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The constant increase of CO2 concentration in the atmosphere is recognized worldwide to severely impact the environment and human health. Zeolites possess a high adsorption capacity for CO2 removal, but their powdery form prevents their use in many practical applications. When binding agents are used, a partial occlusion of the porosity can severely compromise the adsorption capacity. In this regard, a great challenge is producing compact composite adsorbents while maintaining a high specific surface area to preserve the pristine performance of zeolites. Here, this goal was achieved by preparing beads with a high content of zeolite 13X (up to 90 wt %) using a chitosan aerogel as the binding agent. A facile preparation procedure based on the freeze-drying of hydrogel beads obtained by phase inversion led to a peculiar microstructure in which a very fine polymeric framework firmly embeds the zeolite particles, providing mechanical coherence and strength (compressive strain >40% without bead fragmentation, deformation

The study of the reinforcement network in elastomer compounds is one of the most relevant issues for the application of these materials because their properties are strongly dependent on the obtained morphology. To this regard, the viscoelastic and dielectric behavior of vulcanized styrene butadiene rubber (SBR) reinforced with different amounts of carbon nanotubes (CNT) have been investigated and compared with the vulcanized unfilled SBR and the vulcanized SBR samples reinforced with a conventional amount of carbon black (40 phr). Differential scanning calorimetry (DSC) measurements have been carried out to highlight possible differences of the glass transition temperatures for all the reinforced compounds. The percolation threshold value of the nanocomposite samples has been estimated by dielectric analysis. Finally, dynamic mechanical analysis (DMA) measurements have been performed in tensile mode in the temperature range of −60 to 80 °C to obtain both E′ and E′′. From these experimental data, the master curve for each sample has been estimated by using the time–temperature superposition principle in combination with the vertical shift approach. From the analysis of this latter, the activation energy, associated to the thermal movement of the reinforcement network, has been calculated to better elucidate the reinforcement mechanism in the nanocomposites.

In the recent years a considerable effort has been devoted to foster the understanding of the basic mechanisms underlying the dynamical arrest that is involved in glass forming in supercooled liquids and in the sol-gel transition. The elucidation of the nature of such processes represents one of the most challenging unsolved problems in the field of material science. In this context, two important theories have contributed significantly to the interpretation of these phenomena: the Mode-Coupling theory (MCT) and the Percolation theory (PT). These theories are rooted on the two pillars of statistical physics, universality and scale laws, and their original formulations have been subsequently modified to account for the fundamental concepts of Energy Landscape (EL) and of the universality of the fragile to strong dynamical crossover (FSC). In this review, we discuss experimental and theoretical results, including Molecular Dynamics (MD) simulations, reported in the literature for colloidal and polymer systems displaying both glass and sol-gel transitions. Special focus is dedicated to the analysis of the interferences between these transitions and on the possible interplay between MCT and PT. By reviewing recent theoretical developments, we show that such interplay between sol-gel and glass transitions may be interpreted in terms of the extended F13 MCT model that describes these processes based on the presence of a glass-glass transition line terminating in an A3 cusp-like singularity (near which the logarithmic decay of the density correlator is observed). This transition line originates from the presence of two different amorphous structures, one generated by the inter-particle attraction and the other by the pure repulsion characteristic of hard spheres. We show here, combining literature results with some new results, that such a situation can be generated, and therefore experimentally studied, by considering colloidal-like particles interacting via a hard core plus an attractive square well potential. In the final part of this review, scaling laws associated both to MCT and PT are applied to describe, by means of these two theories, the specific viscoelastic properties of some systems.

Interactions between nanoparticles (NPs) determine their self-organization and dynamic processes. In these systems, a quantitative description of the interparticle forces is complicated by the presence of the hydrophobic effect (HE), treatable only qualitatively, and due to the competition between the hydrophobic and hydrophilic forces. Recently, instead, a sort of crossover of HE from hydrophilic to hydrophobic has been experimentally observed on a local scale, by increasing the temperature, in pure confined water and studying the occurrence of this crossover in different water–methanol solutions. Starting from these results, we then considered the idea of studying this process in different nanoparticle solutions. By using photon correlation spectroscopy (PCS) experiments on dendrimer with OH terminal groups (dissolved in water and methanol, respectively), we show the existence of this hydrophobic–hydrophilic crossover with a well defined temperature and nanoparticle volume fraction dependence. In this frame, we have used the mode coupling theory extended model to evaluate the measured time-dependent density correlation functions (ISFs). In this context we will, therefore, show how the measured spectra are strongly dependent on the specificity of the interactions between the particles in solution. The observed transition demonstrates that just the HE, depending sensitively on the system thermodynamics, determines the hydrophobic and hydrophilic interaction properties of the studied nanostructures surface.

