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Title: The moisture outgassing kinetics of a silica reinforced polydimethylsiloxane

Abstract

We investigated a silica-filled polydimethylsiloxane (PDMS) composite M9787 for potential outgassing in a vacuum/dry environment with the temperature programmed desorption/reaction method. The outgassing kinetics of 463 K vacuum heat-treated samples, vacuum heat-treated samples which were subsequently re-exposed to moisture, and untreated samples were extracted using the isoconversional and constrained iterative regression methods in a complementary fashion. Density functional theory (DFT) calculations of water interactions with a silica surface were also performed to provide insight into the structural motifs leading to the obtained kinetic parameters. Kinetic analysis/model revealed that no outgassing occurs from the vacuum heat-treated samples in subsequent vacuum/dry environment applications at room temperature (~300 K). Moreover, the main effect of re-exposure of the vacuum heat-treated samples to a glove box condition (~30 ppm by volume of H2O) for even a couple of days was the formation, on the silica surface fillers, of ~60 ppm by weight of physisorbed and loosely bonded moisture, which subsequently outgasses at room temperature in a vacuum/dry environment in a time span of 10 yr. However, without any vacuum heat treatment and even after 1 h of vacuum pump down, about 300 ppm by weight of H2O would be released from the PDMS in themore » next few hours. Thereafter the outgassing rate slows down substantially. Our presented methodology of using the isoconversional kinetic analysis results and some appropriate nature of the reaction as the constraints for more accurate iterative regression analysis/deconvolution of complex kinetic spectra, and of checking the so-obtained results with first principle calculations such as DFT can serve as a template for treating other complex physical/chemical processes as well.« less

Authors:
 [1];  [1];  [1];  [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
OSTI Identifier:
1336998
Alternate Identifier(s):
OSTI ID: 1325836
Report Number(s):
LLNL-JRNL-692119
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Sharma, H. N., McLean, W., Maxwell, R. S., and Dinh, L. N. The moisture outgassing kinetics of a silica reinforced polydimethylsiloxane. United States: N. p., 2016. Web. doi:10.1063/1.4962736.
Sharma, H. N., McLean, W., Maxwell, R. S., & Dinh, L. N. The moisture outgassing kinetics of a silica reinforced polydimethylsiloxane. United States. doi:https://doi.org/10.1063/1.4962736
Sharma, H. N., McLean, W., Maxwell, R. S., and Dinh, L. N. Wed . "The moisture outgassing kinetics of a silica reinforced polydimethylsiloxane". United States. doi:https://doi.org/10.1063/1.4962736. https://www.osti.gov/servlets/purl/1336998.
@article{osti_1336998,
title = {The moisture outgassing kinetics of a silica reinforced polydimethylsiloxane},
author = {Sharma, H. N. and McLean, W. and Maxwell, R. S. and Dinh, L. N.},
abstractNote = {We investigated a silica-filled polydimethylsiloxane (PDMS) composite M9787 for potential outgassing in a vacuum/dry environment with the temperature programmed desorption/reaction method. The outgassing kinetics of 463 K vacuum heat-treated samples, vacuum heat-treated samples which were subsequently re-exposed to moisture, and untreated samples were extracted using the isoconversional and constrained iterative regression methods in a complementary fashion. Density functional theory (DFT) calculations of water interactions with a silica surface were also performed to provide insight into the structural motifs leading to the obtained kinetic parameters. Kinetic analysis/model revealed that no outgassing occurs from the vacuum heat-treated samples in subsequent vacuum/dry environment applications at room temperature (~300 K). Moreover, the main effect of re-exposure of the vacuum heat-treated samples to a glove box condition (~30 ppm by volume of H2O) for even a couple of days was the formation, on the silica surface fillers, of ~60 ppm by weight of physisorbed and loosely bonded moisture, which subsequently outgasses at room temperature in a vacuum/dry environment in a time span of 10 yr. However, without any vacuum heat treatment and even after 1 h of vacuum pump down, about 300 ppm by weight of H2O would be released from the PDMS in the next few hours. Thereafter the outgassing rate slows down substantially. Our presented methodology of using the isoconversional kinetic analysis results and some appropriate nature of the reaction as the constraints for more accurate iterative regression analysis/deconvolution of complex kinetic spectra, and of checking the so-obtained results with first principle calculations such as DFT can serve as a template for treating other complex physical/chemical processes as well.},
doi = {10.1063/1.4962736},
journal = {Journal of Chemical Physics},
number = 11,
volume = 145,
place = {United States},
year = {2016},
month = {9}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Experimental Study of Carbon Black and Diesel Engine Soot Oxidation Kinetics Using Thermogravimetric Analysis
journal, August 2012

