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

doi:10.11949/0438-1157.20220097

Abstract

Abstract:

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 SiO₂ fillers, 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 SiO₂ surface 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.

Key words: nano-filler, bond-agent, adsorption energy, density functional theory, defect

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 eV；DOTG、DPTU和DPG在炭黑表面的吸附能为-1.01~-1.29 eV；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。

关键词: 纳米填料, 键合剂, 吸附能, 密度泛函理论, 缺陷

CLC Number:

O 485

Jihao ZHAO, Weiqiang TANG, Xiaofei XU, Shuangliang ZHAO, Jionghao HE. Adsorption energy of bonding agent on nano-filler in polymer composites[J]. CIESC Journal, 2022, 73(7): 3174-3181.

赵继昊, 唐伟强, 徐小飞, 赵双良, 贺炅皓. 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[J]. 化工学报, 2022, 73(7): 3174-3181.

Figures/Tables 13

Fig.1 Primordial cells of nanofillers

Fig.2 Molecular structure and electrostatic potential distribution of five bond agents： (a) TEA； (b) T313； (c) DPG； (d) DPTU； (e) DOTG

Fig.3 Adsorption model of bond agent on surface of different nano-fillers

Fig.4 Adsorption energy of bond agents on different layers of ammonium perchlorate

Fig.5 Adsorption of bond agents on different layers of carbon black

Fig.6 Adsorption of bond agents on different layers of SiO2

Fig.7 Carbon black surface defect model： (a) single vacancy defect； (b) divacancy defect； (c) Stone-Wales defect

Table 1 Adsorption energy of organic molecules with different defect types of carbon black

缺陷类型	吸附能/eV
缺陷类型	DPG	DPTU	DOTG
无缺陷	-0.99	-1.12	-1.28
单空位	-0.99	-1.12	-1.27
双空位	-0.97	-1.09	-1.26
Stone-Wales	-1.01	-1.14	-1.30

Fig.8 Adsorption of DPTU on carbon black with different defect types： (a) normal；(b) single vacancy defect；(c) divacancy defect；(d) Stone-Wales defect

Fig.9 Surface modification model of silica

Fig.10 Adsorption energy of three molecules on SiO2 and SiO2@OH

Fig.11 Weak interaction of DPG-SiO2 system and DPG-SiO2@OH system

Table 2 Adsorption energy of organic molecules with different substrates

基底类型	吸附能/eV
基底类型	DPG	DPTU	DOTG
双层炭黑	-1.01	-1.14	-1.29
双层SiO₂	-0.87	-0.89	-0.94
双层SiO₂@OH	-1.16	-1.20	-1.35

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