Super Gas Barrier of a Polyelectrolyte/Clay Coacervate Thin Film.

Transparent polymeric thin films with high oxygen barrier are important for extending the shelf life of food and protecting flexible organic electronic devices. Polyelectrolyte/clay multilayer nanocoatings are shown to exhibit super gas barrier performance, but the layer-by-layer assembly process requires numerous deposition steps. In an effort to more quickly fabricate this type of barrier, a polyelectrolyte/clay coacervate composed of branched polyethyleneimine (PEI), poly(acrylic acid) (PAA), and kaolinite (KAO) clay is prepared and deposited in a single step, followed by humidity and thermal post-treatments. When deposited onto a 179 µm poly(ethylene terephthalate) (PET) film, a 4 µm coacervate coating reduces the oxygen transmission rate (OTR) by more than three orders of magnitude, while maintaining high transparency. This single-step deposition process uses only low-cost, water-based components and ambient conditions, which can be used to for sensitive food and electronics packaging.

Contact electrification between identical polymers as the basis for triboelectric/flexoelectric materials.

Polymer contact electrification offers the possibility to harvest mechanical energy using lightweight, flexible and low-cost materials, but the mechanism itself is still unresolved. Several recent studies confirm heterolytic covalent bond breaking as the mechanism for surface charge formation. Here it is shown that the reason for the formation of surface charge by contacting two identical polymers results from the fluctuation in the surface irregularities, and that contacted materials with a greater porosity or surface roughness differential result in a greater generation of surface charge. Porosity and surface roughness create uneven surface length percentage changes in the lateral direction during deformation, which changes the charge density across the surface during relaxation. Multilayered membranes exhibit flexoelectric properties upon pressing and releasing by generating charge without separating individual membrane layers. This new insight deepens the understanding of polymer contact electrification and highlights better ways to prepare triboelectric or flexoelectric nanogenerator devices.

Unusually fast and large actuation from multilayer polyelectrolyte thin films.

Polymers responsive to external stimuli (e.g., electric field, chemical vapor, light) are of great interest for smart materials such as sensors and soft robotics. A vapor-driven multilayer polymer actuator, capable of fast and large-scale actuation, is described here. This Janus-like actuator is prepared with two polyelectrolyte multilayer systems (polyethylenimine (PEI)/poly(acrylic acid) (PAA) and polyurethane (PU)/poly(acrylic acid) (PAA)) using layer-by-layer assembly (LbL). The differing hydrophilicity of these two nanocoatings results in different swelling behavior in water and organic solvents, which leads to vapor-responsive mechanical motion. The bending/curling degree of this polymeric actuator can be precisely controlled by changing the thickness ratio of the two layers. A vapor sensor was constructed to demonstrate the environmental detection ability of this unique actuator.

Crosslinkable-Chitosan-Enabled Moisture-Resistant Multilayer Gas Barrier Thin Film.

Chitosan-based films exhibit good oxygen barrier that degrades when exposed to high humidity. In an effort to overcome this drawback, a multilayer nanocoating consisting of crosslinkable chitosan (CHQ) and poly(acrylic acid) [PAA] is deposited on polyethylene terephthalate (PET) using layer-by-layer assembly. Chitosan is functionalized with glycidyl methacrylate to introduce acrylic functionalities within the film. The deposited films are crosslinked using a free radical initiator and this crosslinking is confirmed by FTIR and reduced film thickness. A 10-bilayer (BL) crosslinked CHQ/PAA film, which is only 165 nm thick, results in a 36× reduction of the oxygen transmission rate of PET at 90% relative humidity. To achieve these same results without crosslinking, a 15-BL unmodified chitosan (CH)/PAA film, which is almost 5× thicker, must be deposited on PET. This environmentally friendly, transparent nanocoating is promising for food packaging or protection of flexible electronics, especially in high-humidity environments.

Transparent Polyelectrolyte Complex Thin Films with Ultralow Oxygen Transmission Rate.

