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Nanoparticle solvation in polymer-CO2 mixtures.

Xiaofei Xu1, Diego E Cristancho, Stéphane Costeux

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We explored nanoparticle solvation in a poly(methyl methacrylate)-CO2 mixture. Optimal solvation pressure depends on particle size and interactions, with a critical radius identified for specific conditions.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Thermodynamics

Background:

  • Understanding nanoparticle behavior in complex fluid mixtures is crucial for materials design.
  • Poly(methyl methacrylate)-CO2 mixtures present unique phase behavior relevant to nanoparticle solvation.
  • Classical density-functional theory provides a framework for studying nanoscale phenomena in fluids.

Purpose of the Study:

  • To investigate the solvation free energy of a single nanoparticle within a poly(methyl methacrylate)-CO2 mixture at coexistence.
  • To determine the influence of temperature, pressure, and nanoparticle properties on solvation.
  • To identify conditions for optimal nanoparticle solvation and predict critical parameters.

Main Methods:

  • Statistical classical density-functional theory was employed.
  • Simulations were conducted at coexistence conditions for the poly(methyl methacrylate)-CO2 mixture.
  • Solvation free energy was analyzed as a function of temperature, pressure, and nanoparticle radius.

Main Results:

  • Lowest solvation free energy occurs at the triple point pressure under triple-phase coexistence.
  • An optimal pressure for solvation free energy exists beyond the triple line endpoint for subcritical radii.
  • Optimal pressure decreases with increasing nanoparticle radius and nanoparticle-fluid attraction strength.

Conclusions:

  • Nanoparticle solvation in poly(methyl methacrylate)-CO2 mixtures is pressure and temperature-dependent.
  • A critical nanoparticle radius governs the transition to optimal solvation behavior.
  • Interfacial tension in the planar wall limit can estimate this critical radius.