Citation: Ling-fei Zheng, Zheng Wang, Yu-hua Yin, Run Jiang, Bao-hui Li. Monte Carlo Simulations of the Self-assembly of ABA Tri-block Copolymers inside an Oil-in-water Emulsion Droplet[J]. Acta Polymerica Sinica, ;2019, 50(9): 915-924. doi: 10.11777/j.issn1000-3304.2019.19051 shu

Monte Carlo Simulations of the Self-assembly of ABA Tri-block Copolymers inside an Oil-in-water Emulsion Droplet

Key Laboratory of Functional Polymer Materials of Ministry of Education, School of Physics, Nankai University, Tianjin 300071

Corresponding author: Bao-hui Li, baohui@nankai.edu.cn
Received Date: 15 March 2019
Revised Date: 31 March 2019
Available Online: 10 May 2019

The self-assembly of symmetric ABA tri-block copolymers inside an oil-in-water emulsion droplet upon solvent evaporation is investigated by Monte Carlo simulations, and the simulation results are compared with those in AB di-block copolymer systems. A morphological phase diagram is constructed in the two-dimensional space composed of surfactant concentration (φ) and the volume fraction of B segments (f_B). Non-porosity particles, closed-porosity particles, open-porosity particles, capsules, and micelles are observed. The study shows that when f_B ≤ 1/2, the increase of φ leads to a morphological evolution from non-porosity particle to closed-porosity particle and open-porosity particle, while for f_B > 1/2, micelles are observed in a larger φ window. The fraction of bridge chains (v_B) as a function of φ is always much lower than the corresponding bulk value. Moreover, the mean-square radius of gyration (<R_g²>) of the ABA tri-block copolymer chains is much smaller than that of the corresponding AB di-block copolymer chains with the same f_B and φ values under the same condition. Due to the influence of chain conformation, no capsule appears in the ABA tri-block copolymer system when f_B ≤ 1/2, which is different from the case of the corresponding AB di-block copolymer system. The specific surface area of particles with the same morphology falls into almost the same p regime, which indicates that the particle morphology largely determines its specific surface area. By calculating the formation energy of particles, it is confirmed that the surfactants in the system are the key to the formation of porous particles. All these are the same as what have been observed in AB di-block copolymer systems. In addition, the radial density distributions of water molecules in ABA tri-block system and the corresponding AB di-block system are not exactly the same, but the particle sizes are basically identical. The evolution processes including the typical non-porosity particles, closed-porosity particles, and open-porosity particles, as well as the bridging fraction during solvent evaporation are further discussed.
- ABA triblock polymers,
- Self-assembly,
- Surfactants,
- Emulsion droplet,
- Porous particles
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