Through billions of years of evolution and natural selection, biological systems have developed strategies to achieve advantageous unification between structure and bulk properties. The discovery of these fascinating properties and phenomena has triggered increasing interest in identifying characteristics of biological materials, through modern characterization and modeling techniques. In an effort to produce better engineered materials, scientists and engineers have developed new methods and approaches to construct artificial advanced materials that resemble natural architecture and function. A brief review of typical naturally occurring materials is presented here, with a focus on chemical composition, nano-structure, and architecture. The critical mechanisms underlying their properties are summarized, with a particular emphasis on the role of material architecture. A review of recent progress on the nano/micro-manufacturing of bio-inspired hybrid materials is then presented in detail. In this case, the focus is on nacre and bone-inspired structural materials, petals and gecko foot-inspired adhesive films, lotus and mosquito eye inspired superhydrophobic materials, brittlestar and Morpho butterfly-inspired photonic structured coatings. Finally, some applications, current challenges and future directions with regard to manufacturing bio-inspired hybrid materials are provided.

In an effort to create a paintable/printable thermoelectric material, comprised exclusively of organic components, polyaniline (PANi), graphene, and double-walled nanotube (DWNT) are alternately deposited from aqueous solutions using the layer-by-layer assembly technique. Graphene and DWNT are stabilized with an intrinsically conductive polymer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). An 80 quadlayer thin film (≈1 μm thick), comprised of a PANi/graphene-PEDOT:PSS/PANi/DWNT-PEDOT:PSS repeating sequence, exhibits unprecedented electrical conductivity (σ ≈ 1.9 × 10⁵ S m⁻¹) and Seebeck coefficient (S ≈ 120 μV K⁻¹) for a completely organic material. These two values yield a thermoelectric power factor (PF = S ² σ ⁻¹) of 2710 μW m⁻¹ K⁻², which is the highest value ever reported for a completely organic material and among the highest for any material measured at room temperature. These outstanding properties are attributed to the highly ordered structure in the multilayer assembly. This water-based thermoelectric nanocomposite is competitive with the best inorganic semiconductors (e.g., bismuth telluride) at room temperature and can be applied as a coating to any flexible surface (e.g., fibers in clothing). For the first time, there is a real opportunity to harness waste heat from unconventional sources, such as body heat, to power devices in an environmentally-friendly way.

Due to their exceptional orientation of 2D nanofillers, layer-by-layer (LbL) assembled polymer/graphene oxide thin films exhibit unmatched mechanical performance relative to any conventionally produced counterparts with similar composition. Unprecedented mechanical property improvement, by replacing graphene oxide with pristine graphene, is demonstrated in this work. Polyvinylpyrrolidone-stabilized graphene platelets are alternately deposited with poly(acrylic acid) using hydrogen bonding assisted LbL assembly. Transmission electron microscopy imaging and the Halpin-Tsai model are used to demonstrate, for the first time, that intact graphene can be processed from water to generate polymer nanocomposite thin films with simultaneous parallel-alignment, high packing density, and exfoliation. A multilayer thin film with only 3.9 vol% of highly exfoliated, and structurally intact graphene, increases the elastic modulus (E) of a polymer multilayer thin film by 322% (from 1.41 to 4.81 GPa), while maintaining visible light transmittance of ≈90%. This is one of the greatest improvements in elastic modulus ever reported for a graphene-filled polymer nanocomposite with a glassy (E > 1 GPa) matrix. The technique described here provides a powerful new tool to improve nanocomposite properties (mechanical, gas transport, etc.) that can be universally applied to a variety of polymer matrices and 2D nanoplatelets.

Layer-by-layer (LbL) assembly of nanocoatings on fabric substrates has been very successful in terms of reduction of flammability. In particular, an LbL system comprised ammonium polyphosphate as the polyanion and chitosan as the polycation, applied to cotton fabric, dramatically reduced cotton flammability. At this point, the fire-retardant (FR) mechanism of action of this system has never been fully elucidated. Sonicated and nonsonicated coated cotton fabrics were evaluated using a vertical flame test and mass loss calorimeter. Coating morphology was investigated before and after burning. Thermal analyses and chemical analyses in the condensed phase (and in the gas phase) were conducted to reveal the FR mechanism of action. At the cotton surface, a combination of both condensed (formation of aromatic char) and gas phase (release of water and highly flammable gases) mechanisms impart the FR behavior, promoting a kind of “microintumescence” phenomenon. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43783.

