高分子复合材料中键合剂在不同纳米填料表面的吸附能计算  

Adsorption energy of bonding agent on nano-filler in polymer composites

作　　者：赵继昊 唐伟强 徐小飞 赵双良[1,2] 贺炅皓 ZHAO Jihao;TANG Weiqiang;XU Xiaofei;ZHAO Shuangliang;HE Jionghao(School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530028,Guangxi,China;Otsuka Material Technology(Shanghai)Company Limited,Shanghai 200233,China)

机构地区：[1]华东理工大学化工学院,上海200237 [2]广西大学化学化工学院,广西南宁530028 [3]大冢材料科技(上海)有限公司,上海200233

出　　处：《化工学报》2022年第7期3174-3181,共8页CIESC Journal

基　　金：国家自然科学基金项目(21878078,21978079)。

摘　　要：由高分子、填料、键合剂及各种功能助剂组成的高分子复合材料广泛应用于轮胎、含能材料、医疗、环保、建筑、交通等行业。键合剂在填料表面的吸附特性对高分子复合材料的性能有重要影响。分别以未改性的高氯酸铵、炭黑和二氧化硅填料为对象,利用第一性原理计算评估了五种键合剂分子,即三乙醇胺(TEA)、三氟化硼三乙醇胺络合物(T313)、N,N′-二邻甲苯胍(DOTG)、N,N′-二苯基硫脲(DPTU)和二苯胍(DPG),在填料表面的吸附能。计算结果表明,随着填料基底层数的增加,吸附能逐渐增加,最后趋于一个稳定值。其中TEA和T313键合剂在高氯酸铵表面的吸附能为-0.84~-1.37 e V;DOTG、DPTU和DPG在炭黑表面的吸附能为-1.01~-1.29 e V;在二氧化硅表面的吸附能为-0.87~-0.94 eV;在接枝羟基的二氧化硅上的吸附能为-1.16~-1.36 eV。依次考察了单层炭黑点缺陷(单空位缺陷、双空位缺陷、Stone-Wales缺陷)和二氧化硅表面接枝羟基对吸附能的影响,发现单空位和双空位缺陷对吸附能影响不大,而Stone-Wales缺陷和二氧化硅接枝羟基显著增加吸附能。Polymer composites composed of polymer,filler,bond agent and other functional additives are widely used in tire,energetic materials,medical treatment,environmental protection,construction,transportation and other industries.It has been well recognized that the adsorption properties of bond agents on the surfaces of nano-fillers have profound effects on the performance of the entire polymer composites.Herein,three kinds of nano-fillers are considered including the unmodified ammonium perchlorate,carbon black and SiO2fillers,and by means of the first-principles calculation,the adsorption energies of five bond agents(TEA,T313,DOTG,DPTU and DPG)on the surfaces of these filler are evaluated.The calculation results show that with the increase of the number of filler substrate layers,the adsorption energy gradually increases,and finally tends to a stable value.In addition,the influences of point defects(single vacancy defects,double vacancy defects,and Stone-Wales defects)and hydroxyl groups grafted on SiO2surface on the adsorption energy are investigated.It is found that the presence of single vacancy defects or double vacancy defects has little influence on the adsorption energy.However,the Stone-Wales defect and grafted hydroxyl groups can significantly promote the adsorption energy.

关 键 词：纳米填料 键合剂 吸附能 密度泛函理论 缺陷 

分 类 号：O485[理学—固体物理]