Chemical Recycling of Fully Recyclable Bio-Epoxy Matrices and Reuse Strategies: A Cradle-to-Cradle Approach.

Currently, the epoxy resin market is expressing concerns about epoxy resins' non-recyclability, which can hinder their widespread use. Moreover, epoxy monomers are synthesized via petroleum-based raw materials, which also limits their use. So, it is crucial to find more environmentally friendly alternative solution for their formulation. Within this context, the aim of this paper is to exploit a Cradle-to-Cradle approach, which consists of remodeling and reshaping the productive cycle of consumer products to make sure that they can be infinitely reused rather than just being recycled with a downgrading of their properties or uses, according to the principle of the complete circular economy. Indeed, after starting with a fully-recyclable bio-based epoxy formulation and assessing its recyclability as having a process yield of 99%, we obtained a recycled polymer that could be reused, mixing with the same bio-based epoxy formulation with percentages varying from 15 wt% to 27 wt%. The formulation obtained was thoroughly characterized by a dynamic-mechanical analysis, differential scanning calorimetry, and flexural tests. This approach had two advantages: (1) it represented a sustainable disposal route for the epoxy resin, with nearly all the epoxy resin recovered, and (2) the obtained recycled polymer could be used as a green component of the primary bio-based epoxy matrix. In the end, by using replicated general factorial designs (as statistical tools) combined with a proper optimization process, after carrying out a complete thermo-mechanical characterization of the developed epoxy formulations, the right percentage of recycled polymer content was selected with the aim of identifying the most performing epoxy matrix formulation in terms of its thermo-mechanical properties.

Specific Heat Capacity and Thermal Conductivity Measurements of PLA-Based 3D-Printed Parts with Milled Carbon Fiber Reinforcement.

This research focuses on the thermal characterization of 3D-printed parts obtained via fused filament fabrication (FFF) technology, which uses a poly(lactic acid) (PLA)-based filament filled with milled carbon fibers (MCF) from pyrolysis at different percentages by weight (10, 20, 30 wt%). Differential scanning calorimetry (DSC) and thermal conductivity measurements were used to evaluate the thermal characteristics, morphological features, and heat transport behavior of the printed specimens. The experimental results showed that the addition of MCF to the PLA matrix improved the conductive properties. Scanning electron microscopy (SEM) micrographs were used to obtain further information about the porosity of the systems.

Geopolymers-Design, Preparation, and Applications.

Concrete is the most commonly used construction material worldwide, and many efforts have been carried out in recent years to improve its functional properties while also trying to increase its sustainability [...].

Antibacterial and Chemical Characterization of Silica-Quercetin-PEG Hybrid Materials Synthesized by Sol-Gel Route.

This paper aims to synthesize, via the sol-gel method, a biomaterial usable in the medical field. Here, the silica-PEG-quercetin system was evaluated in relation to the different concentrations of PEG (0, 6, 12, 24, 50 wt%) and quercetin (0, 5, 10, 15 wt%), respectively. In addition, Fourier Transform-Infrared spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), and Kirby-Bauer analyses were performed. FT-IR was used to evaluate the hybrid formation and the influence of both PEG and Quercetin in the hybrid synthesized materials, SEM was used to evaluate the morphological properties, while the Kirby-Bauer test was used to understand the ability of the materials to inhibit the growth of the assayed bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Enterococcus faecalis, and Staphylococcus aureus).

An Overview of Thermal Plasma Arc Systems for Treatment of Various Wastes in Recovery of Metals.

Thermal plasma systems are being used for the recovery of metals from complex waste and minerals. The latter contain multiphase metals in various forms that are extremely tedious to separate. Thermal plasma arc melts the waste and minerals for qualitative plasma products for powder industries. In this overview, we briefly report a description of the various thermal plasma systems and their uses in recovering metal from metal-containing materials in the form of waste or minerals. Various plasma arc systems, such as transferred, nontransferred, and extended arc, have enabled the development of an efficient and environmentally friendly way to recover valuable metals from industrial wastes such as red mud and minerals such as ilmenite.

FT-IR Study, Thermal Analysis, and Evaluation of the Antibacterial Activity of a MK-Geopolymer Mortar Using Glass Waste as Fine Aggregate.

