Structural Characterization and Performance of Functionalized Carbon Nanotube Reinforced Tetrapropylene Fluororubber Composites

QI Bo-wei; LV Fang-ge; HONG Min-bo; WANG Shi-jie; LIU Wei

doi:10.14028/j.cnki.1003-3726.2026.26.128

您当前的位置：

首页 >

文章列表页 >

Structural Characterization and Performance of Functionalized Carbon Nanotube Reinforced Tetrapropylene Fluororubber Composites

更新时间：2026-07-27

- Structural Characterization and Performance of Functionalized Carbon Nanotube Reinforced Tetrapropylene Fluororubber Composites
- Polymer Bulletin Vol. 39, Issue 8, Pages: 1493-1503(2026)
- 作者机构：
  
  青岛科技大学高分子科学与工程学院橡塑材料与工程教育部重点实验室　青岛 266042
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2026.26.128
  CLC：
- Received：06 March 2026，
  
  Accepted：30 May 2026，
  
  Online First：10 July 2026，
  
  Published：20 August 2026
- 稿件说明：
移动端阅览
齐柏为, 吕方阁, 洪敏博, 王世杰, 刘伟. 官能团改性碳纳米管增强四丙氟橡胶复合材料的结构表征与性能. 高分子通报, 2026, 39(8), 1493–1503.

Qi, B. W.; Lv, F. G.; Hong, M. B.; Wang, S. J.; Liu, W. Structural characterization and performance of functionalized carbon nanotube reinforced tetrapropylene fluororubber composites. Polym. Bull. (in Chinese), 2026, 39(8), 1493–1503.
齐柏为, 吕方阁, 洪敏博, 王世杰, 刘伟. 官能团改性碳纳米管增强四丙氟橡胶复合材料的结构表征与性能. 高分子通报, 2026, 39(8), 1493–1503. DOI： 10.14028/j.cnki.1003-3726.2026.26.128.

Qi, B. W.; Lv, F. G.; Hong, M. B.; Wang, S. J.; Liu, W. Structural characterization and performance of functionalized carbon nanotube reinforced tetrapropylene fluororubber composites. Polym. Bull. (in Chinese), 2026, 39(8), 1493–1503. DOI： 10.14028/j.cnki.1003-3726.2026.26.128.

摘要

为提升四丙氟橡胶(FEPM)的力学性能与热稳定性能，拓展其在苛刻工况下的工程应用范围，本研究以FEPM为基体相，分别引入未改性碳纳米管(CNTs)及氨基(CNTs-NH

)、羟基(CNTs-OH)、羧基(CNTs-COOH)官能团改性碳纳米管为功能增强相，设计并制备了5组不同配方的FEPM基复合材料，采用开炼混炼—一次硫化—二次硫化的工艺路线完成样品成型。采用橡胶加工

分析仪 (RPA) 进行应变扫描测试、扫描电子显微镜(SEM)观测微观形貌；采用示差扫描量热仪(DSC)、动态热机械分析仪(DMA)和热重分析仪(TGA)测试材料热性能，辅以物理机械性能测试与平衡溶胀法多种表征手段，系统探究了不同官能团改性CNTs对FEPM复合材料分散行为、交联结构、加工性能、热稳定性能、动态力学性能与静态力学性能的调控规律与作用机制。结果表明：官能团改性可通过表面基团的界面作用，显著改善CNTs在FEPM基体中的分散均匀性，抑制纳米填料团聚，其中CNTs-NH

改性效果较优，可缩短硫化时间、提升胶料加工效率，同时提升复合材料交联密度，其10%热失重温度与最大热分解速率温度较标准配方均有较大提升，材料热稳定性能与动态服役性能显著优化；CNTs-OH可同步提升复合材料的拉伸强度与断裂伸长率，实现强度与韧性的良好平衡。改性CNTs与FEPM基体间构建的强界面相互作用，是实现复合材料综合性能提升的核心机制。本研究为高性能氟橡胶复合材料的配方设计与性能调控提供了重要的实验数据与理论支撑，为氟橡胶在高端装备、苛刻环境中的工程应用奠定了技术基础。

Abstract

To improve the mechanical properties and thermal stability of tetrapropylene fluororubber (FEPM) and expand its engineering application scope under harsh working conditions

FEPM was used as the matrix phase in this study. Unmodified carbon nanotubes (CNTs) as well as carbon nanotubes functionalized with amino (CNTs-NH

