纳米离子材料中离子相互作用与流变性能调控

doi:10.7503/cjcu20150856

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (4): 767.doi: 10.7503/cjcu20150856

纳米离子材料中离子相互作用与流变性能调控

刘洋健¹, 阮英波², 张宝庆²(), 乔昕², 刘琛阳²()

1. 北京科技大学化学与生物工程学院, 北京 100083
2. 中国科学院化学研究所, 工程塑料院重点实验室, 北京 100190

收稿日期:2015-11-08 出版日期:2016-04-10 发布日期:2016-03-22
基金资助:
国家自然科学基金(批准号: 51103162)资助

Tuning of Ionic Interaction and Rheological Properties of Nanoscale Ionic Materials^†

LIU Yangjian¹, RUAN Yingbo², ZHANG Baoqing^2,^*(), QIAO Xin², LIU Chenyang^2,^*()

1. School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China
2. Key Laboratory of Engineering Plastics of Chinese Academy of Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2015-11-08 Online:2016-04-10 Published:2016-03-22
Contact: ZHANG Baoqing,LIU Chenyang E-mail:zhangbq@iccas.ac.cn;liucy@iccas.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51103162)

摘要/Abstract

摘要：

制备了2种离子相互作用强度不同的纳米离子材料(相对强度SiO₂-SIT-M2070 > SiO₂-SIT-Ethomeen). 结果表明, 分散相SiO₂在纳米离子材料中稳定存在, 未出现聚集. 纳米离子材料中外层低聚物的结晶受到抑制, 且离子相互作用越强, 结晶抑制作用越明显, 对动态流变性质也有显著影响. 在相同固含量条件下, 纳米离子材料SiO₂-SIT-Ethomeen的动态剪切模量和黏度比SiO₂-SIT-M2070小1~3个数量级. 在动态大应变剪切条件下, 高固含量的SiO₂-SIT-M2070表现出软玻璃流变学特性; 而SiO₂-SIT-Ethomeen体系表现出强应变过冲现象, 并且随着固含量的升高, 其动态模量和黏度出现极大值时所对应的应变值逐渐减小, 而且应变过冲的程度逐渐变小. 因此通过调节组分间离子相互作用可有效地调节纳米离子材料的流变特性.

关键词: 纳米离子材料, 离子相互作用, 流变特性, 应变过冲

Abstract:

We prepared two kinds of silica-based nanoscale ionic materials(NIMs) with increasing SiO₂ contents, and also with different relative ionic interaction strengths between their constituents(SiO₂-SIT-M2070>SiO₂-SIT-Ethomeen for the relative ionic interaction strength). The results of transmission electron microscope(TEM) and small-angle X-ray scattering(SAXS) investigations indicated that there was no obvious nano-particle aggregate in both kinds of NIMs. The differential scanning calorimetry(DSC) results showed that the ionic interactions prohibited the crystallization of out-shell block copolymers in the prepared NIMs. Moreover, the crystallization suppression was more serious with increasing the ionic interaction strength. Ionic interaction also displayed the dramatic influence on the dynamic rheological behavior of as-prepared NIMs. The dynamic shear moduli and viscosities of SiO₂-SIT-Ethomeen were about 1—3 orders of magnitude lower than those of SiO₂-SIT-M2070 with the same solid contents. Under the shear of large dynamic strain, SiO₂-SIT-M2070 with the relatively high solid contents showed the soft glass rheological properties, while SiO₂-SIT-Ethomeen showed the phenomenon of strong strain overshoot. Furthermore, the strain that corresponding with the maximum of dynamic shear moduli and viscosities gradually decreased with the increasing of solid contents, and so did the degree of overshoot. All above results suggested that the rheological properties of NIMs could be effectively controlled by carefully tuning the ionic interactions between their constituents.

Key words: Nanoscale ionic material, Ionic interaction, Rheological property, Strain overshoot

中图分类号:

O631

TrendMD:

刘洋健, 阮英波, 张宝庆, 乔昕, 刘琛阳. 纳米离子材料中离子相互作用与流变性能调控. 高等学校化学学报, 2016, 37(4): 767.

LIU Yangjian, RUAN Yingbo, ZHANG Baoqing, QIAO Xin, LIU Chenyang. Tuning of Ionic Interaction and Rheological Properties of Nanoscale Ionic Materials^†. Chem. J. Chinese Universities, 2016, 37(4): 767.

图/表 7

Fig.1 Titration curves for acid-base reaction between SiO2-SIT and M2070(A) or Ethomeen(B)

Fig.2 TGA curves of SiO2-SIT-M2070(A) and SiO2-SIT-Ethomeen(B)^(A) a. SiO2; b. SiO2-SIT; c. M2070. Mass fraction of SiO2 in SiO2-SIT-M2070(%): d. 20.1; e. 26.3; f. 30.7. (B) a. Ethomeen. Mass fraction of SiO2 in SiO2-SIT-Ethomeen(%): b. 20.5; c. 27.4; d. 31.7; e. 37.4; f. 44.0.

Fig.3 Representative TEM images of SiO2-SIT-M2070(A, B) and SiO2-SIT-Ethomeen(C,D)^ Mass fraction of SiO2 in the materials: (A) 20.1%; (B) 30.7%; (C) 20.5%; (D) 44.0%.

Fig.4 SAXS curves of SiO2-SIT-M2070(A) and SiO2-SIT-Ethomeen(B)^Curves shifted vertically for sake of clarity. (A) Mass fraction of SiO2 in SiO2-SIT-M2070(%): a. 20.1; b. 26.3; c. 30.7. (B) Mass fraction of SiO2 in SiO2-SIT-Ethomeen(%): a. 20.5; b. 27.4; c. 31.7; d. 37.4; e. 44.0.

Fig.5 DSC curves of SiO2-SIT-M2070(A) and SiO2-SIT-Ethomeen(B)^Curves shifted vertically for sake of clarity. (A) Mass fraction of SiO2 in SiO2-SIT-M2070(%): a. 0; b. 20.1; c. 26.3; d. 30.7. (B) Mass fraction of SiO2 in SiO2-SIT-Ethomeen(%): a. 0; b. 20.5; c. 27.4; d. 31.7; e. 37.4; f. 44.0.

Fig.6 Dynamic frequency sweep curves for SiO2-SIT-M2070(A, B) and SiO2-SIT-Ethomeen(C, D)^ (A, C) G', G″-ω; (B, D) η*-ω.

Fig.7 Dynamic strain sweep results of SiO2-SIT-M2070(A) and SiO2-SIT-Ethomeen(B, C)^ (A) G', G″-γ; (B) G', G″-γ; (C) η*-γ.

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纳米离子材料中离子相互作用与流变性能调控

Tuning of Ionic Interaction and Rheological Properties of Nanoscale Ionic Materials^†

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纳米离子材料中离子相互作用与流变性能调控

Tuning of Ionic Interaction and Rheological Properties of Nanoscale Ionic Materials†

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Tuning of Ionic Interaction and Rheological Properties of Nanoscale Ionic Materials^†