Graphene Oxide-Based Membrane as a Protective Barrier against Toxic Vapors and Gases.

Abstract

Traditional protective garments loaded with activated carbons to remove toxic gases are very bulky. Novel graphene oxide (GO) flake-based composite lamellar membrane structure is being developed as a potential component of a garment for protection against chemical warfare agents (CWAs) represented here by simulants, dimethyl methyl phosphonate (DMMP) (a sarin-simulant), and 2-chloroethyl ethyl sulfide (CEES) (a simulant for sulfur mustard), yet allowing a high-moisture transmission rate. GO flakes of dimensions 300-800 nm, 0.7-1.2 nm thickness and dispersed in an aqueous suspension were formed into a membrane by vacuum filtration on a porous poly(ether sulfone) (PES) or poly(ether ether ketone) (PEEK) support membrane for noncovalent π-π interactions with GO flakes. After physical compression of such a membrane, upright cup tests indicated that it can block toluene for 3-4 days and DMMP for 5 days while exhibiting excellent water vapor permeation. Further, they display very low permeances for small-molecule gases/vapors. The GO flakes underwent cross-linking later with ethylenediamine (EDA) introduced during the vacuum filtration followed by physical compression and heating. With a further spray coating of polyurethane (PU), these membranes could be bent without losing barrier properties vis-à-vis the CWA simulant DMMP for 5 days; a membrane not subjected to bending blocked DMMP for 15 days. For the PEEK-EDA-GO-PU-compressed membranes after bending, the separation factors of H2O over other species for low gas flow rates in the dynamic moisture permeation cell (DMPC) are: αH2O-He is 42.3; αH2O-N2 is 110; and αH2O-ethane is 1800. At higher gas flow rates in the DMPC, the moisture transmission rate goes up considerably due to reduced boundary layer resistances and exceeds the threshold water vapor flux of 2000 g/(m2·day) that defines a breathable fabric. This membrane displayed considerable resistance to permeation by CEES as well. The PES-EDA-GO-PU-compressed membrane shows good mechanical property under tensile strength tests.