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A reverse lyotropic liquid crystal formed by cetylpyridiniumchloride in cyclohexane with the assistance of aromatic counterions

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Abstract

The self-assembly of the cationic surfactant cetylpyridiniumchloride (CPC) in cyclohexane was studied using polarizing-microscopy (POM), small angle X-ray scattering (SAXS), and rheology measurements. Homogeneous solutions of CPC/aromatic salts were produced using aromatic salts, specifically, NaBzs, NaNphs, or NaSal. The majority of the samples showed highly viscous gel-like appearances. SAXS measurements together with POM observations indicate hexagonal liquid crystals in both the CPC/NaNphs and CPC/NaSal, while multiple types of aggregates were shown to co-exist in the CPC/NaBzs. These were attributed to the interactions of aromatic counterions with the pyridinium head-group of CPC, resulting in increased size of the CPC head to different extents depending on the aromatic counterions. The formation of core-shell aggregates consequently caused further packing into liquid crystals. The specific role of NaSal that carried an ortho-hydroxyl in its benzene ring is discussed, and the mechanism of trace water molecules bridging neighboring NaSal molecules was revealed according to Fourier transform infrared (FT-IR) measurements. The samples had high viscoelasticity, for example, the steady-state low-shear viscosity at a shear rate of 0.001, ηL, of the samples at W0 = 32 was 3.3 × 105, 2.0 × 104, and 6.8 × 102 Pa·s for CPC/NaBzs, CPC/NaNphs, and CPC/NaSal, respectively, at 25 °C. The corresponding elastic plateau moduli, G′P, were 1.9 × 103, 1.1 × 103, and 1.1 × 102 Pa, respectively. The temperature effect was examined for samples at W0 = 32, which were found to retain high viscosity at higher temperatures, for example, the relative viscosity to solvent cyclohexane, ηr, reached 107 and 105 for CPC/NaBzs and CPC/NaNphs, respectively, at 70 °C.

Cetylpyridiniumchloride (CPC), together with aromatic salt, sodium 2-naphthalenesulfonate, or sodium salicylate, was dissolved in cyclohexane to form inverted hexagonal liquid crystals.

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Funding

Financial support was from the National Natural Science Foundation of China (Grant no. 21473032).

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  1. Institute of Colloid and Interface Chemistry, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, 350108, Fujian Province, China

    Pan-pan Gu & Jian-xi Zhao

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Gu, Pp., Zhao, Jx. A reverse lyotropic liquid crystal formed by cetylpyridiniumchloride in cyclohexane with the assistance of aromatic counterions. Colloid Polym Sci 297, 271–283 (2019). https://doi.org/10.1007/s00396-018-04466-2

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