Mechanical and Physical Changes in Bio-Polybutylene-Succinate Induced by UVC Ray Photodegradation.

Bio-polybutylene succinate (PBS) is a biodegradable polymer obtained from renewable feedstock having physical-mechanical properties like traditional low-density polyethylene (LDPE). PBS is employed by many manufacturing sectors, from biomedical to agri-food and cosmetics. Although some studies have already evaluated the resistance of PBS to photodegradation caused by natural outdoor solar exposure (UVA-UVB), a systematic study on the resistance to degradation caused by exposure to UVC rays, which is the subject of this study, has not yet been carried out. PBS was exposed to UVC either neat or filled with 2% carbon black (CB). Mechanical and physical characterization (tensile, hardness, calorimetry, contact angle, morphology, and surface roughness analyses) indicates that the bulk and surface properties of the polymer matrix changes after exposure to UVC radiations, due to a severe degradation. However, the presence of carbon black compensates for the degradation phenomenon. Because UVC rays are used for the sterilization process, necessary in applications such as biomedical, cosmetic, pharmaceutical, food, and other products, a comparison of the protocol used in this paper with the literature's data has been reported and discussed.

Comparative Investigation of AquaSun Eco-Friendly Antifouling Coating via Rheological and Mechanical Characterization.

Rheological and mechanical comparative tests of the new AquaSun antifouling sol-gel coating coated on shipbuilding steel compared to a commercial silyl acrylate antifouling top coat containing cuprous oxide and copper pyrithione show further evidence of the practical viability of this multifunctional coating for the protection of the immersed surfaces from biofouling. AquaSun is a less rigid or less viscous material than commercial top coat but more adherent to the steel substrate. These results support further investigation of this multifunctional sol-gel coating as an eco-friendly antifouling paint.

Plastics today: Key challenges and EU strategies towards carbon neutrality: A review.

Never as today the need for collaborative interactions between industry, the scientific community, NGOs, policy makers and citizens has become crucial for the development of shared political choices and protection of the environment, for the safeguard of future generations. The complex socio-economic and environmental interconnections that underlie the EU strategy of the last years, within the framework of the Agenda 2030 and the green deal, often create perplexity and confusion that make difficult to outline the definition of a common path to achieve carbon neutrality and "net zero emissions" by 2050. Scope of this work is to give a general overview of EU policies, directives, regulations, and laws concerning polymers and plastic manufacturing, aiming to reduce plastic pollution, allowing for a better understanding of the implications that environmental concern and protection may generate from a social-economical point of view.

Adhesive and Rheological Features of Ecofriendly Coatings with Antifouling Properties.

In this work, formulations of "environmentally compatible" silicone-based antifouling, synthesized in the laboratory and based on copper and silver on silica/titania oxides, have been characterized. These formulations are capable of replacing the non-ecological antifouling paints currently available on the market. The texture properties and the morphological analysis of these powders with an antifouling action indicate that their activity is linked to the nanometric size of the particles and to the homogeneous dispersion of the metal on the substrate. The presence of two metal species on the same support limits the formation of nanometric species and, therefore, the formation of homogeneous compounds. The presence of the antifouling filler, specifically the one based on titania (TiO2) and silver (Ag), facilitates the achievement of a higher degree of cross-linking of the resin, and therefore, a better compactness and completeness of the coating than that attained with the pure resin. Thus, a high degree of adhesion to the tie-coat and, consequently, to the steel support used for the construction of the boats was achieved in the presence of the silver-titania antifouling.

Super-Hydrophobicity of Polyester Fabrics Driven by Functional Sustainable Fluorine-Free Silane-Based Coatings.

Polyester fibers are widely employed in a multitude of sectors and applications from the technical textiles to everyday life thanks to their durability, strength, and flexibility. Despite these advantages, polyester lacks in dyeability, adhesion of coating, hydrophilicity, and it is characterized by a low wettability respect to natural fibers. On this regard, beyond the harmful hydrophobic textile finishings of polyester fabrics containing fluorine-compounds, and in order to avoid pre-treatments, such as laser irradiation to improve their surface properties, research is moving towards the development of fluorine-free and safer coatings. In this work, the (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and various long alkyl-chain alkoxysilanes were employed for the fabrication in the presence of a catalyst of a water-based superhydrophobic finishing for polyester fabrics with a simple sol-gel, non-fluorinated, sustainable approach and the dip-pad-dry-cure method. The finished polyester fabrics surface properties were investigated by static and dynamic water repellency tests. Additionally, the resistance to common water-based liquids, abrasion resistance, moisture adsorption, and air permeability measurements were performed. Scanning electron microscopy was employed to examine the micro- and nano-morphology of the functionalized polyester fabrics surfaces. The obtained superhydrophobic finishings displayed high water-based stain resistance as well as good hydrophobicity after different cycles of abrasion.

