Issue 44, 2017

Why is surface diffusion the same in ultrastable, ordinary, aged, and ultrathin molecular glasses?

Abstract

Recently Fakhraai and coworkers measured surface diffusion in ultrastable glass produced by vapor deposition, ordinary glass with and without physical aging, and ultrathin films of the same molecular glass-former, N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD). Diffusion on the surfaces of all these glasses is greatly enhanced compared with the bulk diffusion similar to that previously found by others, but remarkably the surface diffusion coefficients DS measured are practically the same. The observed independence of DS from changes of structural α-relaxation due to densification or finite-size effect has an impact on the current understanding of the physical origin of enhanced surface diffusion. We have demonstrated before and also here that the primitive relaxation time τ0 of the coupling model, or its analogue τβ, the Johari–Goldstein β-relaxation, can explain quantitatively the enhancement found in ordinary glasses. In this paper, we assemble together considerable experimental evidence to show that the changes in τβ and τ0 of ultrastable glasses, aged ordinary glasses, and ultrathin-films are all insignificant when compared with ordinary glasses. Thus, in the context of the explanation of the enhanced surface diffusion given by the coupling model, these collective experimental facts on τβ and τ0 further explain approximately the same DS in the different glasses of TPD as found by Fakhraai and coworkers.

Graphical abstract: Why is surface diffusion the same in ultrastable, ordinary, aged, and ultrathin molecular glasses?

Supplementary files

Article information

Article type
Paper
Submitted
07 Aug 2017
Accepted
13 Sep 2017
First published
31 Oct 2017
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2017,19, 29905-29912

Why is surface diffusion the same in ultrastable, ordinary, aged, and ultrathin molecular glasses?

K. L. Ngai, M. Paluch and C. Rodríguez-Tinoco, Phys. Chem. Chem. Phys., 2017, 19, 29905 DOI: 10.1039/C7CP05357F

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