Toward chemical recycling of PU foams: study of the main purification options.

The recovery of the polyol component, after glycolysis of polyurethane (PU) foams coming from automotive waste, was investigated. Several separation methods such as simple sedimentation, centrifugation and liquid-liquid extraction, eventually preceded by an acid washing step, were tested. The obtained fractions were characterized by infrared spectroscopy and CHN elemental analysis. Furthermore, multivariate data analysis was carried out on the infrared spectra by principal component analysis to classify the fractions based on purity. IR spectroscopy coupled with principal component analysis was able to estimate the success of the separation and eventual culprits such as contaminations, which were then quantified by CHN elemental analysis. This approach addresses some critical limitations associated with classical analytical techniques such as NMR, TGA, GPC, MALDI-TOF that often require an extremely accurate separation of the depolymerized product fractions. Moreover, IR spectroscopy and CHN elemental analysis techniques are cheap and widespread in standard materials science laboratories. At last, based on the results of the analysis of the regenerated polyol fractions, and on the foaming tests, considerations were made to guide the choice of the purification method according to the application specifications and greenness.

Analytical Characterization of the Intercalation of Neutral Molecules into Saponite.

Organo-modified layered materials characterization poses challenges due to their complexity and how other aspects such as contamination, preparation methods and degree of intercalation influence the properties of these materials. Consequently, a deep understanding of their interlayer organization is of utmost importance to optimize their applications. These materials can in fact improve the stability of photoactive molecules through intercalation, avoiding the quenching of their emission at the solid state, to facilitate their use in sensors or other devices. Two synthetic methods for the preparation of saponites with a cationic surfactant (CTABr) and a neutral chromophore (Fluorene) were tested and the obtained products were initially characterized with several complementary techniques (XRPD, SEM, TGA, IR, UV-Vis, Fluorescence and Raman spectroscopy), but a clear understanding of the organization of the guest molecules in the material could not be obtained by these techniques alone. This information was obtained only by thermogravimetry coupled with gas chromatography and mass spectroscopy (TGA-GC-MS) which allowed identifying the species present in the sample and the kind of interaction with the host by distinguishing between intercalated and adsorbed on the surface.

Low-Cost Biobased Coatings for AM60 Magnesium Alloys for Food Contact and Harsh Environment Applications.

Low-cost, environmentally friendly and easily applicable coating for Mg alloys, able to resist in real world conditions, are studied. Coatings already used for other metals (aluminum, steel) and never tested on Mg alloy for its different surface and reactivity were deposited on AM60 magnesium alloys to facilitate their technological applications, also in presence of chemically aggressive conditions. A biobased PA11 powder coating was compared to synthetic silicon-based and polyester coatings, producing lab scale samples, probed by drop deposition tests and dipping in increasingly aggressive, salty, basic and acid solutions, at RT and at higher temperatures. Coatings were analyzed by SEM/EDX to assess their morphology and compositions, by optical and IR-ATR microscopy analyses, before and after the drop tests. Migration analyses from the samples were performed by immersion tests using food simulants followed by ICP-OES analysis of the recovered simulant to explore applications also in the food contact field. A 30 µm thick white lacquer and a 120 µm PA11 coating resulted the best solutions. The thinner siliconic and lacquer coatings, appearing brittle and thin in the SEM analysis, failed some drop and/or dipping test, with damages especially at the edges. The larger thickness is thus the unique solution for edgy or pointy samples. Finally, coffee cups in AM60 alloy were produced, as real word prototypes, with the best performing coatings and tested for both migration by dipping, simulating also real world aging (2 h in acetic acid at 70° and 24 h in hot coffee at 60 °C): PA11 resulted stable in all the tests and no migration of toxic metals was observed, resulting a promising candidate for many real world application in chemically aggressive environments and also food and beverage related applications.

Light Weight, Easy Formable and Non-ToxicPolymer-Based Composites for Hard X-rayShielding: A Theoretical and Experimental Study.