)

hydroxyl (CNTs-OH)

and carboxyl (CNTs-COOH) groups were introduced as functional reinforcing phases. Five groups of FEPM-based composites with different formulations were designed and prepared

and sample molding was completed through the process route of open mill mixing

primary vulcanization

and post-vulcanization. Strain sweep tests by rubber processing analyzer (RPA)

micromorphology observation by scanning electron microscope (SEM)

as well as thermal property measurements via differential scanning calorimeter (DSC)

dynamic mechanical analyzer (DMA) and thermogravimetric analyzer (TGA) were performed. With mechanical tests and equilibrium swelling method as auxiliary characterization approaches

this work systematically explored the regulation laws and internal mechanisms of functionalized CNTs on the dispersion

crosslinking structure

processing

thermal stability

dynamic and static mechanical performances of FEPM composites. The results show that functional group-modified CNTs can significantly improve the dispersion uniformity of CNTs in the FEPM matrix and inhibit the agglomeration of nanofillers through interfa

cial interactions with the surface groups. Among them

CNTs-NH

exhibited an excellent modification effect: it shortened the vulcanization time

improved the processing efficiency of the rubber compound

and increased the crosslinking density of the composite. The 10% thermal weight loss temperature and the temperature corresponding to the maximum thermal decomposition rate were both significantly increased compared with those of the standard formulation

and the thermal stability and dynamic service performance of the material were remarkably optimized. CNTs-OH simultaneously improved the tensile strength and elongation at break of the composite

achieving a good balance between strength and toughness. The strong interfacial interaction between the modified CNTs and the FEPM matrix is the core mechanism for improving the comprehensive performance of the composites. This study provides important experimental data and theoretical support for the formulation design and performance regulation of high-performance fluororubber composites and lays a technical foundation for the engineering application of fluororubber in high-end equipment and harsh environments.

关键词

Keywords

references

Xiao, Y. ; Liu, B. ; Han, X. ; Sun, Q. ; Zhang, Y. ; Gao, T. ; Yang, W . Performance investigations on fluorine-rubber-tube-laying pumping wet shotcrete filled with microencapsulated phase change materials . Case Stud. Therm. Eng. , 2024 , 60 , 104765 .

Yamamoto, K. ; Asakura, J. ; Miwa, T. ; Saito, M . Unsaturated bond existing in tetrafluoroethylene-propylene-vinylidene fluoride terpolymer . J. Fluor. Chem. , 2004 , 125 ( 5 ), 735 – 740 .

刘心立 , 丁元皓 , 药晓江 , 赵晓林 , 王泽鹏 . 过氧和双酚硫化体系对氟橡胶抗耐性能影响的试验研究 . 山西化工 , 2025 , 45 ( 11 ), 44 – 47 .

Cong, C. B. ; Cui, C. C. ; Meng, X. Y. ; Zhou, Q . Stability of POSS crosslinks and aggregates in tetrafluoroethylene-propylene elastomers/OVPOSS composites exposed to hydrochloric acid solution . Polym. Degrad. Stab. , 2014 , 100 , 29 – 36 .

Chen, Z. H. ; Christensen, L. ; Dahn, J. R . Mechanical and electrical properties of poly(vinylidene fluoride-tetrafluoroethylene-propylene)/super-S carbon black swelled in liquid solvent as an electrode binder for lithium-ion batteries . J. Appl. Polym. Sci. , 2004 , 91 ( 5 ), 2958 – 2965 .

Yu, H. D. ; Liang, S. ; Tian, C . High-temperature co-cured phenolic resin damping composite embedded with fluororubber film . Adv. Compos. Mater. , 2026 , 35 ( 1 ), 139 – 160 .

Bascuñan-Heredia, A. ; Molina, F. ; Inestrosa-Izurieta, M. J. ; Dahrouch, M. ; Henriquez, A. ; Cortés, C. ; Lopez-Manchado, M. A. ; Aguilar-Bolados, H . Enhanced mechanical performance of fluoroelastomer composites with boron–gadolinium-based fillers for cutting-edge applications . Polymers , 2025 , 18 ( 1 ), 6 .

Tocqueville, H. ; Le Quilliec, G. ; Pepin, J . Multi-scale characterisation of the viscoelastic properties of a fluoroelastomer by DMA and dynamic indentation . Polymer , 2026 , 343 , 129399 .

Liu, H. L. ; Liu, Y. ; Li, D. ; Wu, Y. P . Examining the properties of fluorine-modified basalt fiber reinforced fluorine rubber composites . Mater. Today Commun. , 2025 , 49 , 114014 .

武卫莉 , 陈喆 . 硅橡胶/氟橡胶并用胶的制备及力学性能 . 高分子通报 , 2017 , ( 9 ), 33 – 39 .

