秸秆纳米纤维素与炭黑补强天然胶的界面作用
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国家自然科学基金资助项目(51173046);广州市科技项目(201607010208)


Interaction Between Stalks Nanocellose and Natural Rubber Reinforced by Carbon Black
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    摘要:

    基于橡胶复合材料的力学性能、交联密度、粘弹行为、热行为、动态性能和形貌结构,利用红外光谱(FT-IR)、X射线光电子能谱(XPS)、差示扫描量热分析、动态力学分析等对酚醛树脂(PF)改性前后秸秆纳米纤维素(SNC)与炭黑(CB)补强的天然橡胶(NR)的界面影响进行了系统分析,并对SNC,PF与NR的成键形式进行了理论分析。FT-IR分析表明SNC-PF上的羟基(-OH)吸收峰发生了蓝移,XPS谱图中显示改性后SNC中O1s结合能升高,说明SNC与PF之间具有强的氢键作用。与NR/CB/PF体系相比,NR/CB/SNC/PF体系在大形变下具有更高的弹性模量(G′),说明其具有更强的橡胶交联网络,该体系具有更高的受限橡胶层质量分数(χim),说明该材料存在更厚的受限橡胶分子层,意味着其填料更好地分散和填料-基体间更强的相互作用。而NR/CB/SNC/PF复合材料较低的损耗因子(tanδ)、较高的填料-基体间相互作用参数和大应变下较高的上扬临界值(λ-1),都表明其中的填料与NR之间具有更强的相互作用。扫描电镜 (SEM)显示PF的加入使填料包埋在NR基体中,且分散更均匀。说明PF的加入使CB/SNC (填料网络)与NR基体形成互穿聚合物网络,填料与NR基体的相互作用增强,交联密度增加,而使CB补强NR的力学性能得到保持或改善。

    Abstract:

    Based on the mechanical properties, crosslinking density, viscoelastic behavior, thermal behavior, dynamic properties of rubber composites, influence of interfacial interaction between stalks nanocellulose(SNC) and natural rubber(NR)reinforced by carbon black(CB) before and after adding phenol-formaldehyde resin(PF) was analyzed by FT-IR, XPS, DSC and DMA, etc. Bonding forms between SNC and NR by PF was concluded in theory. FT-IR analysis shows that absorption peak of hydroxyl (-OH) in modified SNC has the hypsochromic shift, and XPS spectra display that O1s binding energy of modified SNC increases, indicating that the strong hydrogen bonding interaction between SNC and PF exists. Compared to NR/CB/PF composites, NR/CB/SNC/PF system has higher elastic modulus(G′) in large strain, suggesting that it has a stronger rubber crosslinking network. The higher χim value shows a tighter immobilized polymer layer approaching the filler surface of NR/CB/SNC/PF composites, which leads to better dispersion of SNC and the stronger filler-rubber interfacial bonding. With low tanδ, high filler-matrix interaction parameters and high λ-1 values in upoint of large strain, NR/CB/SNC/PF composites show stronger filler-NR interaction. SEM shows that the addition of PF buries more uniform fillers in NR matrix.In conclusion,with the addition of PF, interpenetrating polymer network is formed by CB/SNC fillers and NR martix, the filler-NR interaction’s improvement makes the enhancement of the crosslinking densities, thus the mechanical properties of the NR composites reinforced by CB are kept constant or strengthened with SNC

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黄仕文, 古 菊.秸秆纳米纤维素与炭黑补强天然胶的界面作用[J].高分子材料科学与工程,2017,33(11):93-100.

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