Last 10 IPCB CT publications on ISI journals
1) Enhancing mechanical properties of recycled sheet molding compound composites through catalytic and ozone activation
G.Rizzo, S.Dattilo, L.Saitta, C.Tosto, E.Pergolizzi, A.Latteri, G.Cicala
DOI:
https://doi.org/10.1002/pc.29411
scraps or end-of-life product (EoL) of glass fiber reinforced polymer composites, such as sheet molding compound (SMC), without gravely impact on energy and costs. However, the resulting material is characterized by a discontinuous bulk, limiting its application to low-value products. In this study, a comprehensive characterization of composites made by fresh unsaturated polyester resin (UPR) and recycled SMC with a content from 10% up to 40% by weight (wt), was carried out. To enhance the chemical interactions between the inert recycled SMC and the fresh UPR, and as consequence their mechanical properties, two different transesterification catalysts, aluminum (III) sec-butoxide and titanium (IV) butoxide at 1.0 wt%, were utilized. To further investigate the interaction between SMC and fresh UPR, an ozone treatment was carried out on SMC before blending and all the composites compared with no-treated reference systems. Among the formulated composites, the one made by 40 wt% of SMC and titanium (IV) butoxide results to be the most performant system with a Tg around 137°C, a modulus of 3.7 GPa and strain at break around 1.42%. These results could innovate the manufacturing of recycled composites with superior mechanical properties, potentially used for applications such as cabinet, panels, or external cladding.
2) Bio-based palladium catalyst in cryogel for cross-coupling reactions
E.G.Tomarchio, C.Zagni, V.Paratore, G.G.Condorelli, S.Carroccio, A.Rescifina
DOI:
https://doi.org/10.1039/D4QM00800F
Biobased catalysts play a crucial role in sustainable chemistry, using natural resources to support eco-friendly processes. While palladium catalysts are essential for various industrial applications, they often pose environmental challenges due to their non-reusability and tendency to degrade. To address these issues, we developed an innovative phenylalanine-based catalyst containing palladium (C-PhebPd) designed for the Suzuki?Miyaura reaction. The natural amino acids, used as monomers, chelate palladium, preventing leaching, unlike other heterogeneous catalysts that use palladium nanoparticles, which can be released over time, leading to catalyst degradation. Such catalyst exhibits outstanding performance in aqueous media at moderate temperatures, facilitating cross-coupling reactions between various aryl halides and arylboronic acids with high yields of up to 99%. The affordable synthetic procedure and C-PhebPd’s stability make it potentially scalable for industrial applications. The robustness of this catalyst was also proved by recyclability tests up to seven cycles. Further investigation into its capabilities could unlock additional insights for various catalytic transformations.
3) Polyvinylimidazole-Based Cryogel as an Efficient Tool for the Capture and Release of Oleuropein in Aqueous Media
V.Giglio, C.Zagni, E.Spina, F.Cunsolo, S.Carroccio
DOI:
https://doi.org/10.3390/polym16162339
A polyvinylimidazole-based cryogel is presented as a pioneering solution for efficient extraction and release of partially water-soluble polyphenols from olive byproducts. Specifically, oleuropein was used as model molecule to evaluate its recovery from water. The material merges the properties of interconnected cryogel structure in adsorbing molecules via fast diffusion flux, with the strong electrostatic interactions acted by imidazole moiety. Such cryogel achieves effective oleuropein binding likely through hydrogen bonding and π-π interactions. Comprehensive assessments of static adsorption kinetics, isotherms, and desorption kinetics underscore the cryogel’s efficacy in oleuropein extraction and release, highlighting its pivotal role in valorizing olive wastewater through sustainable biotechnological applications.
4) Efficient green solvent-free CO2/epoxide cycloaddition catalyzed by a β-cyclodextrin-imidazolium-based ionic liquid
E.G.Tomarchio, C.Zagni, R.Turnaturi, S.Dattilo, V.Patamia, G.Floresta, S.Carroccio, T.Mecca, A.Rescifina
DOI:
https://doi.org/10.1016/j.jiec.2024.08.024
The rising atmospheric carbon dioxide (CO
2) levels significantly contribute to climate change. Converting CO
2 into valuable products offers an attractive strategy to mitigate its environmental impact. Here, we present a highly efficient, solvent-free method for CO
2 fixation into cyclic carbonates using a novel green catalyst, β-cyclodextrin, linked to an imidazolium-based ionic liquid (β-CD-Im
+Br
-). This catalyst facilitates the conversion of various terminal and internal epoxides into cyclic carbonates with exceptional performance. Notably, β-CD-Im
+Br
- achieves up to 98% conversion of styrene oxide to its corresponding carbonate within 24h at 120°C, demonstrating significant activity without needing a co-catalyst. Operating under solvent-free conditions, this method avoids environmentally harmful synthetic pathways by utilizing the hydroxyl groups of cyclodextrins as hydrogen bond donors and employing the bromine counterion to facilitate epoxide ring opening. Mechanistic studies reveal that β-CD-Im
+Br
- enhances catalytic performance by lowering the activation energy of the rate-limiting step through its hydrogen bond acceptor properties. Importantly, the catalyst is both recyclable and reusable, highlighting its cost-effectiveness and environmental benefits. This approach represents a significant advancement in sustainable chemistry, offering a green alternative for CO
2 fixation.