季美琴 , 丁攀攀 , 张斌 , 王永伟 , 赵天琪 . 用于盾构机主驱动密封系统的抗高温撕裂碳纳米管/氟橡胶复合材料的性能研究 . 橡胶工业 , 2025 , 72 ( 12 ), 905 – 910 .

邢华艳 , 刘波 , 苏小龙 , 王雯霞 , 王涵 . 碳纳米管对两种过氧化物硫化氟橡胶性能的影响探讨 . 有机氟工业 , 2024 , ( 4 ), 16 – 22 .

Wang, Y. M. ; Du, X. Y. ; Zhang, L. ; Bao, J. B . Fluoroelastomer-induced microcellular structure in polyolefin elastomer foams: a pathway to reduced shrinkage and enhanced mechanical properties . Polym. Sci. Ser. A , 2024 , 66 ( 6 ), 703 – 713 .

Chen, Y. R. ; Wu, Y. D. ; Li, J. ; Peng, X. Q. ; Wang, S. ; Wang, J. C. ; Jin, H. L . Fluororubber composites: preparation methods, vulcanization mechanisms, and the associated properties . Compos. Part C Open Access , 2024 , 14 , 100461 .

Li, F. S. ; Lu, J. H. ; Wang, H. ; Hu, Y. ; Xia, R . Study on the preparation of macromolecular compatibilizer and its effect on the characteristics of fluoroelastomer (FKM)/silicone rubber (MVQ) blend . J. Polym. Res. , 2024 , 31 ( 4 ), 99 .

Rouihem, F. ; Albarqi, M. M. ; Alsulami, R. A. ; Hosni, F . Lead-free Gamma-ray shielding: comparative analysis of elastomeric and fluoro-rubber materials using FLUKA and EGSnrc simulations . J. Radiat. Res. Appl. Sci. , 2024 , 17 ( 1 ), 100834 .

李夯 , 李鑫亮 , 丛川波 , 廖洪千 , 刘铭超 . 助交联剂对四丙氟橡胶胶料耐高温水性能的影响 . 橡胶工业 , 2025 , 72 ( 6 ), 431 – 436 .

Zhao, S. W. ; Gao, Z. Z. ; Tu, Q. Z. ; Shen, X. M. ; Yin, Q. ; Yang, X. C. ; Liu, Q. ; Yang, F. ; Wang, E. S. ; Peng, W. Q. ; Xu, T . The influence of curvature of multi-walled carbon nanotubes in the matrix on the thermal conductivity of multi-walled carbon nanotube/natural rubber composites . J. Inorg. Organomet. Polym. Mater. , 2026 , Doi: 10.1007/s10904-026-04222-y https://doi.org/10.1007/s10904-026-04222-y .

王龄锋 , 白祝康 , 韩子璇 , 邱章燕 , 吴亚东 , 金辉乐 . 单壁碳纳米管/二氧化硅复合填料改性氟橡胶的性能研究 . 辽宁化工 , 2025 , 54 ( 5 ), 721 – 726 .

徐凤祥 , 张伦 , 程文佳 , 刘明泰 , 尤黎明 , 王雷鹏 . 硫化工艺参数对碳纳米管/炭黑增强四丙氟橡胶材料性能的影响 . 弹性体 , 2023 , 33 ( 1 ), 40 – 44 .

董社霞 , 葛垣 , 刘明泰 , 尤黎明 , 王雷鹏 . 碳纳米管/炭黑增强四丙氟橡胶复合材料的性能 . 弹性体 , 2022 , 32 ( 4 ), 47 – 51 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

A New Diatomaceous Earth Filled Rubber Nanocomposites

Preparation of Sulfonated Mesoporous Silica and Its Regulation on Flame Retardancy and Transparency of Polycarbonate

Performance Regulation of Thermosetting Polyurethanes Using the Bio-based Chain Extender Furandimethanol

Study on the Preservation Performance of Composite Systems for Concentrated Natural Rubber Latex

Influence of Phosphorus-containing Polyol OP550 on the Thermal, Mechanical, and Flame-retardant Performance of Poly(tetramethylene ether glycol)-based Thermoplastic Polyurethane

Related Author

QI Bo-wei

LV Fang-ge

HONG Min-bo

WANG Shi-jie

LIU Wei

Wei-li WU

Zhe CHEN

HAN Ya-xi

Related Institution

Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science and Technology

College of Materials Science and Engineering,Qiqihar University

National & Local Joint Engineering Research Center for Applied Technology of Hybrid Nanomaterials, Henan University

Institute of Nanoscience and Engineering, Henan University

College of Chemistry and Molecular Sciences, Henan University

⁰