Limiting oxygen permeation through plastic films is important for extending the shelf life of food and flexible electronic devices. Polyelectrolyte complex (PEC) thin films can be used to reduce small molecule diffusion through commodity plastic films. PEC thin films are frequently applied using layer-by-layer assembly, which often requires many processing cycles to deposit a film with desired thickness. An aqueous solution of poly(diallydimethylammonium chloride) and poly(acrylic acid) can be deposited in a single-step to quickly fabricate a high-oxygen barrier thin film. These films have an ionically bonded network that forms after polyelectrolyte deposition and exposure to buffer. Increasing buffer concentration and adding salt increases film cohesion and improves transparency by reducing surface roughness. When deposited onto a 178 µm poly(ethylene terephthalate) film, a ∼1.9 µm thick PEC coating imparts a 2 orders of magnitude reduction in oxygen transmission rate. Achieving this level of gas barrier with a single thin coating layer creates numerous opportunities for the protection of sensitive food, pharmaceuticals, and electronics.

Polyelectrolyte Coacervates Deposited as High Gas Barrier Thin Films.

Multilayer coatings consisting of oppositely charged polyelectrolytes have proven to be extraordinarily effective oxygen barriers but require many processing steps to fabricate. In an effort to prepare high oxygen barrier thin films more quickly, a polyelectrolyte complex coacervate composed of polyethylenimine and polyacrylic acid is prepared. The coacervate fluid is applied as a thin film using a rod coating process. With humidity and thermal post-treatment, a 2 µm thin film reduces the oxygen transmission rate of 0.127 mm poly(ethylene terephthalate) by two orders of magnitude, rivalling conventional oxygen barrier technologies. These films are fabricated in ambient conditions using low-cost, water-based solutions, providing a tremendous opportunity for single-step deposition of polymeric high barrier thin films.

Fast Self-Healing of Polyelectrolyte Multilayer Nanocoating and Restoration of Super Oxygen Barrier.

A self-healable gas barrier nanocoating, which is fabricated by alternate deposition of polyethyleneimine (PEI) and polyacrylic acid (PAA) polyelectrolytes, is demonstrated in this study. This multilayer film, with high elastic modulus, high glass transition temperature, and small free volume, has been shown to be a super oxygen gas barrier. An 8-bilayer PEI/PAA multilayer assembly (≈700 nm thick) exhibits an oxygen transmission rate (OTR) undetectable to commercial instrumentation (<0.005 cc (m-2 d-1 atm-1 )). The barrier property of PEI/PAA nanocoating is lost after a moderate amount of stretching due to its rigidity, which is then completely restored after high humidity exposure, therefore achieving a healing efficiency of 100%. The OTR of the multilayer nanocoating remains below the detection limit after ten stretching-healing cycles, which proves this healing process to be highly robust. The high oxygen barrier and self-healing behavior of this polymer multilayer nanocoating makes it ideal for packaging (food, electronics, and pharmaceutical) and gas separation applications.

Super Oxygen and Improved Water Vapor Barrier of Polypropylene Film with Polyelectrolyte Multilayer Nanocoatings.

Biaxially oriented polypropylene (BOPP) is widely used in packaging. Although its orientation increases mechanical strength and clarity, BOPP suffers from a high oxygen transmission rate (OTR). Multilayer thin films are deposited from water using layer-by-layer (LbL) assembly. Polyethylenimine (PEI) is combined with either poly(acrylic acid) (PAA) or vermiculite (VMT) clay to impart high oxygen barrier. A 30-bilayer PEI/VMT nanocoating (226 nm thick) improves the OTR of 17.8 µm thick BOPP by more than 30X, rivaling most inorganic coatings. PEI/PAA multilayers achieve comparable barrier with only 12 bilayers due to greater thickness, but these films exhibit increased oxygen permeability at high humidity. The PEI/VMT coatings actually exhibit improved oxygen barrier at high humidity (and also improve moisture barrier by more than 40%). This high barrier BOPP meets the criteria for sensitive food and some electronics packaging applications. Additionally, this water-based coating technology is cost effective and provides an opportunity to produce high barrier polypropylene film on an industrial scale.

Highly Conductive Graphene and Polyelectrolyte Multilayer Thin Films Produced From Aqueous Suspension.

Rapid, large-scale exfoliation of graphene in water has expanded its potential for use outside niche applications. This work focuses on utilizing aqueous graphene dispersions to form thin films using layer-by-layer processing, which is an effective method to produce large-area coatings from water-based solutions of polyelectrolytes. When layered with polyethyleneimine, graphene flakes stabilized with cholate are shown to be capable of producing films thinner than 100 nm. High surface coverage of graphene flakes results in electrical conductivity up to 5500 S m-1 . With the relative ease of processing, the safe, cost effective nature of the ingredients, and the scalability of the deposition method, this system should be industrially attractive for producing thin conductive films for a variety of electronic and antistatic applications.