Food containers made from glass are separately collected from urban solid waste at 76% in most parts of Europe. The cullet glass finds its way to re-melting, while the debris is often disposed of. With this contribution, we suggest an upcycling process where glass debris is simply ground without any washing operation and added to an alkali-activated paste. Metakaolin-based geopolymer mortar added with coarsely ground glass waste as fine aggregate has been prepared via alkali activation with NaOH and Na-silicate. After 7, 14 and 28 days of room temperature curing time, the 3D geopolymer network was investigated by Fourier-transform infrared spectroscopy (FT-IR). Vibrational spectra revealed the geopolymerization occurrences, results which have been supported by both FT-IR deconvoluted spectra and thermogravimetric analysis (TGA). Finally, the antibacterial properties were investigated against both gram-negative (E. coli) and gram-positive (E. faecalis) bacterial strains. The results suggest the ability of the 28 days cured geopolymers to inhibit the growth of the gram-negative bacterium assayed.

Stabilization Effects of Natural Compounds and Polyhedral Oligomeric Silsesquioxane Nanoparticles on the Accelerated Degradation of Ethylene-Propylene-Diene Monomer.

In this work the analysis on the stabilization activities of some natural antioxidants (rosemary extract, capsaicin, quercetin or oleanolic acid) is presented. A similar contribution of an inorganic structure-polyhedral oligomeric silsesquioxane (POSS) nanoparticles-is also evaluated. The stabilization effects on the oxidation protection were investigated for several formulations based on ethylene-propylene-diene-terpolymer (EPDM). The samples were examined in pristine state or after γ-irradiation, when the accelerated degradation scission of polymer macromolecules followed by the mitigation of oxidation. Three evaluation procedures: chemiluminescence, FTIR spectroscopy and thermal analysis were applied for the characterization of stability efficiency. The delaying effect of oxidative aging in EPDM matrix is illustrated by the values of activation energy, which are correlated with the type and concentration of embedded compounds. The durability of studied EPDM formulations is discussed for the assessment of material life. The improved behavior of structured hybrids useful for the optimization application regimes is essentially based on the antioxidant properties of polyphenolic components in the cases of natural antioxidants or on the penetration of free radical intermediates into the free volumes of POSS.

The Use of Thermal Techniques in the Characterization of Bio-Sourced Polymers.

The public pressure about the problems derived from the environmental issues increasingly pushes the research areas, of both industrial and academic sectors, to design material architectures with more and more foundations and reinforcements derived from renewable sources. In these efforts, researchers make extensive and profound use of thermal analysis. Among the different techniques available, thermal analysis offers, in addition to high accuracy in the measurement, smartness of execution, allowing to obtain with a very limited quantity of material precious information regarding the property-structure correlation, essential not only in the production process, but overall, in the design one. Thus, techniques such as differential scanning calorimetry (DSC), differential thermal analysis (DTA), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were, are, and will be used in this transition from fossil feedstock to renewable ones, and in the development on new manufacturing processes such as those of additive manufacturing (AM). In this review, we report the state of the art of the last two years, as regards the use of thermal techniques in biopolymer design, polymer recycling, and the preparation of recyclable polymers as well as potential tools for biopolymer design in AM. For each study, we highlight how the most known thermal parameters, namely glass transition temperature (Tg), melting temperature (Tf), crystallization temperature (Tc) and percentage (%c), initial decomposition temperature (Ti), temperature at maximum mass loss rate (Tm), and tan δ, helped the researchers in understanding the characteristics of the investigated materials and the right way to the best design and preparation.

Silicon-Containing Polymeric Materials.

When thinking about a chemical element that has contributed to the technological progress over the last two centuries, carbon and all carbon-based materials immediately come to mind [...].

Kinetic Study of the Thermal and Thermo-Oxidative Degradations of Polystyrene Reinforced with Multiple-Cages POSS.

A comprehensive kinetics degradation study is carried out on novel multiple cages polyhedral oligomeric silsesquioxane (POSS)/polystyrene (PS) composites at 5% (w/w) of POSS to assess their thermal behavior with respect to the control PS and other similar POSS/PS systems studied in the past. The composites are synthesized by in situ polymerization of styrene in the presence of POSSs and characterized by 1H-NMR. The characteristics of thermal parameters are determined using kinetics literature methods, such as those developed by Kissinger and Flynn, Wall, and Ozawa (FWO), and discussed and compared with each other and with those obtained in the past for similar POSS/PS composites. A good improvement in the thermal stability with respect to neat polymer is found, but not with respect to those obtained in the past for polystyrene reinforced with single- or double-POSS cages. This behavior is attributed to the greater steric hindrance of the three-cages POSS compared with those of single- or double-cage POSS molecules.

