Depletion interaction in colloid/polymer mixtures: application of density functional theory

Abstract

Insert-route density functional approach (IRDFT), modified fundamental measure theory (MFMT) and thermodynamic perturbation theory (TPT1 and TPT2) are combined to study the depletion force between colloidal particles in hard sphere/hard sphere chain mixtures which represent a model of systems containing colloids dispersed in an athermal polymer solution. The predicted results are compared to simulations showing the reliability of the method used which captures the main characteristics of depletion interaction between colloids induced by polymers. Results of TPT2 are slightly more repulsive and better than that of TPT1 especially when the inter-particle distance is small than the diameter of polymer segment indicating the essential influence of the three-body correlations. Effects of the polymer density, polymer chain length and size ratio of colloid to polymer segment on the depletion force are studied in detail. Due to a little deterioration of the prediction in the high density region, further improvement is anticipated to better balance the competition between the excluded-volume effect and the chain connectivity.

Keywords:

• Depletion interaction
• Colloid/polymer mixtures
• Modified fundamental measure theory
• Thermodynamic perturbation theory

Acknowledgements

This work is supported by the National Natural Science Foundation of China (Projects No. 20236010, 20490200), the Doctoral Research Foundation sponsored by the Ministry of Education of China (Project No. 20050251004), E-institute of Shanghai High Institution Grid (No. 200303) and Shanghai Municipal Education Commission of China.