Abstract
Self-assembly of block copolymers in the presence of solvents forms ordered mesophase structures, also known as lyotropic liquid crystals (LLCs). The aim of this work is to investigate the rheological properties of Pluronic block copolymer/water/oil mesophases with lamellar and hexagonal structures. The flow behavior of lamellar and hexagonal mesophases indicates that they have yield stress. Oscillatory shear experiments show that mesophases have solid-like behavior and exhibit type III non-linear behavior. The elastic modulus of mesophases is probably controlled by the van der Waals interaction between micelles. We suggest that at relatively low frequencies, defects control the rheological behavior of LLCs, while at high frequencies, the contributions in micellar scale are dominant. Applying high strains on the LLCs induces two relaxation times after cessation of flow, decreases the storage modulus in the whole frequency range, and decreases the loss modulus in small-frequency regime with negligible effect at high frequencies. The decrease in moduli is reversible and the system relaxes back to its original elastic modulus at rest. The observed behavior can be attributed to the elimination of defects under high strains and their re-formation during long enough rest times.
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Acknowledgments
The authors thank Dr. Millicent Firestone and Elijah Wade for assistance with SAXS measurements. This work was partly supported by Bureau of Reclamation (Agreement No. R10AC80283). This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Los Alamos National Laboratory, an affirmative action equal opportunity employer, is managed by Triad National Security, LLC for the U.S. Department of Energy’s NNSA, under contract 89233218CNA000001. The rheometer was purchased through National Science Foundation Award #1438584. The authors acknowledge the support of the National Institute of Standards and Technology, U.S. Department of Commerce, in providing the neutron research facilities used in this work. The authors also thank Dr. Yun Liu and Dr. Kathleen Weigandt for their help in rheo-SANS study
Funding
This work was partly supported by the Bureau of Reclamation (Agreement No. R10AC80283). The rheometer was purchased through the National Science Foundation Award #1438584.
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Qavi, S., Foudazi, R. Rheological characteristics of mesophases of block copolymer solutions. Rheol Acta 58, 483–498 (2019). https://doi.org/10.1007/s00397-019-01162-y
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DOI: https://doi.org/10.1007/s00397-019-01162-y