The Release of Trapped Gases from Amorphous Solid Water Films: I. “Top-Down” Crystallization-Induced Crack Propagation Probed using the Molecular Volcano
Abstract
In this (Paper I) and the companion paper (Paper II) we investigate the mechanisms for the release of trapped gases from underneath of amorphous solid water (ASW) films. In prior work, we reported the episodic release of trapped gases in concert with the crystallization ASW, a phenomenon that we termed the "molecular volcano". The observed abrupt desorption is due to the formation of cracks that span the film to form a connected pathway for release. In this paper we utilize the "molecular volcano" desorption peak to characterize the formation of crystallization-induced cracks. We find that the crack length and distribution are independent of the trapped gas (Ar, Kr, Xe, CH4, N2, O2 or CO). Selective placement of the inert gas layer is used to show that cracks form near the top of the film and propagate downward into the film. Isothermal experiments reveal that, after some induction time, cracks propagate linearly in time with an Arrhenius dependent velocity corresponding to an activation energy of 54 kJ/mol. This value is consistent with the crystallization growth rate reported by others and establishes a direct connection between crystallization growth rate and the crack propagation rate. A two-step model in which nucleation and crystallizationmore »
- Authors:
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1072871
- Report Number(s):
- PNNL-SA-92035
39940; KC0301020
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics, 138(10):Article No. 104501
- Additional Journal Information:
- Journal Name: Journal of Chemical Physics, 138(10):Article No. 104501
- Country of Publication:
- United States
- Language:
- English
- Subject:
- Environmental Molecular Sciences Laboratory
Citation Formats
May, Robert A, Smith, R Scott, and Kay, Bruce D. The Release of Trapped Gases from Amorphous Solid Water Films: I. “Top-Down” Crystallization-Induced Crack Propagation Probed using the Molecular Volcano. United States: N. p., 2013.
Web. doi:10.1063/1.4793311.
May, Robert A, Smith, R Scott, & Kay, Bruce D. The Release of Trapped Gases from Amorphous Solid Water Films: I. “Top-Down” Crystallization-Induced Crack Propagation Probed using the Molecular Volcano. United States. https://doi.org/10.1063/1.4793311
May, Robert A, Smith, R Scott, and Kay, Bruce D. 2013.
"The Release of Trapped Gases from Amorphous Solid Water Films: I. “Top-Down” Crystallization-Induced Crack Propagation Probed using the Molecular Volcano". United States. https://doi.org/10.1063/1.4793311.
@article{osti_1072871,
title = {The Release of Trapped Gases from Amorphous Solid Water Films: I. “Top-Down” Crystallization-Induced Crack Propagation Probed using the Molecular Volcano},
author = {May, Robert A and Smith, R Scott and Kay, Bruce D},
abstractNote = {In this (Paper I) and the companion paper (Paper II) we investigate the mechanisms for the release of trapped gases from underneath of amorphous solid water (ASW) films. In prior work, we reported the episodic release of trapped gases in concert with the crystallization ASW, a phenomenon that we termed the "molecular volcano". The observed abrupt desorption is due to the formation of cracks that span the film to form a connected pathway for release. In this paper we utilize the "molecular volcano" desorption peak to characterize the formation of crystallization-induced cracks. We find that the crack length and distribution are independent of the trapped gas (Ar, Kr, Xe, CH4, N2, O2 or CO). Selective placement of the inert gas layer is used to show that cracks form near the top of the film and propagate downward into the film. Isothermal experiments reveal that, after some induction time, cracks propagate linearly in time with an Arrhenius dependent velocity corresponding to an activation energy of 54 kJ/mol. This value is consistent with the crystallization growth rate reported by others and establishes a direct connection between crystallization growth rate and the crack propagation rate. A two-step model in which nucleation and crystallization occurs in an induction zone near the top of the film followed by the propagation of a crystallization/crack front into the film is in good agreement with the temperature programmed desorption results.},
doi = {10.1063/1.4793311},
url = {https://www.osti.gov/biblio/1072871},
journal = {Journal of Chemical Physics, 138(10):Article No. 104501},
number = ,
volume = ,
place = {United States},
year = {Thu Mar 14 00:00:00 EDT 2013},
month = {Thu Mar 14 00:00:00 EDT 2013}
}