Layer-by-layer (LbL) assembly is a powerful and versatile technique to deposit functional thin films, but often requires a large number of deposition steps to achieve a film thick enough to provide a desired property. By incorporating amine salts into the cationic polyelectrolyte and its associated rinse, LbL clay-containing nanocomposite films can achieve much greater thickness (>1 μm) with relatively few deposition cycles (≤6 bilayers). Amine salts interact with nanoclays, causing nanoplatelets to deposit in stacks rather than as individual platelets. This technique appears to be universal, exhibiting thick growth with multiple types of nanoclay, including montmorillonite and vermiculite (VMT), and a variety of amine salts (e.g., hexylamine and diethanolamine). The characteristic order found in LbL-assembled films is maintained despite the incredible thickness. Films assembled in this manner achieve oxygen transmission rates below 0.009 cc m⁻² d⁻¹ atm⁻¹ with just 6 bilayers (BLs) of chitosan/VMT deposited. These thick clay-based thin films also impart exceptional flame resistance. A 2-BL film renders a 3.2 mm polystyrene plate self-extinguishing, while an 8-BL film (3.9 μm thick) prevents ignition entirely. This ability to generate much thicker clay-based multilayers with amine salts opens up tremendous potential for these nanocoatings in real world applications.

The influence of attaching hydrophobic side groups to a polyelectrolyte, used for deposition of a multilayer oxygen gas barrier thin film, was investigated. Polyethyleneimine (PEI) was labeled with pyrene and deposited in “quadlayers” of PEI, poly(acrylic acid), PEI, and sodium montmorillonite clay using layer-by-layer assembly. Thin films made of three repeating quadlayers using unmodified PEI had much lower density (1.24 g/cm³) than pyrene-labeled PEI-based films (1.45 g/cm³), which is believed to be the result of greater chain coiling from the increased hydrophobicity of pendant pyrene groups. This increased density in pyrene-labeled PEI layers allowed three quadlayers to match the oxygen transmission rate of a four quadlayer film made with unmodified PEI. This discovery provides an additional tool for tailoring the barrier behavior of clay-based multilayer thin films that could prove useful for a variety of packaging applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1153–1156

Organic thin film nanocomposites, prepared by liquid-phase exfoliation, were investigated for their superior electrical properties and thermoelectric behavior. Single-walled carbon nanotubes (SWNT) were stabilized by intrinsically conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) in an aqueous solution. The electrical conductivity (σ) was found to increase linearly as 20 to 95 wt % SWNT. At 95 wt % SWNT, these thin films exhibit metallic electrical conductivity (∼4.0 × 10⁵ S m⁻¹) that is among the highest values ever reported for a free-standing, fully organic material. The thermopower (S) remains relatively unaltered as the electrical conductivity increases, leading to a maximum power factor (S²σ) of 140 μW m⁻¹ K⁻². This power factor is within an order of magnitude of bismuth telluride, so it is believed that these flexible films could be used for some unique thermoelectric applications requiring mechanical flexibility and printability. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013

A blistering study was performed on a fluorinated polyimide resin and its carbon-fiber composite in an effort to determine the blister-formation temperature and the influence of blisters on composite performance. The fluorinated resin and carbon-fiber composite exhibit higher glass-transition (435–455°C) and decomposition temperatures (above 520°C) than similar polyimide resins and their carbon-fiber composites currently used. Two techniques were used to determine moisture-induced blister formation. A transverse extensometer with quartz lamps as a heating source measured thickness expansion, as did a thermomechanical analyzer as a function of temperature. Both methods successfully measured the onset of blister formation with varying amounts of absorbed moisture (up to 3 wt%) in the samples. The polyimide resin exhibited blister temperatures ranging from 225 to 362°C, with 1.7–3.0 wt% absorbed moisture, and the polyimide composite had blister temperatures from 246 to 294°C with 0.5–1.5 wt% moisture. The blistering effects of the polyimide composites were found to have little correlation with modulus. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers

Monodispersed copolymer emulsions, each with a different polymer particle size, were used to investigate the effect of particle size on the electrical and thermomechanical properties of carbon black (CB)-filled segregated network composites. These emulsions were synthesized with equal moles of methyl methacrylate and butyl acrylate, with latex particle size ranging from 83 to 771 nm. The electrical percolation threshold was found to decrease from 2.7 to 1.1 vol % CB as the latex particle size was increased. Microstructural images reveal diminished latex coalescence, and improved CB segregation, with increasing latex particle size. In general, coalescence is shown to increase for all systems with increasing CB concentration. Furthermore, all systems exhibited a similar maximum electrical conductivity plateau of 0.7 S cm⁻¹, albeit at lower concentration for larger latex particle size. This ability to tailor percolation threshold with latex particle size provides an important tool for manipulating electrical and mechanical properties of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1547–1554, 2011

High-temperature polymers are being used for a broad range of applications, such as composite matrices for structural applications (e.g., high speed aircraft). Polyimides are a special class of polymers that meet the thermal and oxidative stability requirements for high temperature composite aerospace applications. A weight loss study was performed on a fluorinated polyimide resin and its carbon fiber composite in an effort to determine its thermal stability and degradation mechanisms. Experiments were conducted using a preheated oven and thermogravimetric analysis to obtain the weight loss. Regardless of the method used, the resin and composite exhibited excellent thermal stability (less than 1% weight loss) below 430°C, regardless of 2–20 min of exposure. After 20 min of exposure at 510°C, the composite remained relatively stable with only 5.3% weight loss using the oven technique, whereas the neat polyimide sustained 12.6%. When degradation occurred, it was found to be the result of thermolysis and oxidation (to a lesser extent). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010