Chitosan/POSS Hybrid Hydrogels for Bone Tissue Engineering.

Hybrid hydrogels composed of chitosan (CS) have shown great potential in bone tissue engineering and regeneration. The introduction of polyhedral oligomeric silsesquioxanes (POSS) in the biopolymeric matrix has been demonstrated to improve the rheological and biological properties of the hybrid composites. In this work, we have integrated the favourable features of chitosan (CS) and POSS nanoparticles to design new nanocomposites for bone tissue regeneration, focusing our attention on the effect of POSS concentration within the CS matrix (0.5, 1, and 1.5 equivalents in weight of POSS with respect to CS) on the chemical, physical, rheological, and in vitro biological properties of the final composites. The drug release ability of the synthesized hydrogel scaffolds were also investigated using, as the model drug, ketoprofen, that was included in the scaffold during the gelling procedure, showing a more controlled release for the hybrids with respect to CS (86-91% of drug released after two weeks). The results of the in vitro biological tests performed on human fetal osteoblastic cells (hFOB 1.19) culture demonstrated the great biocompatibility of the hybrid materials. The hybrids, at the different POSS concentrations, showed values of cell mortality superimposable with control cells (11.1 vs. 9.8%), thus revealing the CS/POSS hydrogels as possible candidates for bone tissue engineering applications.

Waterborne Eco-Sustainable Sol-Gel Coatings Based on Phytic Acid Intercalated Graphene Oxide for Corrosion Protection of Metallic Surfaces.

In the past few years, corrosion protection of metal materials has become a global challenge, due to its great economic importance. For this reason, various methods have been developed to inhibit the corrosion process, such as surface treatment approaches, by employing corrosion inhibitors through the deposition of opportunely designed functional coatings, employed to preserve from corrosion damages metallic substrates. Recently, among these techniques and in order to avoid the toxic chromate-based pre-treatment coatings, silane-based coatings and films loaded with organic and inorganic corrosion inhibitors have been widely used in corrosion mitigation water-based surface treatment. In this study, the synthetic approach was devoted to create an embedded, hosted, waterborne, and eco-friendly matrix, obtained by use of the sol-gel technique, through the reaction of functional alkoxysilane cross-linking precursors, namely (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and (3-aminopropyl)triethoxysilane (APTES), in the presence of graphene oxide (GO) intercalated with natural and non-toxic phytic acid (PA) molecules. As a matter of fact, all experimental results from FT-IR spectroscopy, UV-Vis analysis, and SEM confirmed that PA molecules were successfully decorated on GO. Furthermore, polarization measurements and a neutral salt spray test were used to evaluate the anticorrosive performance on aluminum and steel substrates, thus showing that the GO-PA nanofiller improved the barrier and corrosion protection properties of the developed functional silane-based coatings.

Functional Silane-Based Nanohybrid Materials for the Development of Hydrophobic and Water-Based Stain Resistant Cotton Fabrics Coatings.

The textile-finishing industry, is one of the main sources of persistent organic pollutants in water; in this regard, it is necessary to develop and employ new sustainable approaches for fabric finishing and treatment. This research study shows the development of an efficient and eco-friendly procedure to form highly hydrophobic surfaces on cotton fabrics using different modified silica sols. In particular, the formation of highly hydrophobic surfaces on cotton fabrics was studied by using a two-step treatment procedure, i.e., first applying a hybrid silica sol obtained by hydrolysis and subsequent condensation of (3-Glycidyloxypropyl)trimethoxy silane with different alkyl(trialkoxy)silane under acid conditions, and then applying hydrolyzed hexadecyltrimethoxysilane on the treated fabrics to further improve the fabrics' hydrophobicity. The treated cotton fabrics showed excellent water repellency with a water contact angle above 150° under optimum treatment conditions. The cooperative action of rough surface structure due to the silica sol nanoparticles and the low surface energy caused by long-chain alkyl(trialkoxy)silane in the nanocomposite coating, combined with the expected roughness on microscale due to the fabrics and fiber structure, provided the treated cotton fabrics with excellent, almost super, hydrophobicity and water-based stain resistance in an eco-sustainable way.