Composite lightweight materials for X-ray shielding applications were studied anddeveloped with the goal of replacing traditional screens made of lead and steel, with innovativematerials with similar shielding properties, but lighter, more easily formed and workable, with lowerimpact on the environment and reduced toxicity for human health. New epoxy-based compositesadditivated with barium sulfate and bismuth oxide were designed through simulations performedwith software based on Geant4. Then, they were prepared and characterized using differenttechniques starting from digital radiography in order to test the radiopacity of the composites,in comparison with traditional materials. The lower environmental impact and toxicity of theseinnovative screens were quantified by Life Cycle Assessment (LCA) calculation based on the ecoinventdatabase, within the openLCA framework. Optimized mixtures are (i) 20% epoxy/60% bismuthoxide/20% barite, which guarantees the best performance in X-ray shielding, largely overcomingsteel, but higher in costs and a weight reduction of circa 60%; (ii) 20% epoxy/40% bismuth oxide/40%barite which has slightly lower performances in shielding, but it is lighter and cheaper than thefirst one and (iii) the 20% epoxy/20% bismuth oxide/60% barite which is the cheapest material, stillmaintaining the X-ray shielding of steel. Depending on the cost/efficiency request of the specificapplication (industrial ra.

New Hints on the Maya Blue Formation Process by PCA-Assisted In Situ XRPD/PDF and Optical Spectroscopy.

The exact recipe to prepare the ancient Maya Blue (MB), an incredibly resistant and brilliant pigment prepared from indigo (dye) and Palygorskite (clay), is lost to the ages. To unravel the key features of the MB formation process, several inorganic-dye couples were heated to 200 °C and cooled to RT, to investigate their reactivity and the diffusion and degree of sequestration of the dye into the inorganic host. In situ XRPD/PDF and fiber optic reflectance spectroscopy (FORS) data, along with TGA, provided a comprehensive overview on MB formation mechanism. XRPD/PDF gave information on long/short range behaviors of water desorption/adsorption and indigo sequestration, while TGA and in situ FORS gave information on mass and optical changes within temperature. Ex situ dye removal was used to understand the sample stability after the thermal treatment. A statistical approach based on principal component analysis was exploited to efficiently and jointly analyze the ≈3000 collected patterns. MB formation starts below 110 °C with disordered distribution of indigo within the channels, reaching maximum reaction speed and higher ordering at 150 °C. Above 175 °C, color changes and a stronger sequestration of indigo into framework channels are observed, whereas the affinity for water is dramatically reduced. The origin of different colors, hues, and stability in historical MB samples can then be explained in terms of different thermal histories of the starting mechanical indigo/palygorskite mixtures.

Structural Characterisation of Complex Layered Double Hydroxides and TGA-GC-MS Study on Thermal Response and Carbonate Contamination in Nitrate- and Organic-Exchanged Hydrotalcites.

Layered double hydroxides (LDHs) are versatile materials used for intercalating bioactive molecules in the fields of pharmaceuticals, nutraceuticals and cosmetics, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability and improving their pharmacokinetic properties and formulation stability. Moreover, LDHs are used in various technological applications to improve stability and processability. The crystal chemistry of hydrotalcite-like compounds was investigated by X-ray powder diffraction (XRPD), automated electron diffraction tomography (ADT) and thermogravimetric analysis (TGA)-GC-MS to shed light on the mechanisms involved in ion exchange and absorption of contaminants, mainly carbonate anions. For the first time, ADT allowed a structural model of LDH_NO3 to be obtained from experiment, shedding light on the conformation of nitrate inside LDH and on the loss of crystallinity due to the layer morphology. The ADT analysis of a hybrid LDH sample (LDH_EUS) clearly revealed an increase in defectivity in this material. XRPD demonstrated that the presence of carbonate can influence the intercalation of organic molecules into LDH, since CO3 -contaminated samples tend to adopt d spacings that are approximate multiples of the d spacing of LDH_CO3 . TGA-GC-MS allowed intercalated and surface- adsorbed organic molecules to be distinguished and quantified, the presence and amount of carbonate to be confirmed, especially at low concentrations (<2 wt %), and the different types and strengths of adsorption to be classified with respect to the temperature of elimination.

Exposure to Microplastics Made of Plasmix-Based Materials at Low Amounts Did Not Induce Adverse Effects on the Earthworm Eisenia foetida.

