Strain Softening Behaviors of Covalently and Ionically Crosslinked Nitrile Rubber Vulcanizates and Their Nanocomposites

Zhi-yun Li; Yi-hu Song; Qiang Zheng

doi:10.11777/j.issn1000-3304.2025.25189

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Strain Softening Behaviors of Covalently and Ionically Crosslinked Nitrile Rubber Vulcanizates and Their Nanocomposites

Research Article | 更新时间：2026-01-16

- Strain Softening Behaviors of Covalently and Ionically Crosslinked Nitrile Rubber Vulcanizates and Their Nanocomposites
- Acta Polymerica Sinica Vol. 57, Issue 1, Pages: 129-142(2026)
- 作者机构：
  
  高分子合成与功能构造教育部重点实验室浙江大学高分子科学与工程学系杭州 310027
- 作者简介：
  
  Yi-hu Song, E-mail: s_yh0411@zju.edu.cn
  Qiang Zheng, E-mail: zhengqiang@zju.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25189
  CLC：
- CSTR：32057.14.GFZXB.2025.7468
- Received：12 August 2025，
  
  Accepted：20 September 2025，
  
  Published Online：27 November 2025，
  
  Published：20 January 2026
- 稿件说明：
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李志云, 宋义虎, 郑强. 共价和离子交联丁腈橡胶及其纳米复合材料的应变软化行为. 高分子学报, 2026, 57(1), 129-142.

Li, Z. Y.; Song, Y. H.; Zheng, Q. Strain softening behaviors of covalently and ionically crosslinked nitrile rubber vulcanizates and their nanocomposites. Acta Polymerica Sinica (in Chinese), 2026, 57(1), 129-142.
李志云, 宋义虎, 郑强. 共价和离子交联丁腈橡胶及其纳米复合材料的应变软化行为. 高分子学报, 2026, 57(1), 129-142. DOI： 10.11777/j.issn1000-3304.2025.25189. CSTR： 32057.14.GFZXB.2025.7468.

Li, Z. Y.; Song, Y. H.; Zheng, Q. Strain softening behaviors of covalently and ionically crosslinked nitrile rubber vulcanizates and their nanocomposites. Acta Polymerica Sinica (in Chinese), 2026, 57(1), 129-142. DOI： 10.11777/j.issn1000-3304.2025.25189. CSTR： 32057.14.GFZXB.2025.7468.

摘要

离子键等牺牲键常用于调控橡胶材料的力学性能和自愈合行为，但鲜有研究涉及离子键-共价键共交联硫化胶及其纳米复合材料的应变软化行为. 本工作采用2-丙烯酰胺基-2-甲基丙磺酸、氧化锌、氧化二异丙苯制备离子键-共价键共交联丁腈橡胶硫化胶及其炭黑复合材料，研究了离子交联键对交联密度、力学性能和应变软化行为(Payne效应和Mullins效应)的影响. 结果表明，离子交联键的引入可提高交联密度和模量，降低线性黏弹区储能模量的频率依赖性和Payne效应临界应变幅度，减弱非线性黏弹区应变软化程度，促进Payne效应所伴随的动态剪切周期内应变硬化和剪切增稠-变稀转变. 离子交联键可显著增强硫化胶及其纳米复合材料在循环拉伸过程中的Mullins效应，且循环形变材料经低温(60 ℃)短时(10 min)热处理后不再呈现软化特征；而离子键在循环拉伸和短时低温热处理过程中难以通过破坏—重建机理来降低滞后行为. 研究结果可为离子键-共价键共交联硫化胶及其纳米复合材料应变软化机理研究及交联网络结构构筑和非线性黏弹性调控提供实验依据.

Abstract

Sacrificial bonds

including ionic bonds

are often used to regulate the mechanical properties and self-healing behavior of rubber materials. However

the strain-softening mechanism of vulcanizates and their nanocomposites involving ionic crosslinking bonds has rarely been studied. Herein

2-acrylamino-2-methylpropanesulfonic acid

zinc oxide

and dicumyl peroxide were used to prepare nitrile rubber vulcanizates and their carbon black nanocomposites cured by ionic and covalent crosslinks to investigate the effects of ionic crosslinking bonds on crosslinking density

mechanical properties

and strain softening behaviors (Payne effect and Mullins effect). The results showed that the introduction of ionic crosslinking bonds could improve the crosslinking density and modulus

reduce the frequency dependence of the storage modulus in the linear viscoelasticity region

weaken the strain softening behavior in the nonlinear viscoelasticity region

and promote the intracycle strain hardening and shear thickening-thinning transition accompanying the Payne effect. The ionic crosslinking bond also significantly enhanced the Mullins effect of the vulcanizates and their nanocomposites

and the cyclically deformed materials after a short-term (10 min) thermal treatment at a low temperature (60 ℃) do not soften when subjected to cyclic stretching. The results provided an experimental basis for studying the strain softening mechanism of covalently and ionically crosslinked rubbers and their nanocomposites for regulating nonlinear viscoelasticity.

关键词

Keywords

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