高级检索

    植物酸改性增强竹塑复合材料界面性能

    Plant-derived acid modification to enhance interfacial properties of bamboo-plastic composites

    • 摘要:
      目的 竹塑复合材料已广泛应用于建筑及户外制品,其性能优劣的核心在于纤维与基体间的界面结合状态。现有研究多采用传统化学偶联剂改善界面相容性,但存在环境不友好、成本高、作用机制单一等问题,尤其缺乏对“竹纤维−填料−聚合物”多相界面的分析。本研究旨在通过环境友好的两种植物酸对碳酸钙进行表面改性,使其从“填料”转变为“偶联剂”,进而阐明其在改善竹纤维/聚丙烯/碳酸钙(BFs/PP/CaCO3)复合材料界面结合与综合力学性能中的作用机制,为开发绿色环保、低成本的竹塑复合材料提供参考。
      方法 采用柠檬酸钠和DL-苹果酸分别对碳酸钙进行表面改性,并与传统的硅烷偶联剂KH570对比,研究在不同添加量条件下对碳酸钙表面性能的影响。以碳酸钙、竹纤维和聚丙烯为原料,在控制碳酸钙添加量的条件下,制备BFs/PP/CaCO3复合材料,考察其物理力学性能,并对其微观结构、尺寸稳定性和加工性进行表征。最后,阐明其界面性能增强机制,并综合考虑成本与性能。
      结果 通过吸油值与活化度分析,确定柠檬酸钠、DL-苹果酸和KH570的优化添加量分别为碳酸钙质量的15%、5%和10%,且当改性碳酸钙添加量为10%时,复合材料的各项性能达到最优。传统KH570改性组复合材料的拉伸强度达41.30 MPa,弯曲强度和弹性模量分别为63.5 MPa和4.48 GPa;柠檬酸钠与DL-苹果酸改性组则表现出与传统KH570相当的界面结合能力,拉伸强度分别达40.31和39.62 MPa,可媲美工程塑料ABS(38 ~ 45 MPa);弯曲强度和弹性模量分别为63.1MPa、63.5 MPa和4.41 GPa、4.37 GPa,均超过LY/T 2565—2015《竹塑复合材料》中规定数值的2倍。柠檬酸钠改性组在满足力学性能要求的同时具备轻量化优势,密度降至1.08 g/cm3(降幅4.42%),而DL-苹果酸改性组显示出较高的尺寸稳定性,其吸水厚度膨胀率仅0.211%,比未改性组降低46.31%。同时,经DL-苹果酸改性后,复合材料的熔体流动指数达到22.77 g/(10 min),与纯PP的熔体流动指数21.00 g/(10 min)相当,加工性能大幅提升。
      结论 植物酸改性剂显著提高了碳酸钙表面活性,并通过羧基键合Ca2+及羟基与竹纤维形成氢键网络的协同作用下,有效改善了碳酸钙与竹纤维及PP之间的界面相容性,进而提高复合材料的物理力学性能。植物酸不仅部分力学性能与KH570相当,而且DL-苹果酸可赋予复合材料更好的加工性能,柠檬酸钠则可降低约7%的原料成本。

       

      Abstract:
      Objective Bamboo-plastic composites have been widely used in construction and outdoor products, and their performance largely depends on the interfacial bonding state between the fibers and the matrix. Current studies often rely on traditional chemical coupling agents to improve interfacial compatibility, which suffer from environmental unfriendliness, high cost, and limited mechanistic understanding. There remains a notable lack of analysis regarding the multi-phase interface involving “bamboo fiber-filler-polymer”. This study aims to use two environmentally friendly plant-derived acids for the surface modification of calcium carbonate, transforming it from a conventional filler into an active coupling agent. The research further seeks to elucidate its mechanism in enhancing the interfacial bonding and comprehensive mechanical properties of bamboo fiber/polypropylene/calcium carbonate (BFs/PP/CaCO3) composites, thereby providing a reference for developing green, low-cost bamboo-plastic composites.
      Method Sodium citrate and DL-malic acid were used to modify the surface of calcium carbonate, respectively, and their effects on the surface properties of calcium carbonate were compared with those of the traditional silane coupling agent KH570 under varying additive amounts. Using calcium carbonate, bamboo fibers, and polypropylene as raw materials, BFs/PP/CaCO3 composites were prepared under controlled calcium carbonate addition levels. Their physical-mechanical properties were investigated, and their microstructure, dimensional stability, and processability were characterized. Finally, the interfacial enhancement mechanism was clarified, and an optimized production formulation for the composites was proposed by balancing cost and performance.
      Result Through oil absorption value and activation degree analyses, the optimal additive amounts of sodium citrate, DL-malic acid, and KH570 were determined to be 15%, 5%, and 10% of the calcium carbonate mass, respectively. When the modified calcium carbonate addition was 10%, the composite exhibited optimal performance. The traditional KH570-modified group achieved a tensile strength of 41.30 MPa, with flexural strength and elastic modulus reaching 63.5 MPa and 4.48 GPa, respectively. The sodium citrate and DL-malic acid-modified groups demonstrated interfacial bonding capabilities comparable to KH570, with tensile strengths of 40.31 and 39.62 MPa, rivaling engineering plastics like ABS (38−45 MPa). Their flexural strengths and elastic moduli were 63.1 MPa, 63.5 MPa, and 4.41 GPa, 4.37 GPa, respectively, exceeding twice of the values specified in LY/T 2565-2015 Bamboo-Plastic Composites. The sodium citrate-modified group met mechanical performance requirements while offering lightweight advantages, with density reduced to 1.08 g/cm3 (a decrease of 4.42%). The DL-malic acid-modified group exhibited superior dimensional stability, with a water absorption thickness swelling rate of only 0.211%, a 46.31% reduction compared with the unmodified group. Additionally, after DL-malic acid modification, the composite’s melt flow index reached 22.77 g/(10 min), comparable with pure PP of 21.00 g/(10 min), indicating significantly improved processability.
      Conclusion Plant-derived acid modifiers significantly enhance the surface activity of calcium carbonate. Through carboxyl bonding with Ca2+ and hydrogen bonding with bamboo fibers, they improve the interfacial compatibility among CaCO3, bamboo fibers, and polypropylene, thereby enhancing the physico-mechanical properties of composites. These plant-based modifiers achieve mechanical properties comparable with those of KH570 in certain aspects, while also offering additional advantages: DL-malic acid improves processability, and sodium citrate reduces material costs by approximately 7%.

       

    /

    返回文章
    返回