Development of Eco-Friendly Hydrophobic and Fouling-Release Coatings for Blue-Growth Environmental Applications: Synthesis, Mechanical Characterization and Biological Activity.

The need to ensure adequate antifouling protection of the hull in the naval sector led to the development of real painting cycles, which involve the spreading of three layers of polymeric material on the hull surface exposed to the marine environment, specifically defined as primer, tie coat and final topcoat. It is already well known that coatings based on suitable silanes provide an efficient and non-toxic approach for the hydrophobic and antifouling/fouling release treatment of surfaces. In the present work, functional hydrophobic hybrid silica-based coatings (topcoats) were developed by using sol-gel technology and deposited on surfaces with the "doctor blade" method. In particular, those organic silanes, featuring opportune functional groups such as long (either fluorinated) alkyl chains, have a notable influence on surface wettability as showed in this study. Furthermore, the hydrophobic behavior of this functionalized coating was improved by introducing an intermediate commercial tie-coat layer between the primer and the topcoat, in order to decrease the wettability (i.e., decreasing the surface energy with a matching increase in the contact angle, CA) and to therefore make such coatings ideal for the design and development of fouling release paints. The hereby synthesized coatings were characterized by optical microscopy, contact angle analysis and a mechanical pull-off test to measure the adhesive power of the coating against a metal substrate typically used in the nautical sector. Analysis to evaluate the bacterial adhesion and the formation of microbial biofilm were related in laboratory and simulation (microcosm) scales, and assessed by SEM analysis.

Design and Development of Fluorinated and Biocide-Free Sol-Gel Based Hybrid Functional Coatings for Anti-Biofouling/Foul-Release Activity.

Biofouling has destructive effects on shipping and leisure vessels, thus producing severe problems for marine and naval sectors due to corrosion with consequent elevated fuel consumption and higher maintenance costs. The development of anti-fouling or fouling release coatings creates deterrent surfaces that prevent the initial settlement of microorganisms. In this regard, new silica-based materials were prepared using two alkoxysilane cross-linkers containing epoxy and amine groups (i.e., 3-Glycidyloxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane, respectively), in combination with two functional fluoro-silane (i.e., 3,3,3-trifluoropropyl-trimethoxysilane and glycidyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylether) featuring well-known hydro repellent and anti-corrosion properties. As a matter of fact, the co-condensation of alkoxysilane featuring epoxide and amine ends, also mixed with two opportune long chain and short chain perfluorosilane precursors, allows getting stable amphiphilic, non-toxic, fouling release coatings. The sol-gel mixtures on coated glass slides were fully characterized by FT-IR spectroscopy, while the morphology was studied by scanning electron microscopy (SEM), and atomic force microscopy (AFM). The fouling release properties were evaluated through tests on treated glass slides in different microbial suspensions in seawater-based mediums and in seawater natural microcosms. The developed fluorinated coatings show suitable antimicrobial activities and low adhesive properties; no biocidal effects were observed for the microorganisms (bacteria).

Antifouling Systems Based on Copper and Silver Nanoparticles Supported on Silica, Titania, and Silica/Titania Mixed Oxides.

Silica, titania, and mixed silica-titania powders have been used as supports for loading 5 wt% Cu, 5 wt% Ag, and 2.5 wt% Cu-2.5 wt% Ag with the aim of providing a series of nanomaterials with antifouling properties. All the solids were easily prepared by the wetness-impregnation method from commercially available chemical precursors. The resulting materials were characterized by several techniques such as X-ray diffraction analysis, X-ray photoelectron spectroscopy, N2 physisorption, and temperature-programmed reduction measurements. Four selected Cu and Ag SiO2- and TiO2-supported powders were tested as fillers for the preparation of marine antifouling coatings and complex viscosity measurements. Titania-based coatings showed better adhesion than silica-based coatings and the commercial topcoat. The addition of fillers enhances the resin viscosity, suggesting better workability of titania-based coatings than silica-based ones. The ecotoxicological performance of the powders was evaluated by Microtox luminescence tests, using the marine luminescent bacterium Vibrio fisheri. Further investigations of the microbiological activity of such materials were carried out focusing on the bacterial growth of Pseudoalteromonas sp., Alteromonas sp., and Pseudomonas sp. through measurements of optical density at 600 nm (OD600nm).

Agri-Food Wastes for Bioplastics: European Prospective on Possible Applications in Their Second Life for a Circular Economy.

