碳系导电填料混杂填充聚合物共混体系的导电逾渗模型

doi:10.7503/cjcu20150169

摘要/Abstract

摘要：

以排除体积理论为基础, 提出了3种碳系导电填料混杂填充聚合物共混体系的导电逾渗模型, 并利用三维图和二维图对导电逾渗模型进行了描述. 选用炭黑、聚团状碳纳米管和阵列碳纳米管3种导电填料, 以聚碳酸酯(PC)/苯乙烯-丙烯腈共聚物(SAN)(70∶30, 质量比)和PC/聚苯醚(PPO)(70∶30, 质量比)2个共混体系进行研究, 通过不同导电填料在单一聚合物及其共混物中逾渗值的测量, 对导电逾渗模型公式的各个参数进行计算和修正. 导电逾渗模型预测结果与样品实际电阻率基本吻合, 证明了模型的普适性和实用价值. 对于基体相不变的系列聚合物共混体系, 可以通过任意一种导电填料在共混体系中的逾渗值及在基体相聚合物中的逾渗值之比得到模型公式的相关参数, 从而极大地方便了模型的推广和应用.

关键词: 导电逾渗模型, 逾渗值, 炭黑, 碳纳米管, 共混体系

Abstract:

A model was proposed for predicting the electrical percolation of ternary carbon filler mixture in polymer blends based on excluded volume theory. 2D and 3D models were used to describe the percolation model. Carbon black(CB), tangled carbon nanotubes(t-CNTs) and aligned carbon nanotubes(a-CNTs) were used as carbon-type conductive fillers. Taking polycarbonate(PC)/styrene-acrylonitrile(SAN)(70∶30, mass ratio) and PC/polyphenylene oxide(PPO)(70∶30, mass ratio) as the matrices, the equation developed from the percolation model is corrected by measuring the percolation thresholds of each carbon filler in polycarbo-nate and polymer blends. Predictions from the model match the conductivities well, proving the suitability and usefulness of the model. For those polymer blends with the same matrix polymer, the equation can be obtained by the ratio of the percolation threshold of one carbon filler in the polymer blend to that in the matrix polymer. The model can provide an important theoretical basis for structure designing and predicting the electrical properties of conductive polymer composites.

Key words: Electrical percolation model, Percolation threshold, Carbon black, Carbon nanotube, Polymer blend

中图分类号:

O631

TrendMD:

熊卓越, 张博媛, 汪唯佳, 郭朝霞, 于建. 碳系导电填料混杂填充聚合物共混体系的导电逾渗模型. 高等学校化学学报, 2015, 36(8): 1641.

XIONG Zhuoyue, ZHANG Boyuan, WANG Weijia, GUO Zhaoxia, YU Jian. Electrical Percolation Model of Ternary Carbon Filler Mixture in Polymer Blends^†. Chem. J. Chinese Universities, 2015, 36(8): 1641.

图/表 11

Fig.1 Schematic illustration of the percolation model for ternary carbon filler mix-filled PC/SAN(70∶30,

Fig.2 3D model of Eq.(2)

Fig.3 2D model of Eq.(2) for PC/SAN/a-CNTs/t-CNTs composites

Fig.4 SEM images of PC/SAN/CB/t-CNTs/a-CNTs(70∶30∶4∶2∶2)(A) and PC/PPO/CB/t-CNTs/a-CNTs(70∶30∶4∶2∶2)(B)

Fig.5 TEM images of PC/SAN/CB/t-CNTs/a-CNTs(70∶30∶5∶0.1∶0.3)(A) and PC/PPO/CB/t-CNTs/a-CNTs(70∶30∶3.33∶0.133∶0.3)(B)

Fig.6 Percolation curves of CB(A), t-CNTs(B) and a-CNTs(C) filled PC(a), PC/SAN(70∶30)(b) and PC/PPO(70∶30)(c)

Table 1 X values calculated from CB, t-CNTs, a-CNTs and their averages

System	m_CB(%)	m_t-CNTs(%)	m_a-CNTs(%)	Average(X)
PC/SAN(70∶30)	0.64	0.60	0.60	0.61
PC/PPO(70∶30)	0.77	0.77	0.83	0.79

Fig.7 2D figures of mCB=0(A), mCB=1%(B), mt-CNTs=0(C) and mt-CNTs=0.133%(D) in PC/SAN(70∶30)

Table 2 Composition, calculated value of Eq.(3), prediction of percolation and conductivity of each sample in PC/SAN

No.	m_a-CNTs(%)	m_t-CNTs(%)	m_CB(%)	Calculated value	Prediction	Conductivity(lgρ_v)
1	0.100	0.100	0	0.316	No	9.84
2	0.167	0.167	0	0.527	No	9.00
3	0.333	0.333	0	1.05	Yes	3.03
4	0.400	0.300	0	1.16	Yes	3.21
5	0.133	0.067	1.00	0.443	No	9.93
6	0.100	0.133	1.00	0.445	No	9.90
7	0.300	0.300	1.00	1.04	Yes	3.42
8	0.267	0.333	1.00	1.01	Yes	4.30
9	0.100	0	1.00	0.302	No	15.40
10	0.133	0	2.67	0.528	No	9.20
11	0.167	0	7.00	1.01	Yes	2.98
12	0.200	0	6.67	1.04	Yes	3.17
13	0.100	0.133	1.00	0.445	No	9.90
14	0.067	0.133	1.66	0.439	No	10.40
15	0.133	0.133	6.67	1.05	Yes	3.95
16	0.300	0.133	3.33	1.08	Yes	4.35

Fig.8 2D figures of mt-CNTs=0.1%(A) and mCB=2%(B) in PC/PPO(70∶30)

Table 3 Composition, calculated value of Eq.(4), prediction of percolation and conductivity of each sample in PC/PPO

No.	m_a-CNTs(%)	m_t-CNTs(%)	m_CB(%)	Calculated value	Prediction	Conductivity(lgρ_v)
1	0.067	0.100	1.67	0.404	No	16.3
2	0.133	0.100	1.00	0.479	No	10.3
3	0.300	0.100	5.00	1.20	Yes	6.39
4	0.267	0.100	6.00	1.23	Yes	5.88
5	0.067	0.133	2.00	0.471	No	16.2
6	0.100	0.100	2.00	0.504	No	16.4
7	0.267	0.333	2.00	1.10	Yes	5.90
8	0.300	0.300	2.00	1.14	Yes	5.69

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