The implementation of recycling techniques represents a potential solution to the plastic pollution issue. To date, only a limited number of plastic polymers can be efficiently recycled. In the Italian plastic waste stream, the residual, non-homogeneous fraction is called 'Plasmix' and is intended for low-value uses. However, Plasmix can be used to create new materials through mechanical recycling, which need to be tested for their eco-safety. This study aimed to investigate the potential toxicity of two amounts (0.1% and 1% MPs in soil weight) of microplastics (MPs) made of naïve and additivated Plasmix-based materials (Px and APx, respectively) on the earthworm Eisenia foetida. Changes in oxidative status and oxidative damage, survival, gross growth rate and reproductive output were considered as endpoints. Although earthworms ingested both MP types, earthworms did not suffer an oxidative stress condition or growth and reproductive impairments. The results suggested that exposure to low amounts of both MPs can be considered as safe for earthworms. However, further studies testing a higher amount or longer exposure time on different model species are necessary to complete the environmental risk assessment of these new materials.

Crystallization from solution versus mechanochemistry to obtain double-drug multicomponent crystals of ethacridine with salicylic/acetylsalicylic acids.

Salicylic and acetylsalicylic acids and ethacridine have complementary bioactive properties. They can be combined to obtain double-drug multicomponent crystals. Their reactivity in different environments was explored to obtain the possible compounds, stable at different hydration degrees. Solution, liquid-assisted grinding, and dry preparation approaches were applied to the couples of reactants in different stoichiometric ratios. Four compounds were obtained, and three out of them were stable and reproducible enough to determine their structures using SCXRD or PXRD methods. When coupled to ethacridine, salicylic acid gave two stable structures (1 and 3, both showing 1:1 ratio but different hydration degree) and a metastable one (5), while acetylsalicylic acid only one structure from solution (2 in 1:1 ratio), while LAG caused hydrolysis and formation of the same compound obtained by LAG of ethacridine with salicylic acid. While solution precipitation gave dihydrated (1) or monohydrated (2) structures with low yields, LAG of salicylic acid and ethacridine allowed obtaining an anhydrous salt complex (3) with a yield close to 1. The structures obtained by solution crystallizations maximize π(acridine)-π(acridine) contacts with a less compact packing, while the LAG structure is more compact with a packing driven by hydrogen bonds. For all compounds, NMR, ATR-FTIR, and Hirshfeld surface analysis and energy framework calculations were performed.

Microfibers in the Diet of a Highly Aerial Bird, the Common Swift Apus apus.

Microplastic pollution is a pervasive global issue affecting various ecosystems. Despite the escalating production and well-documented contamination in both aquatic and terrestrial environments, the research focused on airborne microplastics and their interaction with terrestrial birds remains limited. In this study, we collected fecal sacs from Common swifts (Apus apus) to investigate their diet and to evaluate the potential ingestion of microplastics by both adults and nestlings. The diet was mainly composed of Hymenoptera and Coleoptera and did not differ among sexes and age classes. The 33% of nestlings' and 52% of adults' fecal sacs contained anthropogenic items, the totality of which was in the shape form of fibers. The 19.4% of the anthropogenic items were chemically characterized as microplastics, either polyethylene terephthalate (PET; two microfibers) or cellophane (four microfibers). Airborne anthropogenic items, including microplastic, might be passively ingested during the Common swift aerial feeding. In addition, our findings suggest that these ingested microparticles have the potential to be transferred to the offspring through food. While further research is essential to elucidate the pathways of microplastic ingestion, our results reinforce the evidence of the transfer of anthropogenic items from the atmosphere to the biota.

Altitudinal variation of microplastic abundance in lakeshore sediments from Italian lakes.

