Molecular dynamics simulations for interfacial structure and affinity between carboxylic acid-modified Al2O3 and polymer melts

T Saito and M Kubo and T Tsukada and E Shoji and G Kikugawa and D Surblys and M Kubo, JOURNAL OF CHEMICAL PHYSICS, 159, 164708 (2023).

DOI: 10.1063/5.0169721

Controlling the dispersion state of nanoparticles in a polymer matrix is necessary to produce polymer nanocomposites. The surface modification of nanoparticles is used to enable their dispersion in polymers. Moreover, molecular dynamics (MD) simulations are useful for revealing the interfacial properties between nanoparticles and polymers to aid in the design of materials. In this study, the effect of surface coverage, modifier length, and polymer species on the interfacial structure and affinity between surface-modified Al2O3 and polymer melts were investigated using all-atom MD simulations. Hexanoic, decanoic, and tetradecanoic acids were used as surface modifiers, and polypropylene (PP), polystyrene (PS), and poly (methyl methacrylate) (PMMA) were used as polymers. The work of adhesion W-adh and the work of immersion W(imm )were selected as quantitative measures of affinity. W-adh was calculated using the phantom-wall approach, and W-imm was calculated by simply subtracting the surface tension of polymers gamma L from W-adh. The results showed that W-adh and W-imm were improved by surface modification with low coverage, owing to a good penetration of the polymer. The effect of modifier length on Wadh and Wimm was small. Whereas Wadh increased in the following order: PP < PS < PMMA, Wimm increased as follows: PMMA < PS < PP. Finally, the trend of Wadh and Wimm was organized using the Flory-Huggins interaction parameter chi between the modifier and the polymer. This study demonstrates that the interfacial affinity can be improved by tuning the surface coverage and modifier species depending on the polymer matrix.

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