Dual-Function Nitrogen Modification of Phenolic Resin Pyrolytic Carbon: A g-C3N4 Protective Phase and Skeletal Nitrogen Doping for Enhanced Oxidation Resistance

Phenolic resin pyrolytic carbon is a key matrix phase in carbon-based refractories and carbon/carbon composites; however, its defect-rich glassy carbon structure exhibits poor oxidation resistance at elevated temperatures. In this work, we report a facile one-step thermal-treatment strategy using melamine as a nitrogen source to prepare nitrogen-modified phenolic resin pyrolytic carbon (NC). The structural evolution and oxidation behavior of samples carbonized at 500–800 °C were systematically investigated by XRD, SEM, TEM, FT-IR, Raman, XPS, BET, and TG-DSC. The results reveal that melamine-derived nitrogen exists in two distinct forms: at 500–700 °C, a carbon nitride-rich phase consistent with graphitic carbon nitride (g-C3N4) forms sheet- and belt-like structures on the carbon surface and partially fills the internal pores; at 800 °C, its long-range crystalline signature disappears, while pyridinic, pyrrolic, and graphitic nitrogen remain in the carbon framework. From 500 to 800 °C, the relative N 1s fraction of pyridinic N decreases from 72.33% to 44.38%, whereas graphitic N increases from 0.47% to 24.09%. Meanwhile, the pore structure evolves from a mesopore-dominated architecture with a limited accessible surface area at 500–600 °C to a micropore-rich structure at 700–800 °C. Relative to unmodified PR-800, NC-800 exhibits an approximately 30 °C higher onset oxidation temperature and an approximately 40 °C higher complete oxidation temperature, together with a lower maximum mass-loss rate and a delayed, broadened exothermic response. These results show that melamine-derived pore regulation and skeletal nitrogen doping jointly retard oxygen transport and suppress oxidation-active defect sites, providing a simple and potentially scalable route for improving the high-temperature oxidation resistance of phenolic resin pyrolytic carbon.