matrix, significantly improves the tensile and impact strengths. The DSC analysis results showed that BC facilitates the crystallization of PBSu biocomposites. Due to the latter, a mild and systematic increase in thermal diffusivity and conductivity was recorded indicating that BC is a conductive material. The molecular mobility of PBSu, local and segmental, does not change significantly in the biocomposites, whereas the BC seems to cause an increase in the overall dielectric permittivity. Finally, it was found that the enzymatic hydrolysis degradation rate of biocomposites increased with the increasing BC content