Chitosan (CS) aerogels were prepared by freeze-drying as potential adsorbents for water purification, and the effect of the strategy of crosslinking was investigated by varying the amount of crosslinker (glutaraldehyde) and the sequence of steps for the preparation of the aerogel. Two procedures were compared, in which the crosslinking step was carried out before or after the freeze-drying of the starting CS solution. When crosslinking was postponed after the freeze-drying step, the adsorption capacity towards an anionic dye, such as indigo carmine, considerably increased (up to +45%), reaching values as high as 534.4 ± 30.5 mg g−1. The same crosslinking strategy ensured a comparable improvement also in nanocomposite aerogels containing graphene oxide (GO), which was added to enhance the mechanical strength and provide adsorption capacity towards cationic dyes. Besides possessing good mechanical strength (compressive modulus higher than 1 MPa), the CS/GO aerogels were able to bind also cationic pollutants such as methylene blue. The maximum uptake capacity increased from 4.3 ± 1.6 to 168.6 ± 9.6 mg of cationic dye adsorbed per gram of adsorbent with respect to pristine CS aerogels.

In the last decade, a great deal of research has been devoted to the design and development of graphene-based polymer nanocomposites characterized by a prescribed arrangement of the graphene-based nanosheets into spatially segregated 3D architectures. The formation of a continuous filler network obtained by confining the nanosheets into a constrained volume of the polymeric matrix is particularly attractive from a technological point of view. The preparation of segregated 3D graphene-based architectures facilitates the proper tailoring of the overall performance of the resulting polymer nanocomposites, providing significant improvements in terms of structural (i.e., mechanical properties) and functional (electrical properties, sensing ability, and adsorption/absorption capacity) features. This review focuses on polymer-based nanocomposites in two categories, namely bulk and porous (foam and aerogels) systems. These all share the common distinctive feature that relies on the peculiar arrangement of the graphene-based nanosheets in the form of a segregated yet continuous 3D assembly. For each class of materials, the main preparation strategies are presented and the resulting structure-property correlations are highlighted and discussed, together with the technological implications, and possible future directions.

Chitosan (CS) is largely employed in environmental applications as an adsorbent of anionic dyes, due to the presence in its chemical structure of amine groups that, if protonated, act as adsorbing sites for negatively charged molecules. Efficient adsorption of both cationic and anionic dyes is thus not achievable with a pristine chitosan adsorbent, but it requires the combination of two or more components. Here, we show that simultaneous adsorption of cationic and anionic dyes can be obtained by embedding Linde Type A (LTA) zeolite particles in a crosslinked CS-based aerogel. In order to optimize dye removal ability of the hybrid aerogel, we target the crosslinker concentration so that crosslinking is mainly activated during the thermal treatment after the fast freezing of the CS/LTA mixture. The adsorption of isotherms is obtained for different CS/LTA weight ratios and for different types of anionic and cationic dyes. Irrespective of the formulation, the Langmuir model was found to accurately describe the adsorption isotherms. The optimal tradeoff in the adsorption behavior was obtained with the CS/LTA aerogel (1:1 weight ratio), for which the maximum uptake of indigo carmine (anionic dye) and rhodamine 6G (cationic dye) is 103 and 43 mg g−1, respectively. The behavior observed for the adsorption capacity and energy cannot be rationalized as a pure superposition of the two components, but suggests that reciprocal steric effects, chemical heterogeneity, and molecular interactions between CS and LTA zeolite particles play an important role.

