Search Results (36)

Weathering steel (WS) is widely used in bridge construction due to its high corrosion resistance, durability, and low maintenance requirements. This paper reviews the performance of WS bridges in Canadian climates, focusing on the formation of protective patina, influencing factors, and long-term maintenance strategies. The protective patina, composed of stable iron oxyhydroxides, develops over time under favorable wet–dry cycles but can be disrupted by environmental aggressors such as chlorides, sulfur dioxide, and prolonged moisture exposure. Key alloying elements like Cu, Cr, Ni, and Nb enhance corrosion resistance, while design considerations—such as drainage optimization and avoidance of crevices—are critical for performance. The study highlights the vulnerability of WS bridges to microenvironments, including de-icing salt exposure, coastal humidity, and debris accumulation. Regular inspections and maintenance, such as debris removal, drainage system upkeep, and targeted cleaning, are essential to mitigate corrosion risks. Climate change exacerbates challenges, with rising temperatures, altered precipitation patterns, and ocean acidification accelerating corrosion in coastal regions. Future research directions include optimizing WS compositions with advanced alloys (e.g., rare earth elements) and integrating climate-resilient design practices. This review highlights the need for a holistic approach combining material science, proactive maintenance, and adaptive design to ensure the longevity of WS bridges in evolving environmental conditions. Full article

The early detection of bronze disease is a significant challenge not only in conservation science but also in various industrial fields that utilize copper alloys (i.e., shipbuilding and construction). Due to the aggressive nature of this corrosion pathway, developing methods for its early detection is pivotal. The presence of copper trihydroxychlorides is the main key indicator of the ongoing autocatalytic process. Commonly used for pigment identification, reflectance imaging spectroscopy (RIS) or fiber optics reflectance spectroscopy (FORS) was recently employed for mapping atacamite distribution in extended bronze corrosion patinas. In this work, we detected the onset of bronze disease using visible–near-infrared (VIS-NIR) multispectral reflectography, which allowed for disclosing features that were poorly detectable to the naked eye. The image cube was analyzed using the spectral correlation mapper (SCM) algorithm to map the distribution of copper trihydroxychlorides. FORS and Raman spectroscopy were employed to characterize the patina composition and validate RIS data. A set of bronze samples, representative of Florentine Renaissance workshops, was specifically realized for the present study and artificially aged at different corrosion stages. Full article

Copper alloys form various corrosion products such as sulfides and chlorides. Chlorides can cause severe structural damage in ‘bronze disease’, making the early identification of corrosion products and conservation treatment important tasks. In this study, standard spectra were established for nine minerals of corrosion products using a portable Raman spectrometer, and their identification was verified by comparing them with benchtop micro-Raman spectra. The main characteristic bands were detected for most corrosion products, and the in situ applicability of the portable Raman spectrometer was demonstrated. However, for some samples, the signal-to-noise ratio was low, while the main characteristic peaks were still identifiable. In particular, dicopper chloride trihydroxides (such as atacamite and clinoatacamite) were clearly distinguished as corrosion products whose early identification is crucial. After the on-site analysis of copper alloy artworks exposed to outdoor environments for over 30 years, corrosion products such as malachite, brochantite, and moolooite were detected, indicating that portable Raman spectrometers are an effective tool for diagnosing conservation conditions. This study demonstrates that portable Raman spectrometers can be effectively used to identify corrosion products and assess the conservation state of copper alloy artworks and are expected to make significant contributions to future conservation and restoration efforts. Full article

