Recent Advances in Gas Barrier Thin Films via Layer-by-Layer Assembly of Polymers and Platelets.

Layer-by-layer (LbL) assembly has emerged as the leading non-vacuum technology for the fabrication of transparent, super gas barrier films. The super gas barrier performance of LbL deposited films has been demonstrated in numerous studies, with a variety of polyelectrolytes, to rival that of metal and metal oxide-based barrier films. This Feature Article is a mini-review of LbL-based multilayer thin films with a 'nanobrick wall' microstructure comprising polymeric mortar and nano-platelet bricks that impart high gas barrier to otherwise permeable polymer substrates. These transparent, water-based thin films exhibit oxygen transmission rates below 5 × 10(-3) cm(3) m(-2) day(-1) atm(-1) and lower permeability than any other barrier material reported. In an effort to put this technology in the proper context, incumbent technologies such as metallized plastics, metal oxides, and flake-filled polymers are briefly reviewed.

Stretchable gas barrier achieved with partially hydrogen-bonded multilayer nanocoating.

Super gas barrier nanocoatings are recently demonstrated by combining polyelectrolytes and clay nanoplatelets with layer-by-layer deposition. These nanobrick wall thin films match or exceed the gas barrier of SiOx and metallized films, but they are relatively stiff and lose barrier with significant stretching (≥ 10% strain). In an effort to impart stretchability, hydrogen-bonding polyglycidol (PGD) layers are added to an electrostatically bonded thin film assembly of polyethylenimine (PEI) and montmorillonite (MMT) clay. The oxygen transmission rate of a 125-nm thick PEI-MMT film increases more than 40x after being stretched 10%, while PGD-PEI-MMT trilayers of the same thickness maintain its gas barrier. This stretchable trilayer system has an OTR three times lower than the PEI-MMT bilayer system after stretching. This report marks the first stretchable high gas barrier thin film, which is potentially useful for applications that require pressurized elastomers.

Super gas barrier and selectivity of graphene oxide-polymer multilayer thin films.

Super gas barrier thin films, fabricated with layer-by-layer assembly of polyethylenimine and graphene oxide, exhibit significantly reduced oxygen and carbon dioxide transmission rates. This thin film's nanobrick wall structure also provides high gas selectivity for hydrogen.

Transparency, gas barrier, and moisture resistance of large-aspect-ratio vermiculite nanobrick wall thin films.

The ability to incorporate large-aspect-ratio vermiculite (VMT) clay into thin films fabricated using the layer-by-layer assembly techinique is reported for the first time. Thin films of branched polyethylenimine (PEI) and VMT were analyzed for their growth rate, clay composition, transparency, and gas barrier behavior. These films consist of >96 wt% clay, are >95% transparent, and, because of their nanobrick wall structure, exhibit super gas barrier behavior at thicknesses of <165 nm. When coupled with flexibility, the optical clarity and super barrier that these coatings can impart make them superb candidates for a variety of packaging applications.

Influence of clay concentration on the gas barrier of clay-polymer nanobrick wall thin film assemblies.

The influence of the clay deposition suspension concentration on gas barrier thin films of sodium montmorillonite (MMT) clay and branched polyethylenimine (PEI), created via layer-by-layer assembly, was investigated. Films grown with MMT suspension concentrations ranging from 0.05 to 2.0 wt % were analyzed for their growth as a function of deposited polymer-clay bilayers (BL) and their thickness, clay concentration, transparency, nanostructure, and oxygen barrier as a function of the suspension concentration. The film thickness doubles and the visible light transmission decreases less than 5% as a function of MMT concentration for 20-BL films. Atomic force and transmission electron microscope images reveal a highly aligned nanobrick wall structure, with quartz crystal microbalance measurements revealing a slight increase in the film clay concentration as the MMT suspension concentration increases. The oxygen transmission rate (OTR) through these 20-BL composites, deposited on a 179 µm poly(ethylene terephthalate) film, decreases exponentially as a function of the MMT clay concentration. A 24-BL film created with 2.0 wt % MMT has an OTR below the detection limit of commercial instrumentation (<0.005 cc/m(2)·day·atm). This study demonstrates an optimal clay suspension concentration to use when creating LbL barrier films, which minimizes deposition steps and the overall processing time.

Super gas barrier of transparent polymer-clay multilayer ultrathin films.

Flexible and transparent polymeric "superbarrier" packaging materials have become increasingly important in recent years. Layer-by-layer assembly offers a facile technique for the fabrication of layered, polymer-clay superbarrier thin films. At only 51 nm thick, these nanocomposite thin films, comprised of 12 polymer and 4 clay layers, exhibit an oxygen permeability orders of magnitude lower than EVOH and SiOx. Coupling high flexibility, transparency, and barrier protection, these films are good candidates for a variety packaging applications.

Note: Influence of rinsing and drying routines on growth of multilayer thin films using automated deposition system.

A versatile, high speed robot for layer-by-layer deposition of multifunctional thin films, which integrates concepts from previous dipping systems, has been designed with dramatic improvements in software, positioning, rinsing, drying, and waste removal. This system exploits the electrostatic interaction of oppositely charged species to deposit nanolayers (1-10 nm thick) from water onto the surface of a substrate. Dip times and number of deposited layers are adjustable through a graphical user interface. In between dips the system spray rinses and dries the substrate by positioning it in the two-tiered rinse-dry station. This feature significantly reduces processing time and provides the flexibility to choose from four different procedures for rinsing and drying. Assemblies of natural montmorillonite clay and polyethylenimine are deposited onto 175 microm poly(ethylene terephthalate) film to demonstrate the utility of this automated deposition system. By altering the type of rinse-dry procedure, these clay-based assemblies are shown to exhibit variations in film thickness and oxygen transmission rate. This type of system reproducibly deposits films containing 20 or more layers and may also be useful for other types of coatings that make use of dipping.