Water pollution is one of the biggest environmental issues of our times. To address such a huge challenge, the full involvement of everyone is required. In this context, we report the results of outreach hands-on activities aimed at presenting to the general public two classes of materials with high potential in the removal of common water pollutants, such as heavy metals and dyes: zeolites and chitosan-based aerogels. Under the guidance of young students of materials science and engineering, participants have performed safe, fast, and easy to understand experiments for the removal of copper ions and dye molecules from water. The discussion of the results, which was adapted time by time to the knowledge and age of the audience, provided all participants with a general understanding of the two phenomena underlying water purification, namely, ion exchange for zeolites and molecular adsorption for chitosan aerogels. Besides raising awareness of young people about water pollution and, more in general, about environmental issues, the proposed activity highlights the key role of materials scientists in providing smart and feasible solutions to tackle everyday problems.

Self-healing coatings that are able to self-repair after being damaged represent an effective solution to provide a reliable and long-lasting protection of the underlying substrate. In this work, we developed self-healing waterborne polyurethane (PU) coatings through the introduction of Diels-Alder bonds in the polymer backbone. Although heat is typically used as trigger, here we exploited photothermal converters to allow also NIR light-induced self-healing. To this aim, we synthesized (3-aminopropyl)-triethoxysilane-modified graphene oxide nanosheets that were subsequently coated by nanometric polydopamine particles, which serve for imparting to the coating the NIR-responsive self-healing feature. Fourier transform infrared and X-ray photoelectron spectroscopy confirmed the successful synthesis of PDA-coated reduced graphene oxide nanoparticles, which were thus exploited to prepare nanocomposite PU coatings on bronze substrates on which they exhibited good adhesion. Once scratched, fast and effective self-healing was ensured upon irradiation with NIR light for only 30 s. In addition, electrochemical impedance spectroscopy analyses proved that the nanocomposite coatings exhibited improved barrier properties which resulted in an enhanced protection of the underlying metal from corrosion.

Organic dyes are extensively used in many industrial sectors, and their uncontrolled disposal into wastewaters raises serious concerns for environmental and human health. Due to the large variety of such pollutants, an effective remediation strategy should be characterized by a broad-spectrum efficacy. A promising strategy is represented by the combination of different adsorbent materials with complementary functionalities to develop composite materials that are expected to remove different contaminants. In the present work, a broad-spectrum adsorbent was developed by embedding zeolite 13X powder (ZX) in a chitosan (CS) aerogel (1:1 by weight). The CS–ZX composite adsorbent removes both anionic (indigo carmine, IC) and cationic (methylene blue, MB) dyes effectively, with a maximum uptake capacity of 221 mg/g and 108 mg/g, respectively. In addition, the adsorption kinetics are rather fast, with equilibrium conditions attained in less than 2 h. The composite exhibits good mechanical properties in both dry and wet state, which enables its handling for reusability purposes. In this regard, preliminary tests show that the full restoration of the IC removal ability over three adsorption–desorption cycles is achieved using a 0.1 M NaOH aqueous solution, while a 1 M NaCl aqueous solution allows one to preserve &gt, 60% of the MB removal ability.

Organic coatings are extensively investigated as possible solution to prevent or at least retard the occurring of corrosion processes on metal surfaces. Their actual breakthrough is still hampered by the risk of barrier properties loss because of local failure of the coating integrity. To address this issue, self-healing coatings, which are intrinsically able to recover from damages upon exposure to external stimuli, are currently gaining increasing attention. Herein, waterborne polyurethanes (PU) are synthesized, and a Diels-Alder adduct is added into the polymeric backbone to endow the material with self-healing functionality. The effect of different diisocyanate in PU synthesis is explored, namely isophorone diisocyanate, 4,4 '-dicyclohexylmethane diisocyanate (HMDI), and hexamethylene diisocyanate. The obtained results highlight the key role of the interactions among soft and hard segments in ultimately defining the coating performances. Actually, the combination of Fourier transform infrared spectroscopy, atomic force microscopy and X-ray diffration analysis reveals that the HMDI-based PU have showed the best balance in terms of H-bonding strength among hard segments and crystallinity degree in the soft ones. This allows to reach a good compromise in terms of mechanical resistance, anticorrosion properties, and self-healing ability.

The subsoil consolidation in the archaeological sites or in areas with historic existing buildings (e.g. Pompeii) needs the use of ground improvement techniques that must guarantee the safeguarding of such relevant areas and structures. One of the best approaches in such cases is low pressure grouting. An experimental multidisciplinary study was carried out with the aim to design and characterize a sustainable chemical grout sodium silicate-based catalysed by NaHCO3. The evolution from sol-to-glassy phase of the grouts was carefully investigated, furthermore the effectiveness of the grout has been verified either by lab tests or by real-scale field trials. The experimental findings suggested that it is possible to properly control the viscosity and gel-time of the grout modulating the amount of catalyst without affecting the final consolidation performances. Furthermore, the results at real-scale validate the safety of the above approach in cultural heritage applications, since it allowed a complete permeation of the soil without worsening its final properties. (C) 2019 Elsevier Ltd. All rights reserved.

