Mechanisms for hyperthermal polyatomic hydrocarbon modification of PMMA surfaces from molecular dynamics simulations
Classical molecular dynamics simulations are performed to determine the mechanisms by which hyperthermal hydrocarbon polyatomics, which are present in low-energy plasmas, chemically modify polymer surfaces. In particular, C2H, CH3, and C3H5 are deposited on an amorphous poly (methyl methacrylate) (PMMA) substrate with kinetic energies of 4, 10, 25, and 50 eV and compared to the deposition of H at the same energies. The short-range forces on the atoms are determined using the second generation reactive empirical many-body potential, while the long-range forces are determined using a Lennard-Jones potential. The simulations predict that at all these incident energies, the chemical modification of the PMMA is limited to within a nanometer of the surface. Atoms, fragments, and incident polyatomics are further predicted to chemically attach to specific sites on the PMMA monomers at low energies and to attach to a wider range of sites at higher energies. However, no appreciable cross-linking between polymer chains is predicted to occur. Variation in the penetration depth of the deposited polyatomics or H is correlated to differences in their size and bond saturation. The greatest extent of chemical modification of the PMMA surface slab is achieved for C2H deposition with 50 eV of kinetic energy.
Kamal Choudhary, Leah B. Hill, Travis W. Kemper, and Susan B. Sinnott
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