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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

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.

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.

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.

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