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Title: Moisture Corrosion of LiH: A Kinetic Investigation by DRIFT Spectroscopy

Abstract

Lithium hydride (LiH) is a unique, ionic compound with applications in a variety of industries. Unfortunately, LiH is very reactive toward H2O even at ppm levels, forming oxide (Li2O) and hydroxide (LiOH) corrosion layers while outgassing H2. An effective means to eliminate unwanted outgassing is vacuum-heating to convert LiOH into Li2O, although subsequent re-exposure to moisture during transport/handling reconverts some Li2O back to LiOH. A corrosion growth model for previously vacuum-baked LiH is necessary for long-term prediction of the hydrolysis of LiH. In this work, a para-linear hydroxide corrosion growth model is proposed for the reaction of previously vacuum-baked LiH samples with moisture. This model, composed of two competing diffusion reaction fronts at the LiOH/Li2O and Li2O/LiH interfaces, is validated experimentally by subjecting a previously vacuum-baked polycrystalline LiH sample to 35 ppm of H2O at room temperature while monitoring the corrosion growth as a function of time with diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy. The para-linear growth model for the hydrolysis of previously vacuum-baked LiH proposed in this report can also serve as a template for the hydrolysis of other hygroscopic oxides grown on metal or metal hydride substrates.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1597620
Report Number(s):
LLNL-JRNL-778562
Journal ID: ISSN 1089-5639; 971570
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 124; Journal Issue: 2; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrochemistry; Moisture; Interfaces; Diffusion; Oxidation

Citation Formats

Matt, Sarah M., Haschke, John M., McLean, William, and Dinh, Long N.. Moisture Corrosion of LiH: A Kinetic Investigation by DRIFT Spectroscopy. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpca.9b09951.
Matt, Sarah M., Haschke, John M., McLean, William, & Dinh, Long N.. Moisture Corrosion of LiH: A Kinetic Investigation by DRIFT Spectroscopy. United States. https://doi.org/10.1021/acs.jpca.9b09951
Matt, Sarah M., Haschke, John M., McLean, William, and Dinh, Long N.. Fri . "Moisture Corrosion of LiH: A Kinetic Investigation by DRIFT Spectroscopy". United States. https://doi.org/10.1021/acs.jpca.9b09951. https://www.osti.gov/servlets/purl/1597620.
@article{osti_1597620,
title = {Moisture Corrosion of LiH: A Kinetic Investigation by DRIFT Spectroscopy},
author = {Matt, Sarah M. and Haschke, John M. and McLean, William and Dinh, Long N.},
abstractNote = {Lithium hydride (LiH) is a unique, ionic compound with applications in a variety of industries. Unfortunately, LiH is very reactive toward H2O even at ppm levels, forming oxide (Li2O) and hydroxide (LiOH) corrosion layers while outgassing H2. An effective means to eliminate unwanted outgassing is vacuum-heating to convert LiOH into Li2O, although subsequent re-exposure to moisture during transport/handling reconverts some Li2O back to LiOH. A corrosion growth model for previously vacuum-baked LiH is necessary for long-term prediction of the hydrolysis of LiH. In this work, a para-linear hydroxide corrosion growth model is proposed for the reaction of previously vacuum-baked LiH samples with moisture. This model, composed of two competing diffusion reaction fronts at the LiOH/Li2O and Li2O/LiH interfaces, is validated experimentally by subjecting a previously vacuum-baked polycrystalline LiH sample to 35 ppm of H2O at room temperature while monitoring the corrosion growth as a function of time with diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy. The para-linear growth model for the hydrolysis of previously vacuum-baked LiH proposed in this report can also serve as a template for the hydrolysis of other hygroscopic oxides grown on metal or metal hydride substrates.},
doi = {10.1021/acs.jpca.9b09951},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 2,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}

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