Polymer-graphene oxide quadlayer thin-film assemblies with improved gas barrier.

Layer-by-layer assembly was used to create quadlayers (QLs) of chitosan (CH), poly(acrylic acid) (PAA), CH, and graphene oxide (GO). Electron microscopy confirmed GO coverage over the film and a highly ordered nanobrick wall structure. By varying pH deviation between CH and PAA, a thick and interdiffused polymer matrix was created because of the altered chain conformation. A 5 CH (pH 5.5)/PAA (pH 3)/CH (pH 5.5)/GO QL assembly (48 nm) exhibits very low oxygen permeability (3.9 × 10(-20) cm(3) cm cm(-2) Pa(-1) s(-1)) that matches SiOx barrier coatings. In an effort to maintain barrier performance under high humidity, GO was thermally reduced to increase hydrophobicity of the film. This reduction step increased H2/CO2 selectivity of a 5 QL film from 5 to 215, exceeding Robeson's upper bound limit. This unique water-based multilayer nanocoating is very promising for a variety of gas purification and packaging applications.

Structural tailoring of hydrogen-bonded poly(acrylic acid)/poly(ethylene oxide) multilayer thin films for reduced gas permeability.

Hydrogen bonded poly(acrylic acid) (PAA)/poly(ethylene oxide) (PEO) layer-by-layer assemblies are highly elastomeric, but more permeable than ionically bonded thin films. In order to expand the use of hydrogen-bonded assemblies to applications that require a better gas barrier, the effect of assembling pH on the oxygen permeability of PAA/PEO multilayer thin films was investigated. Altering the assembling pH leads to significant changes in phase morphology and bonding. The amount of intermolecular hydrogen bonding between PAA and PEO is found to increase with increasing pH due to reduction of COOH dimers between PAA chains. This improved bonding leads to smaller PEO domains and lower gas permeability. Further increasing the pH beyond 2.75 results in higher oxygen permeability due to partial deprotonation of PAA. By setting the assembling pH at 2.75, the negative impacts of COOH dimer formation and PAA ionization on intermolecular hydrogen bonding can be minimized, leading to a 50% reduction in the oxygen permeability of the PAA/PEO thin film. A 20 bilayer coating reduces the oxygen transmission rate of a 1.58 mm natural rubber substrate by 20 ×. These unique nanocoatings provide the opportunity to impart a gas barrier to elastomeric substrates without altering their mechanical behavior.

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.

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.

Super hydrogen and helium barrier with polyelectolyte nanobrick wall thin film.

In an effort to impart light gas (i.e., H2 and He) barrier to polymer substrates, thin films of polyethylenimine (PEI), poly(acrylic acid) (PAA), and montmorrilonite (MMT) clay are deposited via layer-by-layer (LbL) assembly. A five "quadlayer" (122 nm) coating deposited on 51 µm polystyrene is shown to lower both hydrogen and helium permeability three orders of magnitude against bare polystyrene, demonstrating better performance than thick-laminated ethylene vinyl-alcohol (EVOH) copolymer film and even metallized polyolefin/polyester film. These excellent barrier properties are attributed to a "nanobrick wall" structure. This highly flexible coating represents the first demonstration of an LbL deposited film with low hydrogen and helium permeability and is an ideal candidate for several packaging and protection applications.

Thick growing multilayer nanobrick wall thin films: super gas barrier with very few layers.

Recent work with multilayer nanocoatings composed of polyelectrolytes and clay has demonstrated the ability to prepare super gas barrier layers from water that rival inorganic CVD-based films (e.g., SiOx). In an effort to reduce the number of layers required to achieve a very low oxygen transmission rate (OTR (<0.01 cc/m(2)·day·atm)) in these nanocoatings, buffered cationic chitosan (CH) and vermiculite clay (VMT) were deposited using layer-by-layer (LbL) assembly. Buffering the chitosan solution and its rinse with 50 mM Trizma base increased the thickness of these films by an order of magnitude. The OTR of a 1.6-µm-thick, six-bilayer film was 0.009 cc/m(2)·day·atm, making this the best gas barrier reported for such a small number of layers. This simple modification to the LbL process could likely be applied more universally to produce films with the desired properties much more quickly.

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.

Synergistic Fire Resistance of Nanobrick Wall Coated 3D Printed Photopolymer Lattices.