Agri-food wastes (such as brewer's spent grain, olive pomace, residual pulp from fruit juice production, etc.) are produced annually in very high quantities posing a serious problem, both environmentally and economically. These wastes can be used as secondary starting materials to produce value-added goods within the principles of the circular economy. In this context, this review focuses on the use of agri-food wastes either to produce building blocks for bioplastics manufacturing or biofillers to be mixed with other bioplastics. The pros and cons of the literature analysis have been highlighted, together with the main aspects related to the production of bioplastics, their use and recycling. The high number of European Union (EU)-funded projects for the valorisation of agri-food waste with the best European practices for this industrial sector confirm a growing interest in safeguarding our planet from environmental pollution. However, problems such as the correct labelling and separation of bioplastics from fossil ones remain open and to be optimised, with the possibility of reuse before final composting and selective recovery of biomass.

Study of Protective Layers Based on Crosslinked Glutaraldehyde/3-aminopropyltriethoxysilane.

In this paper, we report the synthesis and characterization of novel coatings based on (3-aminopropyl)-triethoxysilane (AP) mixed with different amounts of glutaraldehyde (GA). The synthesized coatings have been layered on a glass substrate and characterized by optical microscopy and roughness measurements, thermogravimetric analyses and differential scanning calorimetry, contact angle analysis, rheological measurement, and an adhesion test. It was observed that the higher the GA content (up to AP:GA ratio of 0.3), the sooner the crosslinking reaction starts, leading to a coating with increased hydrophobic and adhesion features without compromising the final AP cross-linked network. Hence, the obtained results show the effectiveness of AP modification with GA from the perspective of an application as protective coatings.

Polyurethane Foams Loaded with Carbon Nanofibers for Oil Spill Recovery: Mechanical Properties under Fatigue Conditions and Selective Absorption in Oil/Water Mixtures.

Marine pollution due to spillage of hydrocarbons represents a well-known current environmental problem. In order to recover the otherwise wasted oils and to prevent pollution damage, polyurethane foams are considered suitable materials for their ability to separate oils from sea-water and for their reusability. In this work we studied polyurethane foams filled with carbon nanofibers, in varying amounts, aimed at enhancing the selectivity of the material towards the oils and at improving the mechanical durability of the foam. Polyurethane-based foams were experimentally characterized by morphological, surface, and mechanical analyses (optical microscopy observation, contact angle measurement, absorption test according to ASTM F726-99 standard and compression fatigue tests according to ISO 24999 standard). Results indicated an increase in hydrophobic behavior and a good oleophilic character of the composite sponges besides an improved selective absorption of the foam toward oils in mixed water/oil media. The optimal filler amount was found to be around 1 wt% for the homogeneous distribution inside the polymeric foam. Finally, the fatigue test results showed an improvement of the mechanical properties of the foam with the growing carbon filler amount.

Mechanical, Wear and Thermal Behavior of Polyethylene Blended with Graphite Treated in Ball Milling.

Additive manufacturing, civil, and biomechanical applications are among the most important sectors, where the filler's presence can significantly improve the quality of polymeric products blends. The high market demand of new low-cost material to be used as shock absorbers and mechanical joints arouses our curiosity to study a relatively common commercial polymer and filler. The possible improvement by blending high-density polyethylene (HDPE) and graphite was investigated for these sectors. To achieve this objective, we have prepared HDPE/graphite nanocomposites following mechanical treatment to understand which parameter provides the researched properties. As widely reported in the literature, milling treatment leads to the decrease of the particle size and the exfoliation of graphitic layers. Therefore, graphite has been previously treated with a ball mill for different times (1-16 h) to enhance its lubricating action. We checked an improvement in stiffness, yielding strength, thermal stability, and, in particularly, wear resistance that increased by 65% with respect to that of polyethylene (PE). A treatment time of eight hours in ball milling could be enough to give an appreciable improvement. The wear behavior of HDPE with treated graphite has not been deeply investigated so far, and it could be important because HDPE is considered a "carrier polymer" for different low-friction applications.

Mechanical Properties of Protective Coatings against Marine Fouling: A Review.

The accumulation of marine organisms on ship hulls, such as microorganisms, barnacles, and seaweeds, represents a global problem for maritime industries, with both economic and environmental costs. The use of biocide-containing paints poses a serious threat to marine ecosystems, affecting both target and non-target organisms driving science and technology towards non-biocidal solutions based on physico-chemical and materials properties of coatings. The review reports recent development of hydrophobic protective coatings in terms of mechanical properties, correlated with the wet ability features. The attention is focused mainly on coatings based on siloxane and epoxy resin due to the wide application fields of such systems in the marine industry. Polyurethane and other systems have been considered as well. These coatings for anti-fouling applications needs to be both long-term mechanically stable, perfectly adherent with the metallic/composite substrate, and capable to detach/destroy the fouling organism. Prospects should focus on developing even "greener" antifouling coatings solutions. These coatings should also be readily addressable to industrial scale-up for large-scale product distribution, possibly at a reasonable cost.

