Archaeological iron objects were excavated from the Nanhai I ship from the Southern Song Dynasty that sunk in the South China Sea. Most of these artifacts were severely corroded and fragmented. In order to understand their current corrosion state and guide their restoration and protection, optical microscopy, scanning electron microscopy, micro-laser Raman spectroscopy, infrared spectroscopy and X-ray diffraction were all selected for analysis. It was clear that the archaeological iron material was hypereutectic white iron with a carbon content of about 4.3–6.69%, and had experienced low-melt undercooling. There were many internal cracks formed by general corrosion that extended to the iron core, which tended to make the material unstable. At the interface between the iron and rust, there was a black dense layer enriched with chlorine, and a loose yellow outer layer. The dense layer was mainly composed of magnetite, akaganeite and maghemite, while the rust of the loose layer was composed of lepidocrocite, goethite, feroxyhite, maghemite and hematite. The major phases of all corrosion products were akaganeite and lepidocrocite. Numerous holes and cracks in the rust layer exhibited no barrier ability to the outside electrolyte, hence the iron core formed many redox electrochemical sites for general corrosion with the rust. Meanwhile, the dense rust located close to the iron core was broken locally by an enriched chlorine layer that was extremely detrimental to the stability of the archaeological iron. Using electrochemical impedance spectroscopy, it could be determined that the rust layers had no protective effect on the internal iron core under conditions of simulated seawater, and these rust layers even accelerated the corrosion. A mechanism for the rust growth as a result of laboratory testing was proposed to explain the entire corrosion process. In view of the desalination preservation treatment that had been applied for ten years, it was not recommended to maintain a single desalination operation. The archaeological rusted iron of the Nanhai I ship that was excavated from the marine environment should be properly stabilized and protected using corrosion inhibition and rust transformation for iron oxyhydroxides, since the rust structure and the internal iron core retain well together.

A large number of iron pot artifacts were excavated from the “Nanhai I” shipwreck. The rapid embrittlement and pulverization of these objects (that have a good matrix) in the atmospheric environment is worthy of attention. Metallographic analysis showed that the material of the iron pots was hypereutectic white cast iron. Micro-CT observations revealed that there were numerous microcracks and fissures within the seemingly well-preserved iron. These fissures increased and enlarged with prolonged exposure to air. Scanning electron microscopy exhibited that the microcracks were initially created at the “concave surface” formed by the ferrite corrosion, and the cementite was gradually torn by the local accumulation of large internal stresses. Micro-Raman proved that the structure of rust was varied and complex during the generation and development of fissures. The dimension of corrosion products could expand and contract in mutual transformation, forming local internal stress and promoting the expansion of microcracks. This work proposed a reasonable mechanism for the rapid embrittlement and pulverization in the atmospheric environment of such hypereutectic white cast iron artifacts out of the sea, which provided a scientific reference for future protection.

This work took the iron objects from the Nanhai No. 1 shipwreck in the Southern Song Dynasty of China as the sample to test and analyze the application potential of catechin, an environmentally friendly corrosion inhibitor and rust converter. The article used metallographic microscopy to clarify that the structure of the iron artifact was hypereutectic white iron. By means of micro-Raman, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), potentiodynamic polarization and electrochemical impedance spectroscopy, catechin had the ability to react with iron oxyhydroxides such as goethite, akaganeite and lepidocrocite in the rust, forming an amorphous substance with a marked signal about 1380 cm⁻¹ as phenolic-Fe in infrared properties. The new products could make the original rust layer form a laminated dense structure. After the archaeological iron was soaked in 3.0 g/L catechin, the corrosion current density decreased by 37.13% and the corrosion potential shifted positively by 32.67 mV. The anode reaction was more inhibited than the cathode in the polarization curve. The rust resistance in electrochemical impedance increased to 3.75 times and the ion diffusion resistance increased to 6.33 times. The corrosion inhibition efficiency was 21.75% and the rust conversion efficiency was 73.26%. After 36 h of accelerated corrosion, the protection effect of the newly transformed rust layer was still better than that of the original state. Catechin was a mild protection material which showed satisfactory performance for archaeological iron and has a good application prospect.

Ancient iron artifacts need to be protected with a rust layer, often stabilized by tannic acid corrosion inhibition. In humid environments, water vapor could slowly penetrate and trigger galvanic corrosion of metal artefacts. Sealing treatments are generally applied to the artefact surface to isolate water and enhance its corrosion resistance. Superhydrophobic modifications could effectively block the penetration of moisture into the interior of the artefact and provide a nice water barrier. Stearic acid with tannic acid inhibition treatment creates a superhydrophobic protective layer on the surface of rusted iron artifacts and enhances corrosion resistance effectively. Various scientific analyses and testing methods are used in this paper to evaluate the corrosion resistance of rusted surfaces after superhydrophobic modification and investigate the reaction mechanisms. The results indicate that the contact angle of the rusted surface after corrosion inhibition by tannic acid and modified by stearic acid is increased to 152.2°, which means the superhydrophobic protective layer has been successfully constructed. The C/Fe ratio of the rusted surface is increased from 0.21 to 2.10, and the characteristic diffraction peaks of O1s and Fe 2p_3/2 shift toward higher binding energy. Stearic acid is combined with the corrosion product layer by chemical bonding. Chelation between rust products, tannic acid, and steric acid is effective, and the chelate is chemically stable. The superhydrophobic surface forms a lamellar wax-like layer as an air barrier to isolate liquid water, resulting in a significant decrease in corrosion current and an increase in Warburg impedance to 217.9 times the original state, with a protection efficiency of 88.3%. Tannic acid corrosion inhibition and stearic acid superhydrophobic modification have an excellent synergistic protective effect on improving the corrosion resistance of iron artifacts, resulting in better corrosion resistance of iron artifact materials. The research provides new ideas and references for the protection of ancient iron artifacts sealing.

Paraloid B-72 (B72), as a transparent, colorless polymer material, has good film-forming ability when dissolved in acetone and is widely used as a sealing material for metal artifacts. In order to analyze and evaluate the preservation performance of B72 as a sealing material on the substrate of metal artifacts, a variety of electrochemical methods, mainly electrochemical noise (EN), and scanning electron microscopy (SEM) were applied to evaluate the B72 coating. The results showed that the B72 coating had a good preservation effect at the initial stage, and its poor water resistance led to the loss of its effectiveness after a few days of immersion. Compared with conventional electrochemical methods, electrochemical noise is non-destructive, which cannot cause new corrosion on the metal substrate and can well characterize the corrosion rate of the test system, and the results of its time domain and frequency domain analyses can correspond well with the polarization resistance and impedance spectra. Electrochemical noise is an effective method for evaluating the anti-corrosion performance of material preservation coatings.