  • Sharma, Hom N.; Pahalagedara, Lakshitha; Joshi, Ameya
  • Energy & Fuels, Vol. 26, Issue 9
  • DOI: 10.1021/ef3009025

Temperature-programmed desorption of water from fumed silica, silica/titania, and silica/alumina
journal, February 1998

  • Gun'ko, V. M.; Zarko, V. I.; Chuikov, B. A.
  • International Journal of Mass Spectrometry and Ion Processes, Vol. 172, Issue 3
  • DOI: 10.1016/S0168-1176(97)00269-3

A Discussion of the Surface Complexation Modeling in the Paper by Sarkar et al. (1999)
journal, January 2001


H 2 O Outgassing Properties of Fumed and Precipitated Silica Particles by Temperature-Programmed Desorption
journal, October 2000

  • Dinh, Long Ngoc; Balooch, Mehdi; LeMay, James Daniel
  • Journal of Colloid and Interface Science, Vol. 230, Issue 2
  • DOI: 10.1006/jcis.2000.7131

Characterization of Polydimethylsiloxane (PDMS) Properties for Biomedical Micro/Nanosystems
journal, December 2005


H2O outgassing from silica-filled polysiloxane TR55
journal, June 2004

  • Dinh, L. N.; Schildbach, M. A.; Maxwell, R. S.
  • Journal of Colloid and Interface Science, Vol. 274, Issue 1
  • DOI: 10.1016/j.jcis.2003.12.052

ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data
journal, June 2011

  • Vyazovkin, Sergey; Burnham, Alan K.; Criado, José M.
  • Thermochimica Acta, Vol. 520, Issue 1-2
  • DOI: 10.1016/j.tca.2011.03.034

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Residual dipolar coupling for the assessment of cross-link density changes in γ-irradiated silica-PDMS composite materials
journal, June 2002

  • Maxwell, Robert S.; Balazs, Bryan
  • The Journal of Chemical Physics, Vol. 116, Issue 23
  • DOI: 10.1063/1.1477184

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Periodic Density Functional Theory Study of Water Adsorption on the α-Quartz (101) Surface
journal, March 2011

  • Bandura, A. V.; Kubicki, J. D.; Sofo, J. O.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 13
  • DOI: 10.1021/jp1106636

Exfoliation of Clays in Poly(dimethylsiloxane) Rubber Using an Unexpected Couple: A Silicone Surfactant and Water
journal, April 2009

  • Labruyère, Céline; Monteverde, Fabien; Alexandre, Michaël
  • Journal of Nanoscience and Nanotechnology, Vol. 9, Issue 4
  • DOI: 10.1166/jnn.2009.471

Density functional calculations of amines on the (101) face of quartz
journal, December 2014


Surface Hydration and Its Effect on Fluorinated SAM Formation on SiO 2 Surfaces
journal, December 2005

  • Wu, K.; Bailey, T. C.; Willson, C. G.
  • Langmuir, Vol. 21, Issue 25
  • DOI: 10.1021/la0516330

Adsorption and desorption kinetics of H2O on a fully hydroxylated SiO2 surface
journal, August 1996


Mechanism and Kinetic Modeling of Hydrogenation in the Organic Getter/Palladium Catalyst/Activated Carbon Systems
journal, January 2015

  • Dinh, L. N.; Cairns, G. A.; Strickland, R. A.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 6
  • DOI: 10.1021/jp511052a