The class of imidazolium salts contains effective anticorrosion additives for metal substrates. This study evaluated the potential of 1-carboxymethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (HO2CC1MImNTf2) for application in cultural heritage, exploring it as anticorrosion additive in chitosan-based coatings for the protection of copper-based alloys. Under accelerated corrosion conditions with HCl vapor, the chitosan coating with HO2CC1MImNTf2 was less effective than the one with benzotriazole. The coating with a combination of HO2CC1MImNTf2 and benzotriazole resulted in the optimal protective efficacy of the bronze surface, and it also maintained high transparency without changing the bronze appearance.

The effect of small amounts (≤3 wt%) of short hemp fibers on stability of a poly(lactic acid) (PLA) in the molten state is investigated through time-resolved rheology. The decrease over time of the zero-frequency complex viscosity was correlated to severe hydrolytic degradation of the PLA matrix. A kinetic model that accounts for thermal degradation and hydrolysis was fitted to the experimental viscosity data. The significant fiber-induced hydrolysis is due to traces of residual water bound to the fibers inside the composites after the processing steps. A significant mitigation of the fiber-induced PLA hydrolysis can be obtained by carefully drying the hemp fibers before melt compounding and (to a lesser extent) by subjecting the fibers to an alkaline treatment. On the other hand, if the interest is a shorter persistence in the environment, natural fibers can be exploited to accelerate degradation of biocomposites.

Corrosion inhibitors are largely exploited for the development of highly performing polymeric active coatings. One of the major drawbacks, however, relies in their UV sensitivity, which may compromise their ability to effectively prevent corrosion processes. This issue is particularly relevant in the field of cultural heritage preservation, in which polymeric active coating which are able to ensure a reliable and long-lasting protection against corrosion are highly needed. Besides proving that UV-induced photodegradation impressively lowers the corrosion inhibition ability of benzotriazole (BTA), in the present work we show that this phenomenon can be largely prevented by exploiting inorganic nanocarriers. More specifically, BTA molecules loaded into functionalized mesoporous silica nanoparticles are preserved from photodegradation and released in the host coating only in the presence of acid-related external stimuli. Accelerated corrosion tests carried out on a commercial acrylic-based coating containing engineered mesoporous silica nanoparticles loaded with BTA demonstrated that the developed system possesses an excellent anticorrosion ability.

Polyurethanes (PUs) have been extensively exploited for the production of protective coatings thanks to the versatility of their chemistry, which allows to adjust the coating properties depending on the final application. In the last decade, the concerns on the negative impact on the environment and human health of traditional petroleum-based and solvent-borne PUs have fostered the research on more environmentally friendly alternatives. This review article provides an overview of the recent approaches that have been profitably pursued for the development of green PUs coatings for the protection of metal surfaces from corrosion. In particular, waterborne and bio-based polyurethane coatings are addressed, highlighting the main strategies adopted to enhance their anticorrosion ability. Finally, relevant data on the protective performances of green PU coatings are collected and critically discussed.

The reduced graphene oxide (rGO) modified natural rubber composite (NR) filled with high contents of silica was prepared by a wet compounding and latex mixing process using a novel interface modifier cystamine dihydrochloride (CDHC) with coagulation ability. CDHC acts as a coagulation agent through electrostatic interaction with rGO, SiO2, and latex rubber particles during the latex-based preparation process, while in the obtained silica/graphene/natural rubber composites, CDHC acts as an interface modifier. Compared with the composites prepared by the conventional mechanical mixing method, the dispersion of both rGO and SiO2 in the composites made by a wet compounding and latex mixing process is improved. As a result, the obtained silica/graphene/natural rubber composite prepared by this new method has good comprehensive properties. A Dynamic Mechanical Test suggests that the tan &delta, values of the composites at 60 oC decrease, indicating a low rolling resistance with increasing the graphene content at a low strain, but it increases at a higher strain. This unique feature for this material provides an advantage in the rubber tire application.

