title: Edge Charge Neutralization of Clay for Improved Oxygen Gas Barrier in Multilayer Nanobrick Wall Thin Films.
abstract: Layer-by-layer (LbL) assembled polymer-clay multilayer thin films are known to provide transparent and flexible gas barrier. In an effort to further lower the oxygen transmission rate (OTR) of these nanobrick wall thin films, sodium chloride was introduced into montmorillonite (MMT) suspension as an "indifferent electrolyte". At pH 6.5 the amphoteric edge sites of MMT have a neutral net charge, and a moderate concentration of NaCl effectively shields the charge from neighboring platelets, allowing van der Waals forces to attract the edges to one another. This edge-to-edge bonding creates a much more tortuous path for diffusing oxygen molecules. An eight-bilayer (BL) polyethylenimine (PEI)/MMT multilayer coating (∼50 nm thick), assembled with 5 mM NaCl in the aqueous clay suspension, exhibited an order of magnitude reduction in oxygen permeability (∼4 × 10-20cm3·cm/(cm2·Pa·s)) relative to its salt-free counterpart. This result represents the best barrier among polymer-clay bilayer systems, which is also lower than SiOxor AlxOythin films. At higher NaCl concentration, the strong charge screening causes edge-to-face bonding among MMT nanoplatelets, which leads to misalignment in assembled films and increased OTR. This "salty-clay" strategy provides an efficient way to produce better multilayer oxygen barrier thin films by altering ionic strength of the MMT suspension. This simple modification reduces the number of layers necessary for high gas barrier, potentially making these multilayer films interesting for commercial packaging applications.
authors.affiliation: Department of Materials Science and Engineering and ‡Department of Mechanical Engineering, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Yixuan
authors.initials: Y
authors.lastname: Song
authors.affiliation: Department of Materials Science and Engineering and ‡Department of Mechanical Engineering, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: David A
authors.identifier: http://orcid.org/0000-0001-6524-6245
authors.initials: DA
authors.lastname: Hagen
authors.affiliation: Department of Materials Science and Engineering and ‡Department of Mechanical Engineering, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Shuang
authors.initials: S
authors.lastname: Qin
authors.affiliation: Department of Materials Science and Engineering and ‡Department of Mechanical Engineering, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Kevin M
authors.initials: KM
authors.lastname: Holder
authors.affiliation: Department of Materials Science and Engineering and ‡Department of Mechanical Engineering, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Kyle
authors.initials: K
authors.lastname: Falke
authors.affiliation: Department of Materials Science and Engineering and ‡Department of Mechanical Engineering, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Jaime C
authors.identifier: http://orcid.org/0000-0001-5241-9741
authors.initials: JC
authors.lastname: Grunlan
keywords: clay; layer-by-layer assembly; oxygen gas barrier; polyelectrolyte; transmission electron microscope