Edge Charge Neutralization of Clay for Improved Oxygen Gas Barrier in Multilayer Nanobrick Wall Thin Films.

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 × 10-20 cm3·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 SiOx or AlxOy thin 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.

Completely organic multilayer thin film with thermoelectric power factor rivaling inorganic tellurides.

Composed exclusively of organic components, polyaniline (PANi), graphene, and double-walled nanotubes (DWNTs) are alternately deposited from aqueous solutions using a layer-by-layer assembly. The 40 quadlayer thin film (470 nm thick) exhibits electrical conductivity of 1.08 × 10(5) S m(-1) and a Seebeck coefficient of 130 µV K(-1) , producing a thermoelectric power factor of 1825 µW m(-1) K(-2) .

Nanobrick wall multilayer thin films grown faster and stronger using electrophoretic deposition.

In an effort to speed up the layer-by-layer (LbL) deposition technique, electrophoretic deposition (EPD) is employed with weak polyelectrolytes and clay nanoplatelets. The introduction of an electric field results in nearly an order of magnitude increase in thickness relative to conventional LbL deposition for a given number of deposited layers. A higher clay concentration also results with the EPD-LbL process, which produces higher modulus and strength with fewer deposited layers. A 20 quadlayer (QL) assembly of linear polyethyleneimine (LPEI)/poly(acrylic acid)/LPEI/clay has an elastic modulus of 45 GPa, tensile strength of 70 MPa, and thickness of 4.4 µm. Traditional LbL requires 40 QL to achieve the same thickness, with lower modulus and strength. This study reveals how these films grow and maintain a highly ordered nanobrick wall structure that is commonly associated with LbL deposition. Fewer layers required to achieve improved properties will open up many new opportunities for this multifunctional thin film deposition technique.

Controlling effective aspect ratio and packing of clay with pH for improved gas barrier in nanobrick wall thin films.

Polymer-clay thin films constructed via layer-by-layer (LbL) assembly, with a nanobrick wall structure (i.e., clay nanoplatelets as bricks surrounded by a polyelectrolyte mortar), are known to exhibit a high oxygen barrier. Further barrier improvement can be achieved by lowering the pH of the clay suspension in the polyethylenimine (PEI) and montmorillonite (MMT) system. In this case, the charge of the deposited PEI layer is increased in the clay suspension environment, which causes more clay to be deposited. At pH 4, MMT platelets deposit with near perfect ordering, observed with transmission electron microscopy, enabling a 5× improvement in the gas barrier for a 10 PEI/MMT bilayer thin film (85 nm) relative to the same film made with pH 10 MMT. This improved gas barrier approaches that achieved with much higher aspect ratio vermiculite clay. In essence, lower pH is generating a higher effective aspect ratio for MMT due to greater induced surface charge in the PEI layers, which causes heavier clay deposition. These flexible, transparent nanocoatings have a wide range of possible applications, from food and electronics packaging to pressurized bladders.

Low-temperature thermal reduction of graphene oxide nanobrick walls: unique combination of high gas barrier and low resistivity in fully organic polyelectrolyte multilayer thin films.

Layer-by-layer assembly from aqueous solutions was used to construct multilayer thin films (<200 nm) comprising polyethylenimine and graphene oxide. Low-temperature (175 °C) thermal reduction of these films improved gas barrier properties (e.g., lower permeability than SiOx), even under high humidity conditions, and enhanced their electrical conductivity to 1750 S/m. The flexible nature of the aforementioned thin films, along with their excellent combination of transport properties, make them ideal candidates for use in a broad range of electronics and packaging applications.

Shift-Time Polyelectrolyte Multilayer Assembly: Fast Film Growth and High Gas Barrier with Fewer Layers by Adjusting Deposition Time.

In an effort to reduce deposition time and number of layers needed to achieve high gas barrier, multilayer films were deposited using 1 s exposures for the first four bilayers (BLs) and 1 min for subsequent dips. Thin-film assemblies of polyethylenimine (PEI) and poly(acrylic acid) (PAA) were deposited onto poly(ethylene terephthalate) [PET] using the layer-by-layer deposition process. Varying the exposure time of PET to polyelectrolyte solutions (i.e., dip time) significantly alters the growth rate of the multilayer thin films. The PEI/PAA system grows linearly with 1 s dip times and exponentially with longer times. Eight bilayers (650 nm) were required to achieve an undetectable oxygen transmission rate (<0.005 cm3/(m2·day)) using 1 min deposition steps, but this barrier was obtained with only 6 BLs (552 nm) using 1s deposition of the initial layers, reducing total deposition time by 73%. This "shift-time" concept makes layer-by-layer assembly much faster and more commercially feasible.