5) Sustainable biocomposites based on Mater-Bi and grape pomace for a circular economy: Performance evaluation and degradation in soil
V.Titone, M.Rapisarda, L.Pulvirenti, E.Napoli, G.Impallomeni, L.Botta, M.C.Mistretta, P.Rizzarelli
DOI:
https://doi.org/10.1016/j.polymdegradstab.2024.111091
Biodegradable polymers often exhibit inferior properties and higher cost compared to their fossil-derived counterparts. The addition of plant waste and by-products can improve their performances, providing in the meantime functional activity and reducing their cost. In this work, we summarize the preparation of different biocomposites (BioCs) incorporating two diverse amounts (10 % and 20 %) of grape pomace (GP) in a Mater-Bi (MB) sample. GP, MB as well as BioCs were fully characterized. The influence of addition of GP on the properties and degradation in soil of the biocomposites was evaluated in comparison with the neat MB. However, natural antioxidants and other active compounds from GP could be sensitive to temperature. Thus, GP and MB underwent heat treatment at 180 °C to simulate and induce possible degradation during BioCs processing. GP analysis (particle size 50 μm) showed only a slight decrease of antioxidant potency, despite the heat treatment simulating the BioCs processing.
1H NMR of the MB soluble fraction in CDCl
3 displayed the presence of two polymeric components: polylactide (PLA) and poly(butylene adipate-
co-butylene terephthalate) (PBAT). Introduction of GP in the polymer matrix induced a proportional increase of antioxidant property in the BioCs as well as in complex viscosity at low frequencies. Moreover, a slight increase in the elastic modulus was observed with increasing the crystallinity of the samples. Degradation rate in soil, monitored by weight loss, increased with filler content and time. Moreover, NMR showed that, in the recovered sample after 45 days, the composition of PBAT changed, with the terephthalic percentage increased
6) Cyclodextrin-based iodophors with high iodine retention in solid state and in dilute solutions
F.Spitaleri, S.Dattilo, D.Aleo, M.G.Saita, A.Patti
DOI:
https://doi.org/10.1016/j.carbpol.2024.122969
Iodine is a broad-spectrum antiseptic with the advantage of not inducing bacterial resistance, but its use is limited by volatility. This issue can be overcome by using "iodophors", which are molecular systems able to retain iodine and provide its sustained release. Cyclodextrins have proven effective in stabilizing iodine in solution through the formation of complexes, the preparation of which in solid form could offer additional benefits in terms of handling and storage. A series of cyclodextrins (CD) were tested for their ability to form solid complexes with iodine and it was found that the addition of potassium iodide in the solid-state preparation of the complexes significantly increases both iodine incorporation and long-term stability compared to the solids obtained without added potassium iodide. Dilute aqueous solutions of the obtained complexes were monitored for their iodine content in different conditions and excellent stability was observed in some cases. Furthermore, these cyclodextrin-iodine complexes showed no cytotoxic effects on human corneal epithelial cells (HCE-2) while displayed very high antimicrobial (against
Staphylococcus epidermis) and antiviral (against Human adenovirus 5) activities. These findings highlight the potential of cyclodextrins as a versatile platform for the development of solid iodophors as an alternative to the traditional povidone-iodide formulation.
7) Biodegradation of Polystyrene by Plastic-Eating Tenebrionidae Larvae
E.A.Di Liberto, G.Battaglia, R.Pellerito, G.Curcuruto, N.Tz.Dintcheva
DOI:
https://doi.org/10.3390/polym16101404
Polystyrene (PS) is an extremely stable polymer with a relatively high molecular weight and a strong hydrophobic character that makes it highly resistant to biodegradation. In this study, PS was subjected to biodegradation tests by
Tenebrio Molitor (T. Molitor) and
Zophobas Morio (Z. Morio) larvae. Specifically, six different experimental diets were compared: (i)
T. Molitor fed with bran; (ii)
T. Molitor fed only PS; (iii)
T. Molitor fed only PS treated with H
2O
2; (iv)
Z. Morio fed with bran; (v)
Z. Morio fed only PS; and (vi)
Z. Morio fed only PS treated with H
2O
2. Therefore, the mass change of the larvae and the survival rate were measured periodically, while the frass collected after 15 and 30 days was analyzed by different analyses, such as spectroscopy (FTIR), spectrometry (molecular weight and polydispersity), thermal analysis (TGA) and microscopy (scanning electron microscopy observations). The obtained results suggest that in the case of
T. Molitor larvae, larvae feeding on bran showed the highest survival rate of ∼94% at 30 days, while in the case of the
Z. Morio larvae, the highest survival rate was exhibited by larvae eating PS-H
2O
2. Although not strongly pronounced, the M
w and M
n of PS in the frass of both
T. Molitor and
Z. Morio larvae decreased over 30 days, suggesting PS biodegradation. Finally, the morphological analysis shows that PS samples isolated from the frass of
T. Molitor and
Z. Morio larvae showed completely different, rough and irregularly carved surface structures, in comparison to PS before biodegradation.