Dechlorination is a crucial strategy for archeological bronze stabilization to resist corrosion induced by cuprous chloride (CuCl). Conventional samples, either archeological or simulated ones, have deficiencies in revealing dechlorination mechanisms for their complex rust layers and difficulties in quantifying chlorine content. In this work, samples with fixed chlorine amounts were prepared by compressing method to solve overcomplicated and unquantifiable problems. Then, patina profiles and desalinization solutions were analyzed to revisit the dechlorination mechanism across varying solution concentrations and current densities after dechlorination treatments. Results indicate that the sodium hydroxide (NaOH) desalinization method is achieved by converting CuCl to trihydroxychloride (Cu₂(OH)₃Cl). However, this transformation leads to an expansion of the CuCl layer, nearly doubling the CuCl layer thickness at the current density of 25 μA/cm². Dechlorination solution measurements provide information on quantifying chlorine removal and dechlorination progress. Theoretically, the endpoint (c₀) for the NaOH dechlorination method is supposed to be a chloride ion concentration of 358.2 ppm. As the NaOH solution concentrations vary from 10⁻⁶ to 10⁻², CuCl dechlorination progress (E_t=24h) calculations are at about 3% to 6% at 24 h. Applying the current significantly improves the effectiveness of dechlorination at 2.5 μA/cm². However, the chloride ion concentration in the solution starts to decrease after reaching a current density of 12.5 μA/cm², even dropping to 12.07 ppm at 25 μA/cm². According to a theoretical analysis, chlorine evolution during electrolytic processes would be responsible for this phenomenon. Full article

The safety and durability of engineering structures, like bridges, which are designed from weathering steels, are conditioned by the development of a sufficiently protective layer of corrosion products. Air pollution, the microclimate around the bridge, the time of wetness, the structural solution of the bridge, and the position and orientation of the surface within the bridge structure all influence the development of protective layers on the surface of the weathering steel. The condition of the formed patina relies on the working conditions of the structure. In fact, it is exposed to various types of salts that appear during the operation of the facility. In this article, the strength parameters of uncoated weathering steel were tested after accelerated aging of welded steel samples in a salt spray chamber. The tests showed the expected degradation of steel after long-term exposure to salt and changes in the strength parameters such as tensile strength, yield strength, and, importantly, impact strength, both in the steel itself and in the elements of the welded connection. The obtained results showed that the change is influenced by both the conditions in which the samples are made (welding method) and the direction of the welded joint (along or across the rolling direction). Full article

Acid rain is one of the primary corrosive agents on bronze exposed to the atmosphere. Bronze naturally forms a layer of oxides on its surface called patina, protecting it from corrosion. However, when exposed to acid rain, this layer dissolves, making it necessary to use a corrosion inhibitor or stabilize the patina. This study investigated fatty imidazolines derived from agro-industrial waste bran as a corrosion inhibitor of SAE-62 bronze in simulated acid rain (pH of 4.16 ± 0.1). Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curve (PC) measurements were used to evaluate corrosion inhibition efficiency, which was 90% for an inhibitor concentration of 50 ppm. The EIS measurements showed that the fatty imidazolines formed a protective film that stabilized the patina on the bronze surface to a certain extent by hindering the charge transfer process. SEM–EDS analyzed the morphology and composition of the protective oxide layer. The results were complemented by Raman spectroscopy and XRD analysis, indicating cuprite, tenorite, cassiterite, and covellite in the patina layer formed on the bronze surface. The SEM analysis showed that the protective coating on the bronze surface was homogeneous using a 50-ppm inhibitor concentration. The XRD analysis suggested the presence of an organic complex that stabilizes the corrosion products formed on the bronze surface. Full article

This work reports the study of metal fragments from Roman pipes excavated from the archaeological site of Pompeii and currently preserved in the deposits of the National Archaeological Museum of Naples (MANN). The Roman pipe, called the tibia, is a reed wind musical instrument similar to the Greek aulos. It can be made of wood, bone, and/or metal. Materials consisting of metal Cu-based alloys were excavated from archaeological burial environments. This research aims to identify the composition of the alloys, characterize the corrosion patinas, and identify any ancient surface treatments on the fragments. Non-invasive and micro-invasive techniques were used to achieve this aim, i.e., optical microscopy, Raman spectroscopy, attenuated total reflectance Fourier-transform infrared spectrophotometry, scanning electron microscopy, and energy dispersive spectrometry. This research contributes to a deeper understanding of the materials and manufacturing techniques used for these instruments, as well as the degradation processes occurring over the centuries. Full article

