Carboxymethyl Chitosan as a Reversible Template of Calcium Phosphate for Multifunctional Conservation of Carbonate Stone

The accelerated deterioration of carbonate stone artifacts under climate change has long been an urgent issue. Inspired by biomineralization, we developed carboxymethyl chitosan-diammonium hydrogen phosphate (CD) composite and investigated the conservation effectiveness of the CD composite compared to diammonium hydrogen phosphate (DAP) on limestone. The morphologies and microstructures were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FT-IR). The consolidating effectiveness was investigated through a compressive strength test. The protective ability was assessed by disintegration resistance test, acid attack resistance test, salt attack resistance test, and freeze-thaw aging cycle test. SEM observations revealed that carboxymethyl chitosan (CMCS) served as an effective template, inducing the in situ formation of a uniform and continuous calcium phosphate coating on both the surface and interior of the stone. The tests indicated that the CD composite further enhanced the consolidating effectiveness and improved resistance to disintegration and freeze-thaw cycles. Notably, as an amphiphilic polyelectrolyte, CMCS functioned as a pH buffer and a protective barrier against sodium sulfate salts, which improved the resistance to acid and salt attacks. Additionally, the CD composite did not cause significant variations in the esthetic appearance or water vapor permeability. We then applied the CD composite at an actual carbonate stone cultural heritage site, successfully demonstrating the feasibility of CD application and the reversibility of CMCS in a real-world setting. Based on the study's results, our approach provides a new perspective for developing multifunctional and sustainable conservation materials for carbonate stone artifacts.