High Leach-Resistant Fire-Retardant Modified Pine Wood (Pinus sylvestris L.) by In Situ Phosphorylation and Carbamylation

[Image: see text] The exterior application of fire-retardant (FR) timber necessitates it to have high durability because of the possibility to be exposed to rainfall. In this study, water-leaching resistance of FR wood has been imparted by grafting phosphate and carbamate groups of the water-soluble FR additives ammonium dihydrogen phosphate (ADP)/urea onto the hydroxyl groups of wood polymers via vacuum-pressure impregnation, followed by drying/heating in hot air. A darker and more reddish wood surface was observed after the modification. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, solid-state (13)C cross-polarization magic-angle-spinning nuclear magnetic resonance ((13)C CP-MAS NMR), and direct-excitation (31)P MAS NMR suggested the formation of C–O–P covalent bonds and urethane chemical bridges. Scanning electron microscopy/energy-dispersive X-ray spectrometry suggested the diffusion of ADP/urea into the cell wall. The gas evolution analyzed by thermogravimetric analysis coupled with quadrupole mass spectrometry revealed a potential grafting reaction mechanism starting with the thermal decomposition of urea. Thermal behavior showed that the FR-modified wood lowered the main decomposition temperature and promoted the formation of char residues at elevated temperatures. The FR activity was preserved even after an extensive water-leaching test, confirmed by the limiting oxygen index (LOI) and cone calorimetry. The reduction of fire hazards was achieved through the increase of the LOI to above 80%, reduction of 30% of the peak heat release rate (pHRR(2)), reduction of smoke production, and a longer ignition time. The modulus of elasticity of FR-modified wood increased by 40% without significantly decreasing the modulus of rupture.