Bronze is an alloy composed primarily of copper and tin and since its discovery is widespread in the whole world. This alloy can thus be found in many archaeological sites and its study can give information about the technology of production, the trading routes, or the warfare within a region. However, bronze artefacts can undergo severe alteration processes, and the formation of corrosion layers of different copper minerals can prevent the readability of the artefact or even destroy it, as in the case of the ‘bronze disease’. Their preservation is crucial for maintaining a connection to our cultural heritage. In this paper, we present the study of some corroded bronze artefacts found in different burying conditions. They have been analysed through a scanner system that combines two non-invasive techniques, macro XRF (MA-XRF) and visible, near infrared, short wave infrared (VIS-NIR-SWIR) reflectance, to unravel information about the metal and the patina composition, thickness, and distribution. As the corrosion of bronze depends on the burying conditions and the alloy composition, these data are of the utmost importance to understanding the alteration processes occurring in the archaeological site and to ensure the artefacts’ optimal preservation. Full article

In this study, metal disks with different chemical composition (two Ag-based alloys and three Cu-based alloys) were buried in the soil of coastal archaeological sites for a period of 15 years. The aim was to naturally induce the growth of corrosion patinas to obtain a deeper insight into the role of alloying elements in the formation of the patinas and into the degradation mechanisms occurring in the very early stages of burial. To reach the aim, the morphological, compositional and structural features of the patinas grown over 15 years were extensively characterized by optical microscopy, field emission scanning electron microscopy coupled with energy dispersive spectrometry, X-ray diffraction and micro-Raman spectroscopy. Results showed that the Cu amount in Ag-based alloys strongly affected the final appearance, as well as the composition and structure of the patinas. Corrosion mechanisms typical of archaeological finds, such as the selective dissolution of Cu, Pb and Zn and internal oxidation of Sn, occurred in the Cu-based alloys, even if areas enriched in Zn and Pb compounds were also detected and attributed to an early stage of degradation. In addition, some unusual and rare compounds were detected in the patinas developed on the Cu-based disks. Full article

The Colossus of San Carlo Borromeo, named San Carlone for its large dimensions, represents a unique opportunity to study the long-term effects of atmospheric corrosion on patina formation on historic copper sheets. The sculpture’s large dimensions, complex geometry, direct visitor interaction, and exposure conditions generate different microclimates. The purpose of this study is to understand how and to what extent these microclimates affect the formation of the copper patinas. The results show that microclimates play a key role in patina formation: in external surfaces exposed to rain, the main constituent is brochantite, whereas a wider variety of corrosion products have been found in sheltered and internal surfaces, such as antlerite, atacamite, copper oxalate, posnjakite, and anglesite. Full article

The study of characterisation and production of artificial patinas plays a key role in the field of cultural heritage. In particular, artistic patinas should be considered as an integral part of the artworks, as they are deliberately produced by artists and metalworkers as a part of their artistic design. Therefore, it is important to achieve a good knowledge of their composition and corrosion behaviour in order to setup and perform optimal conservation strategies for their preservation. In addition, the possibility of realising laboratory patinas that are as representative as possible of natural corrosion layers is important for the realisation of laboratory specimens which can be used as reliable model systems (mock-ups) for the study of degradation mechanisms and conservative treatments. For this work, both artistic and laboratory patinas have been considered and investigated. In particular, six different artistic patinas produced by Fonderia Artistica Battaglia were characterised. Moreover, a series of laboratory patinas was produced according to chemical procedures adapted from those already reported in the literature. The patina morphology was evaluated by stereomicroscopy observations, their composition was analysed by means of FTIR and XRD analysis and their corrosion behaviour was evaluated by LPR and EIS measurements. Finally, the LPR and EIS analysis have pointed out the low protection provided by the corrosion layers of artistic patinas. In regard to laboratory patinas, the optimized procedures of production were found to be effective for the realization of the main corrosion products of copper-based surfaces. From an electrochemical point of view in particular, quite different electrochemical behaviours were observed on artificial corrosion layers with the same chemical composition. Full article

