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    三聚氰胺–尿素–葡萄糖(MUG)生物质树脂/硅酸钠复合改性杨木的性能与机理研究

    Properties and mechanism of poplar wood modified by melamine-urea-glucose (MUG) biomass resin and sodium silicate compound

    • 摘要:
        目的  研究改性材的微观形貌、化学结构和元素成分等变化,探讨三聚氰胺–尿素–葡萄糖(MUG)生物质树脂复合改性剂对杨木的改性作用机理,旨在为MUG复合改性剂的应用提供依据,促进木材的绿色改性。
        方法  通过将有机硅烷等疏水基团,引入MUG生物质树脂与硅酸钠的复配溶液中,制备硅烷杂化MUG树脂/硅酸钠复合改性剂(GST),对杨木进行真空加压浸渍处理,测试改性杨木的物理力学性能,采用扫描电镜–X射线能谱仪(SEM-EDX)、傅里叶变换红外光谱仪(FTIR)、X射线光电子能谱仪(XPS)和X射线衍射仪(XRD)等,表征改性材的微观形貌、化学结构、元素成分和结晶度,利用微型量热仪(MCC)测试其燃烧性能和热解特性。
        结果  SEM-EDX分析表明:GST改性剂渗透性好,能有效渗入木材细胞腔和细胞壁中;改性材的C、O、Si元素无规分布于木材细胞腔、细胞壁、细胞间隙等处,导管沉积最为明显;改性剂对木材孔隙的填充以及对纤维素非结晶区的充胀,有效提高了木材的尺寸稳定性和力学性能。FTIR分析表明:GST改性材中半纤维素等多糖与改性剂发生了交联反应,减少了C=O、—OH等吸水性基团。XPS分析表明:GST改性材的C1最多,C3最少,木材的多糖类物质、木质素醇羟基、酚羟基以及羰基等活性基团与改性剂发生反应,减少了羰基等活性基团,增加了C—H、C—C结构含量。XRD分析表明:GST改性材衍射峰无明显变化,相对结晶度增大,说明改性剂进入纤维素非结晶区使其分子排列更加有序。MCC分析表明:GST改性材的热释放能力、热释放速率峰值和总热释放量分别下降了65.7%、66.2%和6.2%,800 ℃残炭率提高了122.6%,热释放强度大大降低,火灾危险性减小。
        结论  GST复合改性剂可有效渗入杨木内部,与木材中半纤维素等多糖发生交联反应,减少糖基等活性基团,使非结晶区排列更为有序,从而提升改性杨木的物理力学性能。

       

      Abstract:
        Objective  In order to provide basis for the application of melamine-urea-glucose (MUG) composite modifier and promote wood green modification, the changes of micro morphology, chemical structure and element composition of modified wood were studied, and the modification mechanism of biomass resin compound modifier on wood was discussed.
        Method  By introducing hydrophobic groups such as organosilane into the compound solution of MUG biomass resin and sodium silicate, the silane hybrid modifier (GST) was prepared. Then the poplar wood was modified with it by vacuum pressure impregnating treatment. The physical and mechanical properties of modified wood were tested. Its micro-morphology, chemical structure, element composition and crystallinity were characterized by scanning electron microscopy-energy dispersive X-ray spectrometer (SEM-EDX), Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffractometer (XRD). The combustion performance and pyrolysis characteristics were tested by micro calorimeter (MCC).
        Result  SEM-EDX analysis showed that GST modifier had good permeability and can effectively penetrate into wood cell cavity and cell wall; the C, O and Si element of modified wood were irregularly distributed in wood cell cavity, cell wall and cell gap, and the modifier was most deposited in wood vessels. Due to the effective filling of wood pores and the swelling of cellulose amorphous zone, wood dimensional stability and mechanical properties were improved. FTIR analysis showed that hemicellulose and other polysaccharides in GST modified wood had a cross-linking reaction with the modifier, reducing C=O, —OH and other hydroscopic groups. XPS analysis found that the C1 of GST modified wood was the most and its C3 was the least. During the modification process, the active groups such as polysaccharides, lignin alcohol hydroxyl, phenol hydroxyl and carbonyl reacted with the modifier, reducing the active groups and increasing the contents of C—H and C—C structure. XRD analysis showed that the diffraction peaks of the GST modified wood had no obvious change, its relative crystallinity increased, indicating that the modifier entered the amorphous region of cellulose to make its molecular arrangement more orderly. MCC analysis showed that the heat release capacity, peak heat release rate and total heat release of GST modified wood decreased by 65.7%, 66.2% and 6.2%, respectively, the residual carbon rate at 800 ℃ increased by 122.6%, its heat release intensity was greatly reduced and its fire risk was reduced.
        Conclusion  GST compound modifier can effectively penetrate into poplar wood, cross-linked with its hemicellulose and other polysaccharides, reduce active groups such as sugar groups, and make the arrangement of amorphous regions more orderly, so as to improve its physical and mechanical properties.

       

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