白炭黑/聚氧化丙烯悬浮液的分子弛豫与流变行为

宋义虎; 郑重; 郑强

doi:10.11777/j.issn1000-3304.2022.22443

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白炭黑/聚氧化丙烯悬浮液的分子弛豫与流变行为

研究论文 | 更新时间：2024-01-18

- 白炭黑/聚氧化丙烯悬浮液的分子弛豫与流变行为
- Molecular Relaxation and Rheological Behaviors of Silica/Poly(propylene oxide) Dispersions
- 高分子学报 2023年54卷第5期页码：643-654
- 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：
  
  E-mail: s_yh0411@zju.edu.cn
  zhengqiang@zju.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣51790503);U1908221, 51873190┫
- DOI：10.11777/j.issn1000-3304.2022.22443
  中图分类号：
- 纸质出版日期：2023-05-20，
  
  网络出版日期：2023-02-28，
  
  收稿日期：2022-12-24，
  
  录用日期：2023-02-03
扫描看全文
宋义虎,郑重,郑强.白炭黑/聚氧化丙烯悬浮液的分子弛豫与流变行为[J].高分子学报,2023,54(05):643-654.

Song Yi-hu,Zheng Zhong,Zheng Qiang.Molecular Relaxation and Rheological Behaviors of Silica/Poly(propylene oxide) Dispersions[J].ACTA POLYMERICA SINICA,2023,54(05):643-654.
宋义虎,郑重,郑强.白炭黑/聚氧化丙烯悬浮液的分子弛豫与流变行为[J].高分子学报,2023,54(05):643-654. DOI： 10.11777/j.issn1000-3304.2022.22443.

Song Yi-hu,Zheng Zhong,Zheng Qiang.Molecular Relaxation and Rheological Behaviors of Silica/Poly(propylene oxide) Dispersions[J].ACTA POLYMERICA SINICA,2023,54(05):643-654. DOI： 10.11777/j.issn1000-3304.2022.22443.

摘要

气相二氧化硅/聚醚低聚物悬浮液体系广泛应用于涂料、胶黏剂、锂离子电池、液体防弹衣等诸多领域. 然而，聚醚与白炭黑界面相互作用复杂，所形成的界面吸附层显著影响悬浮液的流变行为，界面层结构与流变行为调控是长期困扰学术界和工业界的难题. 本文工作详细研究了白炭黑/线形丙二醇低聚物(PPG)界面层结构与流变行为，考察了PPG分子量(0.4~4 kg/mol)的影响机制. 研究发现，PPG分子量影响其在白炭黑附近的受限状态和悬浮液流变行为. 分子量为0.4 kg/mol时，PPG通过端羟基与白炭黑表面硅羟基间氢键作用而形成较厚((1.0±0.2) nm)的玻璃化层，玻璃化层几何逾渗导致悬浮液在10 rad/s下呈现溶胶-凝胶转变；分子量为1~2 kg/mol的PPG在白炭黑粒子表面形成较薄((0.8±0.1) nm)的玻璃化层，分子量为3~4 kg/mol的PPG则在白炭黑粒子表面形成受限层，悬浮液在10 rad/s下呈溶胶行为. 玻璃化层几何逾渗和悬浮液溶胶-凝胶转变之间的关系说明，界面层分子受限程度和流变行为均受PPG羟基密度及其与白炭黑界面相互作用的影响.

Abstract

Dispersions based on fumed silica/polyether oligomers are widely used in varying fields including adhesives

coatings

lithium ion batteries

and liquid armors. It has been found that the complicated interfacial interaction between silica and polyether and the resultant interfacial layers strongly influences the rheological responses of the dispersions while it is a long-standing issue to control the interfacial structure and rheological behavior in both the academy and industry. Investigated herein are the interfacial structure and rheological behaviors of silica/linear poly(propylene oxide) (PPG) oligomer dispersions as a function of molecular weight (0.4-4 kg/mol) of PPG and volume fraction of silica. The results show that a change of molecular weight of PPG in a narrow range strongly influences the molecular adsorption and restriction in the vicinity of silica nanoparticles and the rheology of the dispersions. Moreover

PPG with molecular weight of 0.4 kg/mol forms glassy layers of ((1.0±0.2) nm) on the surface of silica nanoparticles

via

hydrogen bonding between terminal hydroxyls of PPG and silanols of silica. The percolation of glassy layers at high silica loadings causes the dispersions to undergo a sol-to-gel transition at 10 rad/s. On the other hand

PPG with molecular weight of 1-2 kg/mol forms incomplete glassy layers of (0.8±0.1) nm in thickness and that of 3-4 kg/mol forms restrained layers surrounding silica nanoparticles

both yielding sol-like rheological responses up to silica volume fraction of 0.16 at 10 rad/s. Furthermore

a comparison between thresholds of percolation of glassy layers and sol-to-gel transition suggests that the degree of molecular restriction nearby silica nanoparticles and therefore the rheological behaviors of the dispersions are determined by density of terminal hydroxyls of PPG and the interaction terminal hydroxyls and silanols of silica.

关键词

白炭黑聚氧化丙烯悬浮液界面流变行为

Keywords

SilicaPoly(propylene oxide)DispersionInterfaceRheological behaviors

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