Supramolecular self-assembly of robust, ultra-stable, and high-temperature-resistant viscoelastic worm-like micelles

Xiaoqin Cao; Weiluo Guo; Qi Zhu; Hongjiang Ge; Hua Yang; Yubin Ke; Xiaohuo Shi; Xingyu Lu; Yujun Feng; Hongyao Yin

doi:10.1016/j.jcis.2023.06.086

Supramolecular self-assembly of robust, ultra-stable, and high-temperature-resistant viscoelastic worm-like micelles

J Colloid Interface Sci. 2023 Nov:649:403-415. doi: 10.1016/j.jcis.2023.06.086. Epub 2023 Jun 17.

Authors

Xiaoqin Cao¹, Weiluo Guo¹, Qi Zhu², Hongjiang Ge³, Hua Yang⁴, Yubin Ke⁴, Xiaohuo Shi⁵, Xingyu Lu⁵, Yujun Feng¹, Hongyao Yin⁶

Affiliations

¹ Polymer Research Institute, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, PR China.
² CNPC Bohai Drilling Engineering Co., Ltd, Tianjin 300450, PR China.
³ Oil Production Technology Institute, Dagang Oil Field Company PetroChina, Tianjin 300280, PR China.
⁴ Spallation Neutron Source Science Center, Dongguan 523803, PR China; Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, PR China.
⁵ Instrumentation and Service Center for Molecular Sciences, Westlake University, Hangzhou 310024, PR China.
⁶ Polymer Research Institute, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, PR China. Electronic address: hyyin@scu.edu.cn.

PMID: 37354797
DOI: 10.1016/j.jcis.2023.06.086

Abstract

Hypothesis: Worm-like micelles are susceptible to heating owing to the fast dynamic exchange of molecules between micelles. Inhibition of such exchange could afford robust worm-like micelles, which is expected to largely improve rheology properties at high temperatures.

Experiments: A cationic surfactant docosyl(trimethyl)azanium chloride (DCTAC) and a strongly hydrophobic organic counterion 3-hydroxy naphthalene-2-carboxylate (SHNC) were used for the worm-like micelles fabrication. The microstructure was characterized using cryogenic transmission electron microscopy and small-angle neutron scattering, and the interactions between DCTAC and SHNC were characterized using nuclear magnetic resonance spectroscopy. Rheometer was employed to measure the rheological properties of the solution.

Findings: SHNC/DCTAC at the molar ration of 1:2 forms ultra-stable worm-like micelles, whose viscosity remain stable at temperature up to 130 °C. SHNC is found to strongly adsorbs on DCTAC micelle with the orientation on the surface of micelle, keeping the naphthalene backbone entire penetration into the palisade layer while both carboxylic and hydroxyl groups protrude out of the micelle. With temperature increasing, this adsorption further strengthens, resulting in the growth contour length and accompanying the enhancement of rheological properties. One SHNC molecule and two DCTAC molecules are speculated to form a stable complex via multiple interactions including hydrophobic, cationic-π, and π-π interactions, which decreases the dynamic exchange of them between micelles. These findings are helpful to understand surfactant aggregates stability and assist the development of novel stable supramolecular nanostructures. Additionally, the excellent thermal stability of this worm-like micellar fluid makes it a potential high-temperature resistant clean fracturing fluid for deep oil reservoirs.

Keywords: Clean fracturing fluid; Non-covalent interaction; Supramolecular self-assembly; Temperature resistance; Worm-like micelles.