Cecilia Monticelli

Recycling plastics waste into concrete represents one of the possible approaches for its valorization, offering both economic and environmental benefits. Although numerous studies have explored the mechanical properties of concrete with plastics waste, its durability performance remains largely unexplored. In this context, this study aims to assess the electrochemical behavior of rebars embedded in reinforced concrete modified by partially replacing natural aggregates with recycled plastics, comparing their behavior to that of conventional concrete. The corrosion of reinforcing steel bars was evaluated by wet and dry cycles (w/d) in calcium chloride solutions, monitoring corrosion potential and potentiostatic polarization resistance, and recording electrochemical impedance spectroscopy (EIS) and polarization curves. In addition, the chloride diffusion tendency and the mechanical performances were assessed in unreinforced samples. The findings indicate that in environments with lower chloride concentrations, concrete with plastic granules provides good protection against rebar corrosion. Although the mechanical results of the studied mixes confirmed that incorporating plastic granules as aggregates in the concrete matrix causes a reduction in compressive strength, as known in the literature, the modified concrete also exhibits improved post-cracking behavior, resulting in enhanced ductility and fracture toughness.

In the field of sustainable construction materials, the production of eco-friendly concretes, obtained by the addition of waste products such as biochar and recycled polymer particles, offers interesting alternatives to traditional materials. Biochar is a carbonaceous solid by-product obtained from the thermo-chemical conversion of biomass and its addition into concrete admixtures can offer an eco-friendly carbon sequestration solution, capable to slightly improve concrete properties. Recycled polymer materials can be used to partially replace conventional aggregates with the aim of obtaining lighter concretes that help to face the disposal challenge presented by this non-degradable plastic waste. However, the influence of these waste additions on the corrosion behavior of steel rebars embedded in these “eco-concretes” is still unexplored. Within this context, this work presents some results of an extensive study dealing with the concrete mechanical and physical properties and the rebar corrosion resistance during cyclic exposures to chloride-containing solutions.

Duplex α + β’ brasses are widely used in drinking water distribution systems for tube fittings, valves, and ancillaries because they are low cost, easy to fabricate, and exhibit high mechanical strength. However, depending on application conditions and alloy composition, they may undergo dealloying and stress corrosion cracking. In this research, three different brass types, two leaded (CW617N and CW602N) alloys and one lead-free brass (CW724R), were investigated to assess their corrosion behavior and susceptibility to stress corrosion cracking (SCC) in simulated drinking water (SDW) solutions containing different chloride concentrations, compatible with drinking water composition requirements according to Moroccan standard NM 03.7.001. The corrosion behavior was assessed by electrochemical tests such as polarization curve recording and electrochemical impedance spectroscopy (EIS) monitoring, coupled to SEM-EDS surface observations. The susceptibility to SCC was investigated by slow strain rate tests (SSRT). The tests showed that corrosion was mainly under diffusion control and chlorides slightly accelerated corrosion rates. All alloys, and particularly CW617N, were affected by SCC under the testing conditions adopted and in general the SCC susceptibility increased at increasing chloride concentration.

Application of protective coatings is the most widely used conservation treatment for outdoor bronzes. Eco-friendly and non-hazardous coatings are currently needed for conservation of outdoor bronze monuments. To fulfil this need, the M-ERA.NET European research project B-IMPACT (Bronze-IMproved non-hazardous PAtina CoaTings) aimed at assessing the protectiveness of innovative coatings for historical and modern bronze monuments exposed outdoors. In this project, two bronze substrates (historical Cu-Sn-Zn-Pb and modern Cu-Si-Mn alloys) were artificially patinated, by acid rain solution using dropping test and by “liver of sulphur” procedure (K₂S aqueous solution) to obtain black patina, respectively. Subsequently, the application of several newly developed protective coatings was carried out and their performance was investigated by preliminary electrochemical tests. In the following steps of the work, the assessment of the best-performing coatings was carried out and their performance was compared to Incralac, one of the most widely used protective coatings in conservation practice. A multi-analytical approach was adopted, considering artificial ageing (carried out in representative conditions, including exposure to rain runoff, stagnant rain and UV radiation) and metal release, as well as visual aspect (so as to include aesthetical impact among the coating selection parameters) and morphological and structural evolution of the coated surfaces due to simulated outdoor exposure. Lastly, also the health impact of selected coatings was assessed by occupational hazard tests. The removability and re-applicability of the best-performing coatings were also assessed. The best alternatives to the conventional Incralac exhibited were: (i) fluoroacrylate blended with methacryloxy-propyl-trimethoxy-silane (FA-MS) applied on patinated Cu-Sn-Zn-Pb bronze and (ii) 3-mercapto-propyl-trimethoxysilane (PropS-SH) applied on patinated Cu-Si-Mn bronze.

