SiO_2的功能化改性及其与聚合物基体的界面研究进展
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摘要
纳米二氧化硅(SiO_2)作为一种最常用的无机纳米材料,受到了各个领域研究者的广泛关注且已得到实际应用。以纳米SiO_2作为改性填料,得到的聚合物纳米复合材料兼具了聚合物基体和纳米SiO_2二者的优点,因而表现出优异的力学性能、热学性能、光学性能以及化学稳定性等。但是纳米SiO_2表面富含大量活性硅羟基,极易团聚,用一般方法难以实现其在纳米尺度上的均匀分散以及与高分子基体材料间良好的界面粘结。因此,在制备纳米SiO_2改性的聚合物基纳米复合材料前,研究者们常通过对SiO_2进行表面改性,以改善其与聚合物基体的界面相容性及其在聚合物基体中的分散性,并赋予其一定的功能性。目前,纳米SiO_2的改性方法有很多,总的来说主要为物理改性和化学改性,而根据改性剂的种类不同,又可以分为有机改性、无机改性和杂化改性三种。聚合物/纳米SiO_2复合材料的优异性能不仅取决于有机聚合物和无机纳米SiO_2两组分的性能,还取决于两者间的界面结构和形态特征。尽管界面相的体积含量只占总体积含量中很少的一部分,但是界面间的相互作用、界面处聚合物结构与基体结构的差异、界面相微观形貌的变化等都会使整个复合体系的宏观性能发生明显的改变。因而针对有机聚合物与无机纳米SiO_2间的界面研究对于纳米复合材料性能的优化设计具有重要的科学意义。近年来,关于聚合物与无机纳米粒子之间的界面研究主要集中在两个方面:一方面是聚合物及无机纳米粒子表面的物理、化学性质对界面处性能的影响;另一方面是聚合物基体与无机纳米粒子之间的界面相互作用对复合材料性能的影响。目前,常通过现代仪器分析技术测试界面相的微观形貌(如粗糙程度、厚度等)及化学结构(如化学键合方式、键能等),或结合分子动力学模拟阐明分子集合体结构以及相互间的微观作用机理,从理论角度更准确地解释界面性能和界面行为,为复合材料的优化设计提供理论基础和新方法。本文归纳了有机改性、无机改性和杂化改性三种方法在纳米SiO_2的功能化方面的研究进展,讨论并对比了不同改性方法的优势和缺点,较全面地综述了当前现代仪器分析表征和分子动力学模拟在聚合物/SiO_2界面作用研究方面的最新进展,最后展望了纳米SiO_2与聚合物基体界面作用未来研究的工作重点。
As one of the most commonly used inorganic nanomaterials,nano-silica(SiO_2) has been widely concerned and applied by researchers in various fields. Nano-SiO_2 has been used as the modified filler,its polymer nanocomposites combine the advantages of both polymer matrix and nano-SiO_2,and thus show excellent mechanical properties,thermal properties,optical properties and chemical stability,etc. However,the surface of nano-SiO_2 is rich in a large amount of active silicone hydroxyl,which is easy to aggregate. So,it's difficult to obtain uniform dispersion on the nanometer scale and good interfacial adhesion between nano-SiO_2 and polymer matrix materials by general methods. Therefore,before the preparation of polymer-based nanocomposites modified by nano-SiO_2,surface modification is required to improve the interfacial compatibility between SiO_2 particles and polymer matrix and its dispersibility in the polymer matrix,and give it a certain degree of functionality. At present,there are many modification methods for nano-SiO_2. In general,it is mainly physical modification and chemical modification,and according to different types of modified agents,it can be divided into organic modification,inorganic modification and hybrid modification.The excellent properties of polymer/nano SiO_2 composites depend not only on the properties of the two components of organic polymer and inorganic nano-SiO_2,but also on the interfacial structure and morphological characteristics between them. Although the volume content of interface phase is only a small part of total volume content,but the interaction between the interfaces,the differences between polymer structure and matrix structure at the interface,and the changes in the microstructure of interface phase and so on will significantly change the macro-performance of whole composite system. Therefore,the interface research between them has important scientific significance for the optimization design of nanocomposite properties. In recent years,the research of interface between polymer and inorganic nanoparticles mainly focused on two aspects. On the one hand,the physical and chemical properties of the surface of polymer and inorganic nanoparticles affect the properties at the interface. On the other hand,the interfacial interaction between polymer matrix and inorganic nanoparticles affects the properties of its composites. At present,the microstructure(such as roughness,thickness,etc.) and chemical structure(such as chemical bonding,bond energy,etc.) of the interface phase are often tested by modern instrumental analysis technology,or the molecular dynamics simulation is used to elucidate the molecular assembly structure and the mechanism of mutual interaction. Which can explain the interface performance and interface behavior more accurately from a theoretical perspective,and provide a theoretical basis and new methods for the optimal design of composites.In this paper,the research progress of organic modification,inorganic modification and hybrid modification on the functionalization of nano-SiO_2 is summarized. The advantages and disadvantages of different modification methods are discussed and compared,and recent advances in the research of polymer/SiO_2 interface in modern instrumental analysis characterization and molecular dynamics simulation are reviewed in detail. Finally,the future research focus of the interaction between nano-SiO_2 and polymer matrix is forecasted.