Microplastic (MP) contamination represents an issue of global concern for both aquatic and terrestrial ecosystems, but only in recent years, the study of MPs has been focused on freshwaters. Several monitoring surveys have detected the presence of a wide array of MPs differing in size, shape, and polymer composition in rivers and lakes worldwide. Because of their role of sink for plastic particles, the abundance of MPs was investigated in waters, and deep and shoreline sediments from diverse lakes, confirming the ubiquity of this contamination. Although diverse factors, including those concerning anthropogenic activities and physical characteristics of lakes, have been supposed to affect MP abundances, very few studies have directly addressed these links. Thus, the aim of the present study was to explore the levels of MP contamination in mountain and subalpine lakes from Northern Italy. Fourteen lakes dislocated at different altitudes and characterized by dissimilar anthropic pressures were visited. Lakeshore sediments were collected close to the drift line to assess MPs contamination. Our results showed the presence of MPs in lakeshore sediments from all the lakes, with a mean (± standard deviation) expressed as MPs/Kg dry sediment accounting to 14.42 ± 13.31 (range 1.57-61.53), while expressed as MPs/m2, it was 176.07 ± 172.83 (range 25.00-666.67). The MP abundance measured for Garda Lake was significantly higher compared to all the other ones (F1,13 = 7.344; P < 0.001). The pattern of contamination was dominated by fibers in all the lakes, but they were the main contributors in mountain lakes. These findings showed that the MP abundance varied according to the altitude of the lakes, with higher levels measured in subalpine lakes located at low altitudes and surrounded by populated areas.

Microplastics originated from Plasmix-based materials caused biochemical and behavioral adverse effects on Daphnia magna.

The implementation of advanced recycling techniques represents a key strategy for mitigating the mismanagement and the environmental impact of plastic waste. A limited array of plastic polymers can be efficiently recycled, while a notable portion of plastic waste remains unrecyclable. In Italy, this residual, heterogeneous fraction is referred to as Plasmix. Because of its complexity and non-homogeneous composition, Plasmix is primarily directed towards low-value applications. However, recent developments in laboratory-scale mechanical recycling have enabled the creation of new plastic materials from Plasmix. Prior to their application, these materials must undergo rigorous eco-safety evaluation. The present study aims to assess the potential toxicity of microplastics (MPs) from Plasmix-based materials on the freshwater crustacean Daphnia magna. Specifically, this study investigated sub-individual and individual effects induced by a 21-day exposure to different concentrations of MPs generated from the grinding of naïve and Additivated Plasmix-based materials (hereafter referred to as Px-MPs and APx-MPs, respectively). Sub-individual endpoints focused on changes in oxidative status, including the modulation of antioxidant and detoxifying enzyme activities, as well as oxidative damage, such as lipid peroxidation. Individual level endpoints included alterations in survival and reproduction. Microscopy analyses confirmed the ingestion of both Px-MPs and APx-MPs by D. magna individuals. An oxidative stress condition raised in organisms exposed to Px-MPs, whereas no effect was observed in individuals exposed to APx-MPs. Although survival was not affected, a significant impairment in reproductive output was detected at the end of exposure to all the concentrations of both MP types. These findings suggest that even low concentrations of Px-MPs and APx-MPs could negatively affect the health status of D. magna, underscoring the need for further research to complete the risk assessment of Plasmix-based materials prior to their use in consumer products.

Structural characterization and thermal and chemical stability of bioactive molecule-hydrotalcite (LDH) nanocomposites.

Layered double hydroxides (LDH) are versatile materials used for intercalating bioactive molecules, both in pharmaceutical and cosmetic fields, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability, and/or obtaining modified release properties. The properties of the intercalation compounds of Mg/Al_LDH and Zn/Al_LDH with different drugs and sunscreens, namely diclofenac, ketoprofen, gliclazide, retinoic acid, furosemide, para-aminobenzoic acid and 2-phenylbenzimidazolsulfonic (Eusolex) acid, have been studied by crystallographic, spectroscopic and thermogravimetric techniques and by solid state NMR, to shed light on their structure, their molecular interactions and their stability from the thermal and chemical viewpoint. The structural features were described with particular attention to the interaction between the organic and inorganic components and to the stability of the intercalation products. For the first time two synchrotron radiation powder diffraction patterns of organic-containing LDH were solved and refined by Rietveld methods to obtain an experimental crystal structure.

Solvothermal synthesis and structural characterization of three polyoxotitanium-organic acid clusters.