Thermal Degradation Processes of Aromatic Poly(Ether Sulfone) Random Copolymers Bearing Pendant Carboxyl Groups.

Thermal degradation processes of poly(ether sulfone) random copolymers having different molar amount of diphenolic acid (DPA) units were studied by direct-pyrolysis/mass spectrometry, stepwise pyrolysis-gas chromatography/mass spectrometry and thermogravimetric techniques. Results highlighted that thermal degradation processes occur in the temperature range from 370 to 650 °C, yielding a char residue of 32-35 wt%, which decreases as the mol% of DPA units rises. The pyrolysis/mass spectra data allowed us to identify the thermal decomposition products and to deduce the possible thermal degradation mechanisms. Thermal degradation data suggest that the decarboxylation process of the pendant acid moiety mainly occurs in the initial step of the pyrolysis of the copolymers studied. Successively, the scission of the generated isobutyl groups occurs in the temperature range between 420 and 480 °C. Known processes involving the main chain random scission of the diphenyl sulfone and diphenyl ether groups were also observed.

State-of-the-Art Polymer Science and Technology in Italy.

The history of polymers in Italy certainly begins with Giulio Natta and the discovery of isotactic polypropylene [...].

Epoxy Based Blends for Additive Manufacturing by Liquid Crystal Display (LCD) Printing: The Effect of Blending and Dual Curing on Daylight Curable Resins.

Epoxy-based blends printable in a Liquid Crystal Display (LCD) printer were studied. Diglycidyl ether of bisphenol A (DGEBA) mixed with Diethyltoluene diamine (DETDA) was used due to the easy processing in liquid form at room temperature and slower reactivity until heated over 150 ° C. The DGEBA/DETDA resin was mixed with a commercial daylight photocurable resin used for LCD screen 3D printing. Calorimetric, dynamic mechanical and rheology testing were carried out on the resulting blends. The daylight resins showed to be thermally curable. Resin's processability in the LCD printer was evaluated for all the blends by rheology and by 3D printing trials. The best printing conditions were determined by a speed cure test. The use of a thermal post-curing cycle after the standard photocuring in the LCD printer enhanced the glass transition temperature T g of the daylight resin from 45 to 137 ° C when post-curing temperatures up to 180 ° C were used. The T g reached a value of 174 ° C mixing 50 wt% of DGEBA/DETDA resin with the photocurable resin when high temperature cure cycle was used.

Bio-Polyethylene (Bio-PE), Bio-Polypropylene (Bio-PP) and Bio-Poly(ethylene terephthalate) (Bio-PET): Recent Developments in Bio-Based Polymers Analogous to Petroleum-Derived Ones for Packaging and Engineering Applications.

In recent year, there has been increasing concern about the growing amount of plastic waste coming from daily life. Different kinds of synthetic plastics are currently used for an extensive range of needs, but in order to reduce the impact of petroleum-based plastics and material waste, considerable attention has been focused on "green" plastics. In this paper, we present a broad review on the advances in the research and development of bio-based polymers analogous to petroleum-derived ones. The main interest for the development of bio-based materials is the strong public concern about waste, pollution and carbon footprint. The sustainability of those polymers, for general and specific applications, is driven by the great progress in the processing technologies that refine biomass feedstocks in order to obtain bio-based monomers that are used as building blocks. At the same time, thanks to the industrial progress, it is possible to obtain more versatile and specific chemical structures in order to synthetize polymers with ad-hoc tailored properties and functionalities, with engineering applications that include packaging but also durable and electronic goods. In particular, three types of polymers were described in this review: Bio-polyethylene (Bio-PE), bio-polypropylene (Bio-PP) and Bio-poly(ethylene terephthalate) (Bio-PET). The recent advances in their development in terms of processing technologies, product development and applications, as well as their advantages and disadvantages, are reported.

Design, Preparation and Thermal Characterization of Polystyrene Composites Reinforced with Novel Three-Cages POSS Molecules.

