Polymer Bulletin

, Volume 76, Issue 1, pp 339–364 | Cite as

An approximate analytical approach to estimate the diffusivity of toxic chemicals in polymer barrier materials from the time evolution of sessile drop profiles

  • Molly N. Richards
  • Michael Bell
  • Rajagopalan Srinivasan
  • Ali Borhan
  • Ramanathan NagarajanEmail author
Original Paper


Any practical technique to determine the diffusivity of chemical warfare agents in protective barrier materials should require handling only miniscule volume of the chemicals and also require data analysis methods that are not computationally burdensome. Such an approach is described here based on imaging the time evolution of ~ 1 μL sessile drop profiles on the barrier surface and using an approximate analytical approach to analyze the time-dependent drop volume and contact angle data for extracting the diffusivity. The approximate analytical approach is validated by comparison against results from computationally intensive finite element simulations available in the literature. The domain of reliable use of the sessile drop technique in terms of the relative importance of the simultaneous evaporation and absorption is assessed using measurements on three challenging toxic chemicals in air and in butyl rubber. The ability of this approach to provide reasonable diffusivity estimates even if the substrate undergoes swelling is explored by studying water sessile drops on a Nafion membrane. The results allow one to conclude that the sessile drop technique coupled to the approximate analytical approach can be reliably used for rapid screening of new barrier materials for protection against chemical warfare agents if the screening is implemented using simulants with low vapor pressures.

Graphical Abstract


Sessile drop Basal radius Diffusivity of chemical agents Diffusivity of toxic chemicals Time evolution of sessile drop profile Evaporation of sessile drops Absorption of sessile drops Model for diffusivity estimation Diffusivity from contact angle Barrier polymers 



This work was supported by Defense Threat Reduction Agency (Project BA10PHM050) and Natick Soldier Research, Development and Engineering Center. Research was performed while MNR, MB, and RS held an Oak Ridge Institute for Science and Education (ORISE) Fellowship. We acknowledge helpful discussions with Dr. Matthew Willis and Dr. Brent Mantooth of Edgewood Chemical and Biological Center about their work described in References [12] and [13].


The research was supported by U. S. Defense Threat Reduction Agency (Project BA10PHM050) and Natick Soldier Research, Development and Engineering Center.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

289_2018_2382_MOESM1_ESM.pdf (232 kb)
Supplementary material 1 (PDF 232 kb)


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Copyright information

© This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply 2018

Authors and Affiliations

  1. 1.Natick Soldier Research, Development and Engineering CenterNatickUSA
  2. 2.Department of PhysicsThe Pennsylvania State UniversityUniversity ParkUSA
  3. 3.Department of Chemical EngineeringThe Pennsylvania State UniversityUniversity ParkUSA

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