Being inspired by nature, a series of experiments was carried out to deposit a calcium oxalate layer on the surface of the stone by the reaction between carbonate rock and oxalate salt. To increase the anti-dissolution properties of the calcium oxalate layer, the use of mixed oxalate solution has been proposed in the literature by two main routes: (1) adding acid agent to ammonium oxalate, which has the advantage of changing the particle structure and reducing layer porosity, and (2) using neutral methyl oxalate solution, which has the advantage of surface coverage due to slowly hydrolysis. In this study, we investigated the sequential application of ammonium oxalate, methyl oxalate, neutral mixed, and calcium acetate acid mixed solution. With this method, calcium carbonate and calcium oxalate solution can react inside the stone to reinforce it. The protective film’s coverage area can then be increased using dimethyl oxalate neutral mixed solution, and the crystal morphology can be modified with calcium oxalate acid mixed solution. The anti-dissolution properties of the coating were investigated using both a custom-designed apparatus and a selective outdoor environment. The coating displayed good acid resistance properties at pH 2–4. After one year of exposure, the coating is firmly bonded with the stone.

Red discolorations are an effloresce phenomenon detect on the surface of stone objects and considered as damage factor in both esthetic and conservation points of view. It is very difficult to remove and seldom report about their weathering mechanism. Recently, numerous of red discolorations have affected the limestone objects of Lingyan Temple in Shandong province, one of the most important building materials in China. In order to set up the appropriate conservation remedy, it is essential to identify the origin, characteristics, composition, and the formation process of red discolorations. Several analytical and investigation techniques, such as X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), Micro-Raman spectroscopy (Raman), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS) were used to better understand the red discolorations. The results demonstrated that the discolorations on limestone surface have been caused by carbonic acid weathering process. The red discolorations consisted mainly of kutnohorite (Ca(Fe,Mg,Mn)CO3) and iron oxides. They showed tabular, lamellar, and granular morphologies, which originated from the in situ carbonic acid weathering of kutnohorite. After rainfall, the Ca, Mg, Mn ions with relatively high solubility were primarily leached from carbonatite phases. It was resulting in the sedimentation of red iron oxides through a chemical reaction and physical adhesion. Based on those analyses, a chelating agent (ethylenediamine tetraacetic acid disodium salt) was chosen to remove theses red discolorations on the stone object.

The presence of calcareous concretions on the surface of marine archaeological ceramics is a frequently observed phenomenon. It is necessary to remove these materials when the deposits obscure the feature of ceramics. Unfortunately, calcareous concretions provide distinctive documentation of the burning history of ceramics. The interaction of acid solution or detachment of the deposit layers in physical ways leads to the loss of archeological information. To prevent the loss of archeological information and to achieve precise and gentle concretion removal, responsive hydrogel cleaning systems have been developed. The hydrogels synthesized are composed of networks of poly(vinyl acetate)/sodium alginate that exhibit desirable water retention properties, are responsive to Ca2+ ions, and do not leave any residues after undergoing cleaning treatment. Four distinct compositions were selected. The study of water retention properties involved quantifying the weight changes. The composition was obtained from Fourier transform infrared spectra. The microstructure was obtained from scanning electron microscopy. The mechanical properties were obtained from rheological measurements. To demonstrate both the efficiency and working mechanism of the selected hydrogels, a representative study of mocked samples is presented first. After selecting the most appropriate hydrogel composite, a cleaning process was implemented on the marine archaeological ceramics. This article demonstrates the advantages of stimuli-responsive hydrogels in controlling the release of acid solution release, thereby surpassing the limitations of traditional cleaning methods.

The deposition of a calcium oxalate layer on dolomite demonstrates potential application in stone culture heritage conservation. However, due to insufficient coverage and the presence of cracks, the film’s usefulness is restricted. In this investigation, we used a simple two-step procedure to create a cohesive and uncracked film. The findings show that the protective layer provides better coverage of the dolomite surface without causing cracks and significantly improves acid resistance. Furthermore, after the simple two-step treatment, the color and adhesive strength of dolomite substrates remained nearly unchanged.

Calcium oxalate film was prepared by a novel two-step method on the surface of the marble substrate. The seed film was coated by a chemical reaction process, providing a good connection to the marble surface. Meanwhile, calcium oxalate solution was interwoven into the seed film to form a continuous network at room temperature. The x-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis results indicated that the calcium oxalate film prepared by the two-step method showed a more intensive crystallinity degree and homogenous than that by the traditional oxalate treatment method (a scattered seed film). Subsequently, it was found such calcium oxalate film is feasible for preventing the marble substrate from chemical weathering. Furthermore, the change of the chromatic value, water absorption properties and adhesion strength of the marble substrates by the film is minimal. This method overcomes the limitations of traditional oxalate treatment process and has great potential for the protection of marble artifacts.