Three new titanium oxo-clusters Ti4O2(OiPr)10(OOCPhMe)2 (I), Ti6O4(OEt)8(OOCPhMe)8 (II) and Ti6O6(OEt)6(OOCCHPh2)6 (III) were obtained by easy one-step solvothermal reactions of titanium(iv) isopropoxide, alcohols and carboxylic acids. The three compounds were characterized by single-crystal and powder X-ray diffraction, TGA/DSC, optical and electron microscopy, and FTIR and NMR spectroscopy. X-ray powder diffraction and spectroscopy confirmed the purity of the compounds. Structural analysis indicates that in all compounds the titanium(iv) ions are six-coordinated (distorted octahedra). (I) is a tetranuclear complex containing a Ti4(µ4-O)(µ2-O) core, which is linked by two (µ2-OOCPhMe), four (µ2-OiPr) and six OiPr ligands. (II) and (III) are hexanuclear complexes with different cores, respectively Ti6(µ3-O)2(µ2-O)2 and Ti6(µ3-O)6. The coordination sphere of the Ti atoms is filled by eight (µ2-OOCPhMe), two (µ2-OEt) and six OEt in (II) and six (µ2-OOCHPh2) and six OEt in (III). Different steric hindrance of substituents attached to the carboxyl group or different concentrations lead to three main different cluster geometries with two ligands. The tetranuclear and the hexanuclear clusters were obtained with the OOCPhMe ligand, while the hexagonal prism cluster was obtained with the OOCCHPh2 ligand. Hirshfeld surface calculations indicated that the packing is driven by C-O⋯H-C weak hydrogen bonds. The clusters can be used as molecular models of organic molecules bonded to titania surface, used in organic photovoltaic (dye sensitized solar cells) or other optoelectronic applications.

CO2 adsorption in Y zeolite: a structural and dynamic view by a novel principal-component-analysis-assisted in situ single-crystal X-ray diffraction experiment.

The increasing efficiency of detectors and brightness of X-rays in both laboratory and large-scale facilities allow the collection of full single-crystal X-ray data sets within minutes. The analysis of these `crystallographic big data' requires new tools and approaches. To answer these needs, the use of principal component analysis (PCA) is proposed to improve the efficiency and speed of the analysis. Potentialities and limitations of PCA were investigated using single-crystal X-ray diffraction (XRD) data collected in situ on Y zeolite, in which CO2, acting as an active species, is thermally adsorbed while cooling from 300 to 200 K. For the first time, thanks to the high sensitivity of single-crystal XRD, it was possible to determine the sites where CO2 is adsorbed, the increase in their occupancy while the temperature is decreased, and the correlated motion of active species, i.e. CO2, H2O and Na+. PCA allowed identification and elimination of problematic data sets, and better understanding of the trends of the occupancies of CO2, Na+ and water. The quality of the data allowed for the first time calculation of the enthalpy (ΔH) and entropy (ΔS) of the CO2 adsorption by applying the van 't Hoff equation to in situ single-crystal data. The calculation of thermodynamic values was carried out by both traditional and PCA-based approaches, producing comparable results. The obtained ΔH value is significant and involves systems (CO2 and Y zeolite) with no toxicity, superb stability and chemical inertness. Such features, coupled with the absence of carbonate formation and framework inertness upon adsorption, were demonstrated for the bulk crystal by the single-crystal experiment, and suggest that the phenomenon can be easily reversed for a large number of cycles, with CO2 released on demand. The main advantages of PCA-assisted analysis reside in its speed and in the possibility of it being applied directly to raw data, possibly as an `online' data-quality test during data collection, without any a priori knowledge of the crystal structure.

High-Throughput Preparation of New Photoactive Nanocomposites.

New low-cost photoactive hybrid materials based on organic luminescent molecules inserted into hydrotalcite (layered double hydroxides; LDH) were produced, which exploit the high-throughput liquid-assisted grinding (LAG) method. These materials are conceived for applications in dye-sensitized solar cells (DSSCs) as a co-absorbers and in silicon photovoltaic (PV) panels to improve their efficiency as they are able to emit where PV modules show the maximum efficiency. A molecule that shows a large Stokes' shift was designed, synthesized, and intercalated into LDH. Two dyes already used in DSSCs were also intercalated to produce two new nanocomposites. LDH intercalation allows the stability of organic dyes to be improved and their direct use in polymer melt blending. The prepared nanocomposites absorb sunlight from UV to visible and emit from blue to near-IR and thus can be exploited for light-energy management. Finally one nanocomposite was dispersed by melt blending into a poly(methyl methacrylate)-block-poly(n-butyl acrylate) copolymer to obtain a photoactive film.