Novel polystyrene (PS)/polyhedral oligomeric silsequioxanes (POSSs) nanocomposites were designed and prepared by in situ polymerization, using, for the first time, three-cage POSS molecules. The synthesized compounds were first characterized by Fourier transform infrared spectroscopy (FTIR) and 1H NMR spectroscopy to verify the obtaining of the designed products before their thermal performance was evaluated and compared with those of pristine PS and the corresponding single-cage POSSs nanocomposites. The thermal behaviour was checked by the means of the differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) was also used to confirm the hypothesis about the dispersion/aggregation of the POSS molecules into the polymer matrix. The parameters chosen to evaluate the thermal stability of the investigated compounds, namely temperature at 5% of mass loss (T5%) and solid residue at 700 °C, showed a significant increase in the stability of the polymers reinforced with the three-cages POSS, in comparison to both PS and single-cage POSS reinforced PSs, which therefore turn out to be promising molecular fillers for nanocomposite production.

Durability of LDPE/UHMWPE Composites under Accelerated Degradation.

This study presents a detailed analysis of thermal and radiation resistances of low density polyethylene (LDPE)/ultra-high molecular weight polyethylene (UHMWPE) blends containing hydroxyapatite as functional filler and rosemary acting as antioxidant against oxidative degradation. Three main procedures, chemiluminescence (CL), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC), were applied for the determination of the degree of degradation when these materials are subjected to heat and radiation action. The crystallinity was also assessed for the characterization of diffusion peculiarities. The contributions of the mixing components are discussed based on their oxidation strength. The activation energies required for the oxidative degradation of the studied formulations were calculated.

Life-Cycle Assessment in the Polymeric Sector: A Comprehensive Review of Application Experiences on the Italian Scale.

In recent years, a growing media campaign has demonized the use of plastic tout court, as solely responsible for environmental problems. Behind what is now vulgarly called plastic there are actually many applications and uses without which our daily life would be greatly penalized in the most common and routine actions. Our belief, in the role of researchers who have made polymers and their derivatives their main research object, is that sustainable use of polymeric materials is not only possible but is above all necessary. For this reason, in this review which is part of the Special Issue "State-of-the-Art Polymer Science and Technology in Italy", we offer a rundown of life-cycle assessment (LCA) studies on polymers used in the most important production and commercial sectors carried out in the last few years by Italians researchers.

Optimization of ZnO Nanorods Growth on Polyetheresulfone Electrospun Mats to Promote Antibacterial Properties.

Zinc oxide (ZnO) nanorods grown by chemical bath deposition (CBD) on the surface of polyetheresulfone (PES) electrospun fibers confer antimicrobial properties to the obtained hybrid inorganic-polymeric PES/ZnO mats. In particular, a decrement of bacteria colony forming units (CFU) is observed for both negative (Escherichia coli) and positive (Staphylococcus aureus and Staphylococcus epidermidis) Grams. Since antimicrobial action is strictly related to the quantity of ZnO present on surface, a CBD process optimization is performed to achieve the best results in terms of coverage uniformity and reproducibility. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) provide morphological and compositional analysis of PES/ZnO mats while thermogravimetric analysis (TGA) is useful to assess the best process conditions to guarantee the higher amount of ZnO with respect to PES scaffold. Biocidal action is associated to Zn2+ ion leaching in solution, easily indicated by UV-Vis measurement of metallation of free porphyrin layers deposited on glass.

Functionalized polyhedral oligosilsesquioxane (POSS) based composites for bone tissue engineering: synthesis, computational and biological studies.

Functionalized polyhedral oligosilsesquioxanes (POSS) containing an isoxazolidine nucleus have been synthesized by microwave assisted 1,3-dipolar cycloaddition of N-methyl-C-alkoxycarbonyl nitrone 1 with POSS containing olefin moieties. The results of cycloaddition processes were rationalized by computational studies at the DFT level. The covalent conjugation of chitosan with the cycloadduct 3a leads to composite material CS-POSS 7 which was gelified using genipin as cross linking agent. The suitability of the system for bone tissue engineering purposes was evaluated by in vitro drug release studies using ketoprofen as a model drug and cytotoxicity assays performed on human fetal osteoblastic cells. The preliminary biological tests showed the lack of cytotoxicity of the hybrid material and suggest its potential role in bone tissue engineering applications.

POSS-Based Polymers.

The combination of functional polymers with inorganic nanostructured compounds has become a major area of research and technological development owing to the remarkable properties and multifunctionalities deriving from their nano and hybrid structures [...].