8) A simple rheological method for the experimental assessment of the fiber percolation threshold in short fiber biocomposites
L.Vitiello, M.Salzano de Luna, V.Ambrogi, G.Filippone
DOI:
https://doi.org/10.1016/j.compscitech.2023.110345
The identification of the percolation threshold (Φc) in short fiber composites is a challenging problem in Composite Science. Above Φc the fibers form a continuous network that causes substantial changes in mechanical and transport properties. Besides, percolation of natural fibers in biodegradable polymer matrices allows water and other pro-degradative species to access the inner parts of the material from the external environment, accelerating biodegradation. Whether such a speeding up is desired or not, assessing Φc in composites is of utmost importance. Unfortunately, natural fibers are not conductive and exhibit highly variable shape and physical properties. This prevents the use of many experimental and theoretical approaches for the estimate of Φc. Here we propose an original rheological approach borrowed from the viscoelastic modelling of polymer nanocomposites. The method was applied to two systems made of poly(lactic acid) filled with hemp or kenaf fibers (average length <500μm, average length-to-diameter ratio <5). The estimate of Φc (∼10.1 and 19.5 vol% for the hemp- and kenaf-based composite, respectively) required a single set of simple linear viscoelastic measurements, and the computed values were in good agreement with those obtained through time-consuming (measurement times >3 weeks) dielectric spectroscopy analyses (∼10.1 and 18.5 vol%).
9) Understanding the Effects of Adding Metal Oxides to Polylactic Acid and Polylactic Acid Blends on Mechanical and Rheological Behaviour, Wettability, and Photo-Oxidation Resistance
E.Morici, G.Pecoraro, S.Carroccio, E.Bruno, P.Scarfato, G.Filippone, N.Tz Dintcheva
DOI:
https://doi.org/10.3390/polym16070922
Biopolymers are of growing interest, but to improve some of their poor properties and performance, the formulation of bio-based blends and/or adding of nanoparticles is required. For this purpose, in this work, two different metal oxides, namely zinc oxide (ZnO) and titanium dioxide (TiO2), at different concentrations (0.5, 1, and 2%wt.) were added in polylactic acid (PLA) and polylactic acid/polyamide 11 (PLA/PA11) blends to establish their effects on solid-state properties, morphology, melt behaviour, and photo-oxidation resistance. It seems that the addition of ZnO in PLA leads to a significant reduction in its rigidity, probably due to an inefficient dispersion in the melt state, while the addition of TiO2 does not penalize PLA rigidity. Interestingly, the addition of both ZnO and TiO2 in the PLA/PA11 blend has a positive effect on the rigidity because of blend morphology refinement and leads to a slight increase in film hydrophobicity. The photo-oxidation resistance of the neat PLA and PLA/PA11 blend is significantly reduced due to the presence of both metal oxides, and this must be considered when designing potential applications. The last results suggest that both metal oxides could be considered photo-sensitive degradant agents for biopolymer and biopolymer blends.
10) TiO2-MoS2-PMMA Nanocomposites for an Efficient Water Remediation
V.Spanò, M.Cantarella, M.Zimbone, F.Giuffrida, G.Sfuncia, G.Nicotra, A.Alberti, S.Scalese, L.Vitiello, S.Carroccio, G.Impellizzeri
DOI:
https://doi.org/10.3390/polym16091200
An improvement of water supply and sanitation and better management of water resources, especially in terms of water reuse, is one of the priorities of the European Green Deal. In this context, it is crucial to find new strategies to recycle wastewater efficiently in a low-cost and eco-friendly manner. The immobilization of inorganic nanomaterials on polymeric matrices has been drawing a lot of attention in recent years due to the extraordinary properties characterizing the as-obtained nanocomposites. The hybrid materials, indeed, combine the properties of the polymers, such as flexibility, low cost, mechanical stability, high durability, and ease of availability, with the properties of the inorganic counterpart. In particular, if the inorganic fillers are nanostructured photocatalysts, the materials will be able to utilize the energy delivered by light to catalyze chemical reactions for efficient wastewater treatment. Additionally, with the anchoring of the nanomaterials to the polymers, the dispersion of the nanomaterials in the environment is prevented, thus overcoming one of the main limits that impede the application of nanostructured photocatalysts on a large scale. In this work, we will present nanocomposites made of polymers, i.e., polymethyl methacrylate (PMMA), and photocatalytic semiconductors, i.e., TiO
2 nanoparticles (Evonik). MoS
2 nanoflakes were also added as co-catalysts to improve the photocatalytic performance of the TiO
2. The hybrid materials were prepared using the sonication and solution casting method. The nanocomposites were deeply characterized, and their remarkable photocatalytic abilities were evaluated by the degradation of two common water pollutants: methyl orange and diclofenac. The relevance of the obtained results will be discussed, opening the route for the application of these materials in photocatalysis and especially for novel wastewater remediation.
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