title: Mechanochemistry at Solid Surfaces: Polymerization of Adsorbed Molecules by Mechanical Shear at Tribological Interfaces.
abstract: Polymerization of allyl alcohol adsorbed and sheared at a silicon oxide interface is studied using tribo-tests in vapor phase lubrication conditions and reactive molecular dynamics simulations. The load dependences of product formation obtained from experiments and simulations were consistent, indicating that the atomic-scale processes observable in the simulations were relevant to the experiments. Analysis of the experimental results in the context of mechanically assisted thermal reaction theory, combined with the atomistic details available from the simulations, suggested that the association reaction pathway of allyl alcohol molecules induced by mechanical shear is quite different from chemically induced polymerization reactions. Findings suggested that some degree of distortion of the molecule from its equilibrium state is necessary for mechanically induced chemical reactions to occur and such a distortion occurs during mechanical shear when molecules are covalently anchored to one of the sliding surfaces.
authors.affiliation: School of Engineering, University of California , Merced, California 95343, United States.
authors.forename: Jejoon
authors.identifier: http://orcid.org/0000-0001-6323-7572
authors.initials: J
authors.lastname: Yeon
authors.affiliation: Department of Chemical Engineering and Materials Research Institute, Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Xin
authors.initials: X
authors.lastname: He
authors.affiliation: School of Engineering, University of California , Merced, California 95343, United States.
authors.forename: Ashlie
authors.initials: A
authors.lastname: Martini
authors.affiliation: Department of Chemical Engineering and Materials Research Institute, Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Seong H
authors.identifier: http://orcid.org/0000-0002-8575-7269
authors.initials: SH
authors.lastname: Kim
keywords: ReaxFF MD simulations; mechanochemistry; shear-induced chemical reactions; tribology; vapor phase lubrication