4.7 Article

Scission energies of surfactant wormlike micelles loaded with nonpolar additives

Journal

JOURNAL OF COLLOID AND INTERFACE SCIENCE
Volume 604, Issue -, Pages 757-766

Publisher

ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcis.2021.07.001

Keywords

Self-assembly; Amphiphiles; Molecular theory; Additives; Supramolecular shape; Shape transition

Funding

  1. Agencia Nacional de Promocion Cientifica y Tecnologica (ANPCyT) [PICT 0154-2016, PICT 1520-2019]
  2. CONICET-NIH Level 1 Bilateral Cooperation Grant
  3. National Science Foundation [1941731]
  4. Division Of Materials Research
  5. Direct For Mathematical & Physical Scien [1941731] Funding Source: National Science Foundation

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This study investigates the effects of additives on the scission energy and rheological properties of surfactant wormlike micelles using molecular theory, showing qualitative agreement with experimental observations. The research reveals different mechanisms by which highly and mildly hydrophobic additives affect the scission energy of wormlike micelles.
Hypothesis: The previously observed effects of nonpolar additives on the scission energy and rheological properties of surfactant wormlike micelles can be explained in terms of the spatial distribution of the additive within the micelles. The dependence of the scission energy with the molecular organization of the system can be analyzed with a molecular theory capable of describing the thermodynamics and structure of the micelles. Theory: A new theoretical method to determine the scission energy of surfactant wormlike micelles is introduced. This methodology is based on a molecular theory that explicitly considers molecular details of all components of the micelles, and their inter-and intramolecular interactions without the use of fitting and/or empirical macroscopic parameters. Findings: The predicted effects of the concentration, molecular structure and hydrophobicity of the additive on the scission energy of cetyltrimethylammonium bromide (CTAB) wormlike micelles are found to be in qualitative agreement with previous experimental observations. In particular, our theory captures the decrease of micellar length with increasing content of highly hydrophobic additives and the non monotonic dependence of the viscosity with additive hydrophobicity. The latter effect arises because highly and mildly hydrophobic additives affect the scission energy of wormlike micelles via markedly different molecular mechanisms. (c) 2021 Elsevier Inc. All rights reserved.

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