气相白炭黑/低分子量聚乙二醇悬浮体系的分子弛豫与流变行为

徐贝; 宋义虎; 郑强

doi:10.11777/j.issn1000-3304.2017.17008

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气相白炭黑/低分子量聚乙二醇悬浮体系的分子弛豫与流变行为

研究论文 | 更新时间：2021-01-26

- 气相白炭黑/低分子量聚乙二醇悬浮体系的分子弛豫与流变行为
- Molecular Relaxation and Rheological Behaviors of Fumed Silica/Low-molecular Weight Polyethylene Glycol Suspensions
- 高分子学报 2017年第11期页码：1832-1840
- 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：
  
  宋义虎, E-mail: s_yh0411@zju.edu.cn Yi-hu Song, E-mail: s_yh0411@zju.edu.cn
- 基金信息：
  
  国家自然科学基金(51333004);国家自然科学基金(51573157);国家自然科学基金(51373149);浙江省自然科学基金(R14E030003);贵州省重点科技项目(2013-6016)
- DOI：10.11777/j.issn1000-3304.2017.17008
  中图分类号：
- 纸质出版日期：2017-11-20，
  
  收稿日期：2017-1-9，
  
  修回日期：2017-3-5，
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徐贝, 宋义虎, 郑强. 气相白炭黑/低分子量聚乙二醇悬浮体系的分子弛豫与流变行为[J]. 高分子学报, 2017,(11):1832-1840.

Bei Xu, Yi-hu Song, Qiang Zheng. Molecular Relaxation and Rheological Behaviors of Fumed Silica/Low-molecular Weight Polyethylene Glycol Suspensions[J]. Acta Polymerica Sinica, 2017,(11):1832-1840.
徐贝, 宋义虎, 郑强. 气相白炭黑/低分子量聚乙二醇悬浮体系的分子弛豫与流变行为[J]. 高分子学报, 2017,(11):1832-1840. DOI： 10.11777/j.issn1000-3304.2017.17008.

Bei Xu, Yi-hu Song, Qiang Zheng. Molecular Relaxation and Rheological Behaviors of Fumed Silica/Low-molecular Weight Polyethylene Glycol Suspensions[J]. Acta Polymerica Sinica, 2017,(11):1832-1840. DOI： 10.11777/j.issn1000-3304.2017.17008.

摘要

采用亲水气相二氧化硅（FS）、非缠结聚乙二醇（PEG，重均分子量400）制备悬浮体系，考察FS体积分数（

）对PEG本体相

-松弛、结晶行为及悬浮体系流变行为的影响.结果表明，FS可延缓PEG本体相

-松弛，提高玻璃化转变温度，并显著增加浮体系黏度，降低本体PEG相结晶与熔融焓.低填充时，FS起成核作用；高填充时，FS延迟PEG分子扩散，并降低结晶温度.FS对PEG结晶的不同作用发生在悬浮体系溶胶-凝胶转变附近，此时悬浮液非线性动态流变行为呈现显著的硬化软化特性，线性动态流变行为呈现最为显著的频率依赖性.通过建立线性动态流变行为叠加曲线，揭示了FS对PEG分子链扩散行为的显著推迟作用.

Abstract

Suspensions were prepared by mixing hydrophilic fumed silica (FS) with low-molecular polyethylene glycol (PEG

weight-averaged molecular weight 400). By differential scanning calorimeter and broadband dielectric spectrometer

influences of FS volume fraction (

) on

-relaxation and crystallization behaviors of bulk PEG phase were investigated. Furthermore

influences of

on the linear and nonlinear rheology behaviors of the suspensions were also investigated using stress-controlled rheometer. For the bulk PEG phase

-relaxation is retarded and glass transition temperature (

) is increased due to the addition of FS. On the other hand

FS significantly retard the diffusion of global PEG molecules

which leads to a great increase in viscosity of the suspensions along with significant reductions in crystallization and fusion enthalpy of the bulk PEG phase. The suspensions demonstrate different rheology and crystallization behaviors with varying

. The low-filled suspensions exhibit an apparent sol-like rheological response

in which FS plays a nucleating role to promote PEG crystallization. However

the high-filled suspensions apparently behave like gels

in which FS restrains the chain diffusion and crystallization. The role of FS changes in the vicinity of

=0.16

where the system undergoes an apparent sol-to-gel transition. In the close vicinity of this transition

the nonlinear dynamic rheology shows the most obvious strain hardening

while the linear dynamic rheology demonstrates the most significant frequency-dependence. Due to the extremely complicated nonlinear rheological response of the suspensions

it is hard to observe the pure hydrodynamics region experimentally

and in the frequency range achieved

complex viscosity (

) as a function of

at given frequencies does not fit classical hydrodynamics equations that do not consider the effect of nanoparticles on the polymer chains diffusion. To account for the effect of nanoparticles on the diffusion of PEG chains

data of liner dynamic rheology of the suspensions are shifted horizontally and vertically to create master curves with pure PEG as the reference. The creation of master curves reveals that FS greatly retards the diffusion of global PEG chains in the constrained bulk phase

which plays a major role in the reinforcement and dissipation of the suspensions. In addition to the dynamically retarded bulk PEG chains

both the inter-particle friction in the low-filled sols and the in-cage rattling motion of nanoparticles in the high-filled gels additionally contribute to the dissipation behavior of the suspensions

resulting in the complicated dynamic rheological behavior.

关键词

气相二氧化硅聚乙二醇界面层剪切增稠分子松弛

Keywords

Fumed silicaPolyethylene glycolInterfacial layerShear thickeningMolecular relaxation

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