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion &alpha, P and the specific heat differences CP&minus, CV, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid &ldquo, phases&rdquo, namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the CP&minus, CV isobars behaviors clearly support the existence of both a liquid&ndash, liquid transition and of a liquid&ndash, liquid critical point.

Two types of innovative coatings based on fluoroethylene/vinylether alternating copolymers are investigated as protective systems for bronze works-of-art. The influence of a polyhedral oligomeric silsesquioxane (POSS), i.e. open-cube trisilanol-heptaisooctyl-POSS, on the surface, mechanical, optical and electrochemical properties of coatings is examined. It is found that the isooctyl groups in the organic shell of POSS cause an increase in the hydrophobicity of the surface. On the other hand, nanoindentation tests show that the reduced modulus, hardness and plasticity index decrease with the addition of POSS, while abrasion resistance is slightly improved. Haze of coatings increases when POSS nanoparticles are present. More importantly, a beneficial effect of POSS addition on the protective efficiency against corrosion is assessed by exposure of coatings to acidic vapours and electrochemical treatments. In this regard, potentiodynamic polarisation clearly shows that the protective efficiency is systematically larger for coatings comprising POSS. The ex situ IR reflection-absorption spectroelectrochemistry shows that cuprous oxide can eventually form at the coating|bronze interface, which is identified through the spectroelectrochemistry of unprotected bronze. Keywords: Bronze, Protective coating, Nanocomposite, Fluoropolymer, POSS nanoparticle, Nanoindentation

The efficacy of chitosan-based hydrogels in the removal of dyes from aqueous solutions has been investigated as a function of different parameters. Hydrogels were obtained by gelation of chitosan with a non-toxic gelling agent based on an aqueous basic solution. The preparation procedure has been optimized in terms of chitosan concentration in the starting solution, gelling agent concentration and chitosan-to-gelling agent ratio. The goal is to properly select the material- and process-related parameters in order to optimize the performances of the chitosan-based dye adsorbent. First, the influence of such factors on the gelling process has been studied from a kinetic point of view. Then, the effects on the adsorption capacity and kinetics of the chitosan hydrogels obtained in different conditions have been investigated. A common food dye (Indigo Carmine) has been used for this purpose. Noticeably, although the disk-shaped hydrogels are in the bulk form, their adsorption capacity is comparable to that reported in the literature for films and beads. In addition, the bulk samples can be easily separated from the liquid phase after the adsorption process, which is highly attractive from a practical point of view. Compression tests reveal that the samples do not breakup even after relatively large compressive strains. The obtained results suggest that the fine tuning of the process parameters allows the production of mechanical resistant and highly adsorbing chitosan-based hydrogels.

The elasticity and structure of graphite nanoplatelets networks in polymer matrices are studied through linear viscoelastic analyses. GNPs-filled polystyrene nanocomposites at different filler content are prepared through a combination of solution and melt mixing techniques. Electrical volume conductivity experiments prove that a continuous path of conductive nanoplatelets builds up across the matrix above a critical filler content. GNP networks, however, are too tenuous to be detected through conventional dynamic-mechanical spectroscopy in the melt state. Nevertheless, we are able to estimate their elasticity by exploiting the predictive feature of a simple two-phase rheological model. Our approach, validated through the building of a master curve of the elastic modulus of samples at different composition, allows to isolate the elastic contribution of the bare GNP network, whose dynamics reveal that its elasticity follows critical behaviour as predicted by percolation theory.

The dispersibility of unfunctionalized multi-walled carbon nanotubes in a polymer matrix is studied focusing on the role of the morphology and structure of the primary aggregates. The particles, synthesized by fluidized bed catalytic chemical vapor deposition and purified through a scalable one-pot method, are dispersed in polystyrene by melt mixing. The filler percolation threshold, assessed through rheological analyses and dielectric spectroscopy, is one order of magnitude lower than that of commercially available nanotubes with similar features. This is ascribed to the hierarchical structure of the primary aggregates, which facilitates both the infiltration of the polymer in the earlier stages of mixing and the pulling out of the nanotubes required for their individualization. The high dispersibility is not achieved to the detriment of the nanotube integrity, and the nanocomposites exhibit enhanced thermal stability and dynamic mechanical properties at low amounts of filler.