氧化石墨烯/多壁碳纳米管影响天然橡胶性能的实验研究

高浩; 时文欣; 宋维浩; 李利

doi:10.13801/j.cnki.fhclxb.20210615.001

氧化石墨烯/多壁碳纳米管影响天然橡胶性能的实验研究

doi: 10.13801/j.cnki.fhclxb.20210615.001

青岛科技大学　机电工程学院，青岛 266100

基金项目: 国家自然科学基金 (51345006)

详细信息

通讯作者:
李利，博士，教授，博士生导师，研究方向为高分子材料加工机械　 E-mail：lindabob@126.com

中图分类号: TB332
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出版历程
- 收稿日期: 2021-05-06
- 修回日期: 2021-05-26
- 录用日期: 2021-06-03
- 网络出版日期: 2021-06-15
- 刊出日期: 2022-03-23

Effect of graphene oxide/multi-walled carbon nanotubes on the properties of natural rubber and experimental research

College of Electromechanical Engineering, Qingdao University of Science & Technology, Qingdao 266100, China

摘要

摘要: 氧化石墨烯(GO)和多壁碳纳米管(MWCNTs)因其良好的力学性能和导热性能，被广泛应用于橡胶填料。为了提高硫化效率，改善天然橡胶的物理性能，本论文将不同配比的GO和MWCNTs与橡胶混炼制备了一种GO/MWCNTs橡胶复合材料。通过测试混炼胶以及硫化胶的各项物理性能得出结论，GO填料与MWCNTs填料二者存在协同作用，并且不同配比的GO与MWCNTs对胶料性能的影响也不同，当MWCNTs填料定量加入6wt%时，随着GO含量的增加：硫化胶的最大转矩M_H与交联密度ΔM值呈增大趋势；焦烧时间t_c10和正硫化时间t_c90先降低，在3wt%后t_c90略有回升，且当GO与MWCNTs含量分别为3wt%和6wt%时，对硫化效率的提升最为明显；当二者同时加入6wt%时，混炼胶与硫化胶的导热率分别提高了25.1%和23.3%；硫化胶的100%定伸应力、300%定伸应力出现升高趋势，在3wt%之后略微下降。综合来看，当GO与MWCNTs添加量分别为3wt%与6wt%时，填料粒子对橡胶的补强效果最佳，其良好的导热性能增强了硫化反应的均匀性，实现了硫化过程的节能减耗。
- 橡胶复合材料 /
- 协同作用 /
- 导热性 /
- 硫化效率 /
- 橡胶填料 /
- 石墨烯 /
- 多壁碳纳米管
Abstract: Graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs) are widely used in rubber fillers due to their good mechanical properties and thermal conductivity. In order to increase the vulcanization efficiency and improve the physical properties of natural rubber, a GO/MWCNTs rubber composite was prepared by mixing graphene oxide and multi-walled carbon nanotubes with rubber in different proportions. Through testing the phy-sical properties of the rubber compound and the vulcanized rubber, it is concluded that there is a synergistic effect between MWCNTs filler and GO filler, and different ratios of GO and MWCNTs have different effects on the performance of the rubber compound. When MWCNTs filler is added quantitatively at 6wt%, with the increase of GO content: the maximum torque M_H of the vulcanized rubber and the crosslinking density ΔM value increased; the scorch time t_c10 and the normal vulcanization time t_c90 decreased first, and t_c90 rose slightly after 3wt%. When the content of GO and MWCNTs are 3wt% and 6wt%, the improvement of vulcanization efficiency is most obvious; when the two are added at 6wt% at the same time, the thermal conductivity of the compound and the vulcanized rubber are increased by 25.1% and 23.3% respectively; the 100% of the vulcanized rubber is fixed. Tensile stress and 300% constant elongation stress have a rising trend, and slightly decrease after 3wt%. Taken together, when GO and MWCNTs are added at 3wt% and 6wt%, respectively, the filler particles have the best reinforcement effect on the rubber. Its good thermal conductivity enhances the uniformity of the vulcanization reaction and realizes energy saving and consumption reduction in the vulcanization process.
- rubber composite /
- synergy /
- thermal conductivity /
- vulcanization efficiency /
- rubber filler /
- graphene oxide /
- multi-walled carbon nanotubes

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图 1 氧化石墨烯/多壁碳纳米管 (GO/MWCNTs) 填料网络示意图

Figure 1. Schematic diagram of graphene oxide/multi-walled carbon nanotubes (GO/MWCNTs) packing network

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图 2 GO含量对GO/MWCNTs橡胶复合材料最大扭矩M_H(a)、交联密度ΔM (b)、焦烧时间t_c10(c) 以及正硫化时间t_c90(d) 的影响

Figure 2. Influence of GO content of GO/MWCNTs rubber composite on the maximum torque M_H(a), crosslink density ΔM (b), scorching time t_c10 (c) and positive vulcanization time t_c90 (d)

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图 3 不同温度下GO/MWCNTs配比对GO/MWCNTs橡胶复合材料导热率的影响

Figure 3. Influence of GO/MWCNTs ratio on the thermal conductivity of GO/MWCNTs rubber composite at different temperature

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图 4 GO/MWCNTs的协同作用示意图

Figure 4. Diagram of synergy for GO/MWCNTs

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图 5 温度对GO/MWCNTs橡胶复合材料导热率的影响

Figure 5. Influence of temperature on the thermal conductivity of GO/MWCNTs rubber composite

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图 6 GO/MWCNTs配比对GO/MWCNTs橡胶复合材料100%定伸应力 (a)、300%定伸应力 (b)、拉伸强度 (c)、拉断伸长率 (d)、撕裂强度 (e) 和硬度 (f) 的影响

Figure 6. Influence of GO/MWCNTs ratio on 100% constant elongation stress (a), 300% tensile stress (b), tensile strength (c), tesile elongation (d), tearing strength (e) and hardness (f) of GO/MWCNTs rubber composite

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表 1 GO/MWCNTs的不同配比

Table 1. Different ratios of GO/MWCNTs

Number	0#	1#	2#	3#	4#	5#	6#	7#
MWCNTs/wt%	0	6	6	6	6	6	6	6
GO/wt%	0	0	1	2	3	4	5	6

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表 2 GO/MWCNTs橡胶复合材料混炼胶的门尼黏度

Table 2. Mooney viscosity for compounding of GO/MWCNTs rubber composites

MWCNTs /wt%	GO /wt%	Mooney viscosity/ ML100℃1+4
6	0	46.52
	1	45.23
	2	43.47
	3	42.49
	4	41.55
	5	40.98
	6	38.38
Notes: M—Mooney; L—Large rotor; 1—Preheating for 1 min; 4—Trial for 4 min.

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