As one of the most commonly used inorganic nanomaterials,nano-silica(SiO_2) has been widely concerned and applied by researchers in various fields. Nano-SiO_2 has been used as the modified filler,its polymer nanocomposites combine the advantages of both polymer matrix and nano-SiO_2,and thus show excellent mechanical properties,thermal properties,optical properties and chemical stability,etc. However,the surface of nano-SiO_2 is rich in a large amount of active silicone hydroxyl,which is easy to aggregate. So,it's difficult to obtain uniform dispersion on the nanometer scale and good interfacial adhesion between nano-SiO_2 and polymer matrix materials by general methods. Therefore,before the preparation of polymer-based nanocomposites modified by nano-SiO_2,surface modification is required to improve the interfacial compatibility between SiO_2 particles and polymer matrix and its dispersibility in the polymer matrix,and give it a certain degree of functionality. At present,there are many modification methods for nano-SiO_2. In general,it is mainly physical modification and chemical modification,and according to different types of modified agents,it can be divided into organic modification,inorganic modification and hybrid modification.The excellent properties of polymer/nano SiO_2 composites depend not only on the properties of the two components of organic polymer and inorganic nano-SiO_2,but also on the interfacial structure and morphological characteristics between them. Although the volume content of interface phase is only a small part of total volume content,but the interaction between the interfaces,the differences between polymer structure and matrix structure at the interface,and the changes in the microstructure of interface phase and so on will significantly change the macro-performance of whole composite system. Therefore,the interface research between them has important scientific significance for the optimization design of nanocomposite properties. In recent years,the research of interface between polymer and inorganic nanoparticles mainly focused on two aspects. On the one hand,the physical and chemical properties of the surface of polymer and inorganic nanoparticles affect the properties at the interface. On the other hand,the interfacial interaction between polymer matrix and inorganic nanoparticles affects the properties of its composites. At present,the microstructure(such as roughness,thickness,etc.) and chemical structure(such as chemical bonding,bond energy,etc.) of the interface phase are often tested by modern instrumental analysis technology,or the molecular dynamics simulation is used to elucidate the molecular assembly structure and the mechanism of mutual interaction. Which can explain the interface performance and interface behavior more accurately from a theoretical perspective,and provide a theoretical basis and new methods for the optimal design of composites.In this paper,the research progress of organic modification,inorganic modification and hybrid modification on the functionalization of nano-SiO_2 is summarized. The advantages and disadvantages of different modification methods are discussed and compared,and recent advances in the research of polymer/SiO_2 interface in modern instrumental analysis characterization and molecular dynamics simulation are reviewed in detail. Finally,the future research focus of the interaction between nano-SiO_2 and polymer matrix is forecasted.
引文
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