Fabrication and Deformation of 3D Multilayered Kirigami Microstructures.

Mechanically guided 3D microassembly with controlled compressive buckling represents a promising emerging route to 3D mesostructures in a broad range of advanced materials, including single-crystalline silicon (Si), of direct relevance to microelectronic devices. During practical applications, the assembled 3D mesostructures and microdevices usually undergo external mechanical loading such as out-of-plane compression, which can induce damage in or failure of the structures/devices. Here, the mechanical responses of a few mechanically assembled 3D kirigami mesostructures under flat-punch compression are studied through combined experiment and finite element analyses. These 3D kirigami mesostructures consisting of a bilayer of Si and SU-8 epoxy are formed through integration of patterned 2D precursors with a prestretched elastomeric substrate at predefined bonding sites to allow controlled buckling that transforms them into desired 3D configurations. In situ scanning electron microscopy measurement enables detailed studies of the mechanical behavior of these structures. Analysis of the load-displacement curves allows the measurement of the effective stiffness and elastic recovery of various 3D structures. The compression experiments indicate distinct regimes in the compressive force/displacement curves and reveals different geometry-dependent deformation for the structures. Complementary computational modeling supports the experimental findings and further explains the geometry-dependent deformation.

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.

Influence of Graphene Reduction and Polymer Cross-Linking on Improving the Interfacial Properties of Multilayer Thin Films.

Graphene is a versatile composite reinforcement candidate due to its strong mechanical, tunable electrical and optical properties, and chemical stability. However, one drawback is the weak interfacial bonding, which results in weak adhesion to substrates. This could be overcome by adding polymer layers to have stronger adherence to the substrate and between graphene sheets. These multilayer thin films were found to have lower resistance to lateral scratch forces when compared to other reinforcements such as polymer/clay nanocomposites. Two additional processing steps are suggested to improve the scratch resistance of these films: graphene reduction and polymer cross-linking. Graphene/polymer nanocomposites consisting of polyvinylamine (PVAm) and graphene oxide (GO) were fabricated using the layer-by-layer assembly (LbL) technique. The reduced elastic modulus and hardness of PVAm/GO films were measured using nanoindentation. Reducing GO enhances mechanical properties by 60-70% while polymer cross-linking maintains this enhancement. Both graphene reduction and polymer cross-linking show significant improvement to scratch resistance. Particularly, polymer cross-linking leads to films with higher elastic recovery, 50% lower adhesive and plowing friction coefficient, 140 and 50% higher adhesive and shear strength values, respectively, and lower material pileup and scratch width/depth.

Nanomechanical Behavior of High Gas Barrier Multilayer Thin Films.

Nanoindentation and nanoscratch experiments were performed on thin multilayer films manufactured using the layer-by-layer (LbL) assembly technique. These films are known to exhibit high gas barrier, but little is known about their durability, which is an important feature for various packaging applications (e.g., food and electronics). Films were prepared from bilayer and quadlayer sequences, with varying thickness and composition. In an effort to evaluate multilayer thin film surface and mechanical properties, and their resistance to failure and wear, a comprehensive range of experiments were conducted: low and high load indentation, low and high load scratch. Some of the thin films were found to have exceptional mechanical behavior and exhibit excellent scratch resistance. Specifically, nanobrick wall structures, comprising montmorillonite (MMT) clay and polyethylenimine (PEI) bilayers, are the most durable coatings. PEI/MMT films exhibit high hardness, large elastic modulus, high elastic recovery, low friction, low scratch depth, and a smooth surface. When combined with the low oxygen permeability and high optical transmission of these thin films, these excellent mechanical properties make them good candidates for hard coating surface-sensitive substrates, where polymers are required to sustain long-term surface aesthetics and quality.

Ultrastrong, Chemically Resistant Reduced Graphene Oxide-based Multilayer Thin Films with Damage Detection Capability.

Multilayer thin films of graphene oxide (GO) and poly(vinylamine) (PVAm) were deposited via layer-by-layer assembly. Poly(vinylamine) pH was used to tailor film thickness and GO layer spacing. Graphene oxide concentration in the films was controlled through simple pH adjustment. Thermal reduction of the PVAm/GO multilayer thin films rendered them electrically conductive, which could be further tailored with PVAm pH. These reduced films also exhibited exceptionally high elastic modulus of 30 GPa and hardness of 1.8 GPa, which are among the highest of any graphene-filled polymer composite values ever reported. Cross-linking of these films with glutaraldehyde improved their chemical resistance, allowing them to survive strongly acidic or salty solutions. Additionally, scratches in the films can be instantaneously detected by a simple electrical resistance measurement. These films are promising for a variety of packaging and electronic applications.