Photopolymer additive manufacturing has become the subject of widespread interest in recent years due to its capacity to enable fabrication of difficult geometries that are impossible to build with traditional manufacturing methods. The flammability of photopolymer resin materials and the lattice structures enabled by 3D printing is a barrier to widespread adoption that has not yet been adequately addressed. Here, a water-based nanobrick wall coating is deposited on 3D printed parts with simple (i.e., dense solid) or complex (i.e., lattice) geometries. When subject to flammability testing, the printed parts exhibit no melt dripping and a propensity toward failure at the print layer interfaces. Moving from a simple solid geometry to a latticed geometry leads to reduced time to failure during flammability testing. For nonlatticed parts, the coating provides negligible improvement in fire resistance, but coating of the latticed structures significantly increases time to failure by up to ≈340% compared to the uncoated lattice. The synergistic effect of coating and latticing is attributed to the lattice structures' increased surface area to volume ratio, allowing for an increased coating:photopolymer ratio and the ability of the lattice to better accommodate thermal expansion strains. Overall, nanobrick wall coated lattices can serve as metamaterials to increase applications of polymer additive manufacturing in extreme environments.

Nanobrick Wall Multilayer Thin Films with High Dielectric Breakdown Strength.

Current thermally conductive and electrically insulating insulation systems are struggling to meet the needs of modern electronics due to increasing heat generation and power densities. Little research has focused on creating insulation systems that excel at both dissipating heat and withstanding high voltages (i.e., have both high thermal conductivity and a high breakdown strength). Herein, a polyelectrolyte-based multilayer nanocomposite is demonstrated to be a thermally conductive high-voltage insulation. Through inclusion of both boehmite and vermiculite clay, the breakdown strength of the nanocomposite was increased by ≈115%. It was also found that this unique nanocomposite has an increase in its breakdown strength, modulus, and hydrophobicity when exposed to elevated temperatures. This readily scalable insulation exhibits a remarkable combination of breakdown strength (250 kV/mm) and thermal conductivity (0.16 W m-1 K-1) for a polyelectrolyte-based nanocomposite. This dual clay insulation is a step toward meeting the needs of the next generation of high-performance insulation systems.

Intumescent multilayer nanocoating, made with renewable polyelectrolytes, for flame-retardant cotton.

Thin films of fully renewable and environmentally benign electrolytes, cationic chitosan (CH) and anionic phytic acid (PA), were deposited on cotton fabric via layer-by-layer (LbL) assembly in an effort to reduce flammability. Altering the pH of aqueous deposition solutions modifies the composition of the final nanocoating. CH-PA films created at pH 6 were thicker and had 48 wt % PA in the coating, while the thinnest films (with a PA content of 66 wt %) were created at pH 4. Each coating was evaluated at both 30 bilayers (BL) and at the same coating weight added to the fabric. In a vertical flame test, fabrics coated with high PA content multilayers completely extinguished the flame, while uncoated cotton was completely consumed. Microcombustion calorimetry confirmed that all coated fabric reduces peak heat release rate (pkHRR) by at least 50% relative to the uncoated control. Fabric coated with pH 4 solutions shows the greatest reduction in pkHRR and total heat release of 60% and 76%, respectively. This superior performance is believed to be due to high phosphorus content that enhances the intumescent behavior of these nanocoatings. These results demonstrate the first completely renewable intumescent LbL assembly, which conformally coats every fiber in cotton fabric and provides an effective alternative to current flame retardant treatments.

Layer-by-Layer Deposition: A Promising Environmentally Benign Flame-Retardant Treatment for Cotton, Polyester, Polyamide and Blended Textiles.

A detailed review of recent developments of layer-by-layer (LbL) deposition as a promising approach to reduce flammability of the most widely used fibers (cotton, polyester, polyamide and their blends) is presented. LbL deposition is an emerging green technology, showing numerous advantages over current commercially available finishing processes due to the use of water as a solvent for a variety of active substances. For flame-retardant (FR) purposes, different ingredients are able to build oppositely charged layers at very low concentrations in water (e.g., small organic molecules and macromolecules from renewable sources, inorganic compounds, metallic or oxide colloids, etc.). Since the layers on a textile substrate are bonded with pH and ion-sensitive electrostatic forces, the greatest technological drawback of LbL deposition for FR finishing is its non-resistance to washing cycles. Several possibilities of laundering durability improvements by different pre-treatments, as well as post-treatments to form covalent bonds between the layers, are presented in this review.