Voxel resolution in the directed self-assembly of liquid crystal polymer networks and elastomers.

Monomeric mixtures formulated to prepare a liquid crystal polymer network (LCN) or elastomer (LCE) can be "programmed" by surface alignment to retain complex and arbitrary spatial distributions of the director orientation upon polymerization. The localized control of orientation in a given volume (voxel) within these materials is the subject of intense research, currently motivated by the prospect of distinctive mechanical responses (both active and passive). Here, we report on a rapid and scalable photopatterning method to prepare alignment surfaces with a throughput of 10 mm2 s-1, using a commercial spatial light modulator and projection optics. Enabled by this method, we detail that the resolution limit of the inscribed director profile is not dictated by the optical system but is determined by the elastic-mediated orientational relaxation of the liquid crystalline materials. A simple model is experimentally validated and the implications for device design are discussed.

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.

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.

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.

Sub-second and ppm-level optical sensing of hydrogen using templated control of nano-hydride geometry and composition.

The use of hydrogen as a clean and renewable alternative to fossil fuels requires a suite of flammability mitigating technologies, particularly robust sensors for hydrogen leak detection and concentration monitoring. To this end, we have developed a class of lightweight optical hydrogen sensors based on a metasurface of Pd nano-patchy particle arrays, which fulfills the increasing requirements of a safe hydrogen fuel sensing system with no risk of sparking. The structure of the optical sensor is readily nano-engineered to yield extraordinarily rapid response to hydrogen gas (<3 s at 1 mbar H2) with a high degree of accuracy (<5%). By incorporating 20% Ag, Au or Co, the sensing performances of the Pd-alloy sensor are significantly enhanced, especially for the Pd80Co20 sensor whose optical response time at 1 mbar of H2 is just ~0.85 s, while preserving the excellent accuracy (<2.5%), limit of detection (2.5 ppm), and robustness against aging, temperature, and interfering gases. The superior performance of our sensor places it among the fastest and most sensitive optical hydrogen sensors.

All-Optical Control of Shape.

Photoresponsive liquid crystal elastomers (LCEs) are a unique class of anisotropic materials capable of undergoing large-scale, macroscopic deformations when exposed to light. Here, surface-aligned, azobenzene-functionalized LCEs are prepared via a radical-mediated, thiol-acrylate chain transfer reaction. A long-lived, macroscopic shape deformation is realized in an LCE composed with an o-fluorinated azobenzene (oF-azo) monomer. Under UV irradiation, the oF-azo LCE exhibits a persistent shape deformation for >72 h. By contrasting the photomechanical response of the oF-azo LCE to analogs prepared from classical and m-fluorinated azobenzene derivatives, the origin of the persistent deformation is clearly attributed to the underlying influence of positional functionalization on the kinetics of cis→trans isomerization. Informed by these studies and enabled by the salient features of light-induced deformations, oF-azo LCEs are demonstrated to undergo all-optical control of shape deformation and shape restoration.

Enabling and Localizing Omnidirectional Nonlinear Deformation in Liquid Crystalline Elastomers.

Liquid crystalline elastomers (LCEs) are widely recognized for their exceptional promise as actuating materials. Here, the comparatively less celebrated but also compelling nonlinear response of these materials to mechanical load is examined. Prior examinations of planarly aligned LCEs exhibit unidirectional nonlinear deformation to mechanical loads. A methodology is presented to realize surface-templated homeotropic orientation in LCEs and omnidirectional nonlinearity in mechanical deformation. Inkjet printing of the homeotropic alignment surface localizes regions of homeotropic and planar orientation within a monolithic LCE element. The local control of the self-assembly and orientation of the LCE, when subject to rational design, yield functional materials continuous in composition with discontinuous mechanical deformation. The variation in mechanical deformation in the film can enable the realization of nontrivial performance. For example, a patterned LCE is prepared and shown to exhibit a near-zero Poisson's ratio. Further, it is demonstrated that the local control of deformation can enable the fabrication of rugged, flexible electronic devices. An additively manufactured device withstands complex mechanical deformations that would normally cause catastrophic failure.

Layered liquid crystal elastomer actuators.

Liquid crystalline elastomers (LCEs) are soft, anisotropic materials that exhibit large shape transformations when subjected to various stimuli. Here we demonstrate a facile approach to enhance the out-of-plane work capacity of these materials by an order of magnitude, to nearly 20 J/kg. The enhancement in force output is enabled by the development of a room temperature polymerizable composition used both to prepare individual films, organized via directed self-assembly to retain arrays of topological defect profiles, as well as act as an adhesive to combine the LCE layers. The material actuator is shown to displace a load >2500× heavier than its own weight nearly 0.5 mm.

Electrical Control of Shape in Voxelated Liquid Crystalline Polymer Nanocomposites.

Liquid crystal elastomers (LCEs) exhibit anisotropic mechanical, thermal, and optical properties. The director orientation within an LCE can be spatially localized into voxels [three-dimensional (3-D) volume elements] via photoalignment surfaces. Here, we prepare nanocomposites in which both the orientation of the LCE and single-walled carbon nanotube (SWNT) are locally and arbitrarily oriented in discrete voxels. The addition of SWNTs increases the stiffness of the LCE in the orientation direction, yielding a material with a 5:1 directional modulus contrast. The inclusion of SWNT modifies the thermomechanical response and, most notably, is shown to enable distinctive electromechanical deformation of the nanocomposite. Specifically, the incorporation of SWNTs sensitizes the LCE to a dc field, enabling uniaxial electrostriction along the orientation direction. We demonstrate that localized orientation of the LCE and SWNT allows complex 3-D shape transformations to be electrically triggered. Initial experiments indicate that the SWNT-polymer interfaces play a crucial role in enabling the electrostriction reported herein.

Pixelated Polymers: Directed Self Assembly of Liquid Crystalline Polymer Networks.

Polymeric materials are pervasive in modern society, in part attributable to the diverse range of properties that are accessible in these materials. Polymers can be stiff or soft, dissipative or elastic, adhesive or nonstick. Localizing the properties of polymeric materials can be achieved by a number of methods, including self-assembly, lithography, or 3-d printing. Here, we detail recent advances in the preparation of "pixelated" polymers prepared by the directed self-assembly of liquid crystalline monomers to yield cross-linked polymer networks (liquid crystalline polymer networks, LCN, or liquid crystalline elastomers, LCE). Through the local and arbitrary control of the orientation of the liquid crystalline units, monolithic elements can be realized with spatial variation in mechanical, thermal, electrical, optical, or acoustic properties. Stimuli-induced variation of these properties may enable paradigm-shifting end uses in a diverse set of applications.

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.

Water-Based Melanin Multilayer Thin Films with Broadband UV Absorption.

Natural melanin is difficult to process due to its poor solubility and poorly understood structure. Synthetic melanin has been produced more recently, which is dispersible in mildly alkaline water and has many of the same properties of natural melanin. In this study, thin films of synthetic melanin and poly(allylamine hydrochloride) were deposited layer-by-layer from dilute aqueous solutions in ambient conditions. This is likely the first time melanin has been deposited from water to produce a functional nanocoating. These films display broadband UV light absorption, absorbing over 63% of incident light that is most damaging to human eyes with a thickness of 108 nm. In an effort to demonstrate the utility of these melanin-based nanocoatings, a 30 bilayer film is shown to increase the useful life of a conductive poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) film by 550%. This novel method of depositing melanin should open the door to a variety of useful applications.