The protectiveness of coatings based on 3-mercaptopropyl-trimethoxysilane (PropS-SH) applied on bronze artworks was enhanced by investigating and tuning a variety of factors. In particular, the coating performances were optimized by proper additive choice among oxide nanoparticles (CeO₂, La₂O₃, TiO₂) and microparticles (fly ash (FA)), and by varying the aging time of the nanoparticle suspensions before coating application and the RT curing time of the coatings. Moreover, the possibility of conservation of the silane solution under refrigerated conditions was assessed. The aggressive environment was a tenfold concentrated synthetic acid rain (AR × 10). The techniques adopted comprised electrochemical tests (polarization curve recording and EIS tests) and SEM-Energy Dispersion Spectroscopy (EDS) observations. In the case of FA microparticles, never used before as additives in silane coatings, further tests were performed in FA suspensions in AR × 10 to clarify the contribution of these particles to PropS-SH coating protectiveness. The tests included pH measurements, elemental chemical analyses, and electrochemical tests on bare bronze. Improved performances of PropS-SH coatings were achieved by La₂O₃, CeO₂, and FA addition, with La₂O₃ affording the best results during 20 days of immersion. The positive influence of FA was connected to its alkaline character and to the release of soluble silicates.

The corrosion protection of coatings can be reinforced by the addition of entrapped corrosion inhibitors. β-cyclodextrin (β-CD) can form inclusion complexes with small inhibiting organic molecules that, when entrapped in coatings, allow the inhibitor release and adsorption at corrosion initiation sites. In this paper, several Nuclear Magnetic Resonance (NMR)-based experiments (e.g., Complexation-Induced Shifts (CIS), NMR titration, Diffusion-Ordered Spectroscopy (DOSY)) were performed to study the stability and geometry of a complex formed by β-cyclodextrin with 5-mercapto-1-phenyl-tetrazole (MPT). The complex was also detected by Electrospray Ionization (ESI) mass spectrometry and characterized by Fourier Transform Infrared (FTIR) spectra. Its influence on the protectiveness of a silane coating against bronze corrosion was evaluated in plain (AR) and concentrated (ARX10) synthetic acid rain, under different exposure conditions. In particular, the time evolution of the polarization resistance values during 20 days in ARX10 and the polarization curves recorded at the end of the immersions evidenced a higher protectiveness of the coating with the β-CD–MPT complex in comparison to that containing only MPT or only β-CD. The cyclic AR spray test carried out on coated bronze coupons with cross-cut scratches evidenced the absence of underfilm corrosion starting from the scratches only in the complex-containing coating.

Some α + β’ brass components of drinking water distribution systems in Morocco underwent early failures and were investigated to assess the nature and extent of the corrosion attacks. They exhibited different corrosion forms, often accompanied by extensive β’ dezincification. In order to offer viable alternatives to these traditional low cost materials, the corrosion behavior of two representative α + β’ brass components was compared to that of brass alloys with nominal compositions CuZn36Pb2As and CuZn21Si3P, marketed as dezincification resistant. CuZn21Si3P is a recently developed eco-friendly brass produced without any arsenic or lead. Electrochemical tests in simulated drinking water showed that after 10 days of immersion CuZn21Si3P exhibited the highest polarization resistance (R_p) values but after longer immersion periods its R_p values became comparable or lower than those of the other alloys. After 150 days, scanning electron microscope coupled to energy dispersive spectroscopy (SEM-EDS) analyses evidenced that the highest dezincification resistance was afforded by CuZn36Pb2As (longitudinal section of extruded bar), exhibiting dealloying and subsequent oxidation of β’ only at a small depth. Limited surface dealloying was also found on CuZn21Si3P, which underwent selective silicon and zinc dissolution and negligible inner oxidation of both α and κ constituent phases, likely due to peculiar galvanic effects.

This paper reports the effects of thermal aging between 650 and 850 °C on the localized corrosion behavior of lean duplex stainless steel (LDSS 2404). Critical pitting temperature (CPT) and double loop electrochemical potentiokinetic reactivation (DL-EPR) tests were performed. The localization of pitting attack and intergranular corrosion (IGC) attack after DL-EPR was investigated by optical (OM) and scanning electron microscopy (SEM) and by focused ion beam (FIB) coupled to SEM. Thermal aging caused the precipitation of mainly chromium nitrides at grain boundaries. Aging at 650 °C or short aging times (5 min) at 750 °C caused nitride precipitation mainly at α/α grain boundaries as a result of fast diffusion of chromium in this phase. Aging at 850 °C or aging times from 10 to 60 min at 750 °C also allowed the precipitation at the α/γ interface. Nitrides at γ/γ grain boundaries were observed rarely and only after long aging times (60 min) at 850 °C. Electrochemical tests showed that in as-received samples, pitting attack only affected the α phase. Conversely, in aged samples, pitting and IGC attack were detected close to nitrides in correspondence of α/α and α/γ grain boundaries depending on aging temperatures and times.