Guanyl-urea phosphate (GUP) was introduced into furfurylated wood in order to improve fire retardancy. Modified wood was produced via vacuum-pressure impregnation of the GUP–furfuryl alcohol (FA) aqueous solution, which was then polymerized at elevated temperature. The water leaching resistance of the treated wood was tested according to European standard EN 84, while the leached water was analyzed using ultra-performance liquid chromatography (UPLC) and inductively coupled plasma–sector field mass spectrometry (ICP-SFMS). This new type of furfurylated wood was further characterized in the laboratory by evaluating its morphology and elemental composition using optical microscopy and electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDX). The chemical functionality was detected using infrared spectroscopy (FTIR), and the fire resistance was tested using cone calorimetry. The dimensional stability was evaluated in wet–dry soaking cycle tests, along with the mechanical properties, such as the Brinell hardness and bending strength. The fire retardancy of the modified furfurylated wood indicated that the flammability of wood can be depressed to some extent by introducing GUP. This was reflected in an observed reduction in heat release rate (HRR2) from 454.8 to 264.9 kW/m2, without a reduction in the material properties. In addition, this leaching-resistant furfurylated wood exhibited higher fire retardancy compared to conventional furfurylated wood. A potential method for producing fire-retardant treated furfurylated wood stable to water exposure has been suggested.
7 October 2021 in Wood Material Science & Engineering
Furfurylated wood has been used widely for exterior purposes due to its superior dimensional stability and biological durability, though its fire resistance is not enhanced. Here, the introduction of the fire-retardant additive guanyl-urea phosphate (GUP) into furfurylated wood is reported. The treatment improved both the thermal and fire stabilities of the modified wood, as supported by the results of thermal gravimetric analysis (TGA) and limiting oxygen index (LOI) before and after accelerated ageing testing (according to EN 84) to determine the water resistance of the treatment. The results indicated that the hydroscopic GUP remained within the wood structure and provided superior thermal and fire properties. The work suggests the idea of combining GUP and furfuryl alcohol (FA), which has the prospective to impart substantial fire-retardancy to the furfurylated wood, thus increasing the potential for exterior applications.
In this study, the wood–water interactions in Scots pine sapwood modified with maleic anhydride (MA) and sodium hypophosphite (SHP) was studied in the water-saturated state. The water in wood was studied with low field nuclear magnetic resonance (LFNMR) and the hydrophilicity of cell walls was studied by infrared spectroscopy after deuteration using liquid D2O. The results of LFNMR showed that the spin–spin relaxation (T2) time of cell wall water decreased by modification, while T2 of capillary water increased. Furthermore, the moisture content and the amount of water in cell walls of modified wood were lower than for unmodified samples at the water-saturated state. Although the amount of accessible hydroxyl groups in modified wood did not show any significant difference compared with unmodified wood, the increase in T2 of capillary water indicates a decreased affinity of the wood cell wall to water. However, for the cell wall water, the physical confinement within the cell walls seemed to overrule the weaker wood–water interactions.
3 January 2021 in European Journal of Wood and Wood Products
Wood has the ability to absorb and desorb moisture, which can affect its dimensional size when in use. Limiting this can provide products with greater shape stability and less stresses on external coatings. One method that has been investigated for achieving this has been through chemical modification. In this work, the dimensional stabilisation imparted to Scots pine sapwood by chemical modification with maleic anhydride (MA) combined with sodium hypophosphite (SHP) was investigated. The influence of concentration of MA, treatment temperature and treatment period on weight percent gain (WPG) and bulking coefficient (BC) during treatment with MA and SHP of wood was studied. Furthermore, dimensional stability was determined by the water soak/oven dry method (wet-dry cycle) through five cycles in order to determine the hydrolytic stability of the ester bond and any potential cross-linking reactions. Wood blocks (20 × 20 × 10 mm) modified with MA combined with SHP exhibited lower weight loss following water soaking than unmodified blocks or MA-treated blocks. Wood blocks modified with MA and SHP showed the best anti-swelling efficiency and minimum wet-volume (water-saturated). However, as the concentration of SHP increased, dimensional stability was diminished without any increase in weight percentage gain after water soaking. When combined with FTIR results, it appeared that the modification with MA and SHP seemed to form cross-linking between wood constituents, though high concentration of SHP did not seem to result in additional cross-linking.
The reaction of wood with maleic anhydride (MA) and sodium hypophosphite (SHP) has been identified as a viable modification method, with macroscopical properties indicating formation of cross-linking to explain the results. However, the chemical reaction between wood and the modification reagents has not been studied yet. To resolve this, the reaction was studied with solid-state 13C cross-polarization magic-angle-spinning (CP-MAS) and 31P MAS nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) to reveal the formation of bonds between wood components, MA and SHP during the treatments to explain the formation of cross-linking and the possible fixation of phosphorus in wood. XPS, solid state 13C and 31P MAS NMR revealed the maleation of wood in the absence of SHP, whilst its presence led to forming a succinic adduct observed through the C-P bond formation, as evidenced by the loss of the maleate C=C bonds at around 130 ppm and the upfield shift of the peak at 165–175 ppm, which was also significantly smoothed, as well as the increase in a peak at 26 ppm due to the reaction between the maleate group and SHP; however, the C-P-C bond could not be unambiguously rationalized from the obtained data. On the other hand, a resonance line at 16 ppm in 31P MAS NMR and the peaks in the XPS P 2p spectrum suggested the formation of a cross-linked structure at low concentrations of SHP, which was more likely to be phosphonate (C-P-O) than organophosphinic acid (C-P-C). The results herein provide a greater fundamental understanding of the mechanisms involved in the reaction of wood, MA and SHP, providing further scope for improved treatment systems in the future.