Copper trihydroxychlorides, which are known as “bronze disease”, are dangerous corrosion products that compromise the stability and conservation of bronze sculptures. Here, we performed artificial patina corrosion experiments on quaternary bronze (Cu-Zn-Sn-Pb) to examine the corrosion behavior of the chloride patina commonly found in bronze objects in marine environments. The chromaticity and reflectance of the patina in the context of the corrosion products indicate that copper trihydroxychloride, which is commonly found in a single color in marine environments, was produced early in the corrosion experiment. Furthermore, the corrosion of bronze had different effects on the alloying elements, contrary to pure copper corrosion. The chloride patina formed a single patina layer of copper trihydroxychlorides. This patina layer was divided into the outer porous powder and inner uniform layers. Furthermore, the interaction of oxygen in the atmosphere with the corrosion layer and internal oxidation of tin in the alloy promoted powdering. These results provide important basic data for research on sculpture conservation and corrosion characteristics, such as changes in color, chemical composition, and corrosion products on the patina surfaces of outdoor bronze sculptures. Full article

This study reports the analytical approach towards nine coins found in wreck A of Fontanamare for understanding the complex corrosion processes that take place in underwater conditions. Optical microscopy (OM) combined with micro-Raman (µ-Raman) spectroscopy, X-ray diffractometry (XRD), and scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM and EDS) were used to analyze the nature and the microstructure of the corrosion patina in comparison with the non-degraded state of coins. Three main types of corrosion patina based on copper, lead chloride, and carbonate were identified: black, white, and green, and the obtained results demonstrate the complex corrosion processes that take place in underwater conditions. To better understand the role played by different chemical and physical parameters in the corrosion of bronze artefacts in an underwater environment, this study attempts to understand the nature of the patinas on the coins in relation to the specific structural and environmental parameter variation. Full article

Protective coatings for bronze relics should adhere to the basic principles of cultural relic preservation, such as not altering the color and appearance of the artifacts, and being moderately combined with the artifacts to resist erosion due to external environments (such as water and gas). This paper presents the development of a physically crosslinked supramolecular hydrogel produced from guanidinium-based chitosan (GC). The hydrogel exhibits the excellent adsorption protection of bronze, and the addition of clay enhances the water barrier properties of the chitosan film. The supramolecular interaction between sodium polyacrylate/GC/clay confers corrosion buffering capability to the hydrogel coating in corrosive environments, and the gel coating can be self-healing at room temperature for 24 h. The fabricated nanocomposites were comprehensively characterized using various methods (Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, etc.). The electrochemical properties of coated specimens were evaluated, and the impedance spectrum revealed a large impedance arc indicating high charge resistance, which has a corrosion resistance effect. Full article

Copper alloys interact with air pollutants to form corrosion products and, consequently, a patina on outdoor bronze sculptures. In this study, corrosion experiments were conducted to clarify the corrosion behaviors of artificial sulfide patina in an urban–industrial environment on a quaternary bronze alloy (Cu–Zn–Sn–Pb) with a composition and metallurgical properties similar to those of outdoor bronze sculptures. The correlation between the chromaticity and reflectance of the patina revealed increasing brochantite with the corrosion of the patina and an association between the chromaticity a^* and patina growth. Cuprite and brochantite were distinguished, and the point at which brochantite covered the patina surface was determined. The quantitative changes in brochantite were mainly influenced by physical causes such as the crystal size and patina layer thickness as well as by Cu²⁺ ions working as color formation ions moving to the outermost layer. Atmospheric corrosion of the alloy resulted in reduced Cu and Zn contents and increased Sn and Pb contents. The patina consisted of brochantite in the outermost layer and cuprite and cassiterite in the inner layers. These findings should clarify corrosion characteristics such as the surface color, composition, and changes in corrosion products of outdoor bronze sculptures and contribute toward their preservation. Full article