Mechanical Characterization of Nanocomposite Joints Based on Biomedical Grade Polyethylene under Cyclical Loads.

Polymeric joints, made of biomedical polyethylene (UHMWPE) nanocomposite sheets, were welded with a diode laser. Since polyethylene does not absorb laser light, nanocomposites were prepared containing different percentages by weight of titanium dioxide as it is a laser absorbent. The joints were first analyzed with static mechanical tests to establish the best percentage weight content of filler that had the best mechanical response. Then, the nanocomposites containing 1 wt% titanium dioxide were selected (white color) to be subjected to fatigue tests. The experimental results were also compared with those obtained on UMMWPE with a different laser light absorbent nano filler (carbon, with greater laser absorbing power, gray in color), already studied by our research team. The results showed that the two types of joints had an appreciable resistance to fatigue, depending on the various loads imposed. Therefore, they can be chosen in different applications of UHMWPE, depending on the stresses imposed during their use.

Wear Resistant Nanocomposites Based on Biomedical Grade UHMWPE Paraffin Oil and Carbon Nano-Filler: Preliminary Biocompatibility and Antibacterial Activity Investigation.

In the present paper, we investigate the effectiveness of nanocomposites (composed of ultra-high molecular weight polyethylene (UHMWPE) mixed with carbon nano-filler (CNF) and medical grade paraffin oil (PO), from the biological point of view. Wear measurements were carried out without (air) and with lubricant (distilled water, natural, and artificial lubricant), and antibacterial activity and cytotoxicity were evaluated. The results highlighted that the presence of CNF is important in the nanocomposite formulation because it reduces the wear rate and prevents oxidative degradation during its processing. An amount of 1.0 wt % of CNF is best because it reaches the optimal distribution within the polymeric matrix, resulting in the best wear resistant, bio-active, and anti-bacterial nanocomposite among all investigated samples.

Chitosan/PAMAM/Hydroxyapatite Engineered Drug Release Hydrogels with Tunable Rheological Properties.

In this paper, a new formulation of biodegradable and bioresorbable chitosan-based hydrogel for controlled drug release was investigated. A chitosan-dendrimer-hydroxyapatite hydrogel, obtained by covalently grafting chitosan powder with an hyperbranched PAMAM dendrimer followed by in-situ precipitation of hydroxyapatite and gelification, was synthesized and characterized by FTIR, NMR, TGA, XRD and rheological studies. The hydrogels have been also doped with an anti-inflammatory drug (ketoprofen) in order to investigate their drug release properties. Chemical and chemical-physical characterizations confirmed the successful covalent functionalization of chitosan with PAMAM and the synthesis of nanostructured hydroxyapatite. The developed hydrogel made it possible to obtain an innovative system with tunable rheological and drug-releasing properties relative to the well-known formulation containing chitosan and hydroxyapatite powder. The developed hydrogel showed different rheological and drug-releasing properties of chitosan matrix mixed with hydroxyapatite as a function of dendrimer molecular weight; therefore, the chitosan-dendrimer-hydroxyapatite hydrogel can couple the well-known osteoconductive properties of hydroxyapatite with the drug-release behavior and good processability of chitosan-dendrimer hydrogels, opening new approaches in the field of tissue engineering based on biopolymeric scaffolds.

Threads Made with Blended Biopolymers: Mechanical, Physical and Biological Features.

Poly (Lactic Acid), PLA, and Poly (ε-CaproLactone), PCL, compatibilized with Ethyl Ester l-Lysine Triisocyanate (LTI) can be employed as biomaterials. We mixed PLA with PCL and LTI in a twin extruder and by a melt spinning process obtained threads with an average diameter of about 0.3 mm. In order to study the possible application of these threads, mechanical tensile (with the calorimetric and morphological investigations) and biological tests were performed. The results highlighted these biopolymers as promising materials for sutures since they can be rigid and elastic (especially by increasing the PCL amount in the blend), and they are bioactive, able to inhibit bacterial growth. This paper represents a starting point to optimize the blend composition for biomedical suture application.