Nanostructured Polymer Films Research Articles

Surface proton hopping conduction mechanism dominant polymer electrolytes created by self-assembly of bicontinuous cubic liquid crystals.

For the development of the next generation of fuel cells, it is essential to create an innovative design principle of polymer electrolytes that is beyond extension of the existing strategy. In the present study, we focused on the surface hopping proton conduction mechanism where an activation energy for proton conduction is greatly reduced by decreasing the distance between SO3- groups. Our gyroid nanostructured polymer film (Film-G), with a hydrophilic surface where the SO3- groups are aligned densely and precisely, shows high proton conductivity of the order of 10-2 S cm-1 when the water content is about 15 wt%. We reveal that the high proton conductivity of Film-G is attributed to the exhibition of an extremely-fast surface hopping conduction mechanism due to the reduced activation energy barrier along the gyroid minimal surface. This finding should introduce a game-changing novel opportunity in polymer electrolyte design.

Strategy for Nonenzymatic Harvesting of Cells via Decoupling of Adhesive and Disjoining Domains of Nanostructured Stimulus-Responsive Polymer Films.

The nanostructured polymer film introduces a novel mechanism of nonenzymatic cell harvesting by decoupling solid cell-adhesive and soft stimulus-responsive cell-disjoining areas on the surface. The key characteristics of this architecture are the decoupling of adhesion from detachment and the impermeability to the integrin protein complex of the adhesive domains. This surface design eliminates inherent limitations of thermoresponsive coatings, namely, the necessity for the precise thickness of the coating, grafting or cross-linking density, and material of the basal substrate. The concept is demonstrated with nanostructured thermoresponsive films made of cell-adhesive epoxy photoresist domains and cell-disjoining poly(N-isopropylacrylamide) brush domains.

Improvement of Nanostructured Polythiophene Film Uniformity Using a Cruciform Electrode and Substrate Rotation in Atmospheric Pressure Plasma Polymerization.

In atmospheric pressure (AP) plasma polymerization, increasing the effective volume of the plasma medium by expanding the plasma-generating region within the plasma reactor is considered a simple method to create regular and uniform polymer films. Here, we propose a newly designed AP plasma reactor with a cruciform wire electrode that can expand the discharge volume. Based on the plasma vessel configuration, which consists of a wide tube and a substrate stand, two tungsten wires crossed at 90 degrees are used as a common powered electrode in consideration of two-dimensional spatial expansion. In the wire electrode, which is partially covered by a glass capillary, discharge occurs at the boundary where the capillary terminates, so that the discharge region is divided into fourths along the cruciform electrode and the discharge volume can successfully expand. It is confirmed that although a discharge imbalance in the four regions of the AP plasma reactor can adversely affect the uniformity of the polymerized, nanostructured polymer film, rotating the substrate using a turntable can significantly improve the film uniformity. With this AP plasma reactor, nanostructured polythiophene (PTh) films are synthesized and the morphology and chemical properties of the PTh nanostructure, as well as the PTh-film uniformity and electrical properties, are investigated in detail.

Numerical Study on Broadband Antireflection of Moth-Eye Nanostructured Polymer Film with Flexible Polyethylene Terephthalate Substrate

The application of moth-eye nanostructured polymer film on the flexible polyethylene terephthalate (PET) substrate is an effective way to improve its antireflection (AR) performance. However, many factors affect the AR properties of the moth-eye structure in the actual manufacturing process. Moreover, the antireflection research based on PET substrate has been relatively lacking compared with the silicon substrate. In this paper, we simulate and analyze the AR performance of the moth-eye nanostructured polymer film on PET substrate by using the finite-difference time-domain method within the wavelength range of 400–1100 nm. Simulation results show that the parabola-shaped moth-eye structure (PSMS) can suppress the Fresnel reflection significantly. Moreover, the height and filling ratios are the dominant factors that affect the AR performance of PSMS. Additionally, the base diameter, residual layer thickness, and the refractive index of PSMS polymer film also affect the reflectivity of PET slightly. As a result, an optimal PSMS with base diameter of 400 nm, height of 300 nm, and the hexagonal close-packed arrangement is appropriate, and the solar-weighted reflectivity of PET can be suppressed to 0.21%, which shows a prominent advantage over the bare PET (≈6%). Therefore, this research has promising potential for improving the optical performance of optoelectronic devices by using nanostructured polymer materials.

Controlling the optical properties of nanostructured oxide-based polymer films

A bulk scale process is implemented for the production of nanostructured film composites comprising unary or multi-component metal oxide nanoparticles dispersed in a suitable polymer matrix. The as-received nanoparticles, namely Al_2O_3, SiO_2 and TiO_2 and binary combinations, are treated following specific chemical and mechanical processes in order to be suspended at the optimal size and composition. Subsequently, a polymer extrusion technique is employed for the fabrication of each film, while the molten polymer is mixed with the treated metal oxide nanoparticles. Transmission and reflection measurements are performed in order to map the optical properties of the fabricated, nanostructured films in the UV, VIS and IR. The results substantiate the capability of the overall methodology to regulate the optical properties of the films depending on the type of nanoparticle formation which can be adjusted both in size and composition.

Creation of Gyroid Nanostructured Polymer Films from Lyotropic Liquid Crystals Containing a Polymerizable Ionic Liquid as a Solvent

Bicontinuous cubic liquid-crystalline assemblies were obtained by mixing a polymerizable ionic liquid with a glycolipid. Polymerization of the ionic liquid in the molecular assemblies was achieved by UV irradiation in the presence of a photoinitiator, which provided a quasi-polymer film preserving the bicontinuous cubic assemblies with a gyroid nanostructure.

Gemini Thermotropic Smectic Liquid Crystals for Two-Dimensional Nanostructured Water-Treatment Membranes.

We have developed a two-dimensional (2D) liquid-crystalline (LC) nanostructured water-treatment membrane showing high virus rejection ability (over 99.99997% for bacteriophage Qβ) and improved water permeation. Polymerizable gemini amphiphiles have been designed and synthesized. They have H-shaped gemini-type structures of thermotropic smectic liquid crystals composed of cationic imidazolium moieties. One of the gemini amphiphiles shows a smectic A phase with an interdigitated bilayer structure. A cross-linked self-standing 2D nanostructured polymer film has been obtained by in situ photopolymerization of the gemini amphiphile in the smectic phase. The length of linkers in gemini amphiphiles affects the formation of LC phases. The 2D nanostructured membrane also showed selective salt rejection.

Gyroid nanostructured soft membranes formed by controlling the degree of crosslinking polymerization of bicontinuous cubic liquid-crystalline monomers

The self-organization of liquid-crystalline monomers and subsequent polymerization is a unique strategy for creating nanostructured polymer membranes with novel functions and innovative properties. In this study, we developed gyroid nanostructured soft polymer films based on this strategy. Two types of amphiphile zwitterion monomers were designed and synthesized: a single-type amphiphile zwitterion monomer (S-ZI) and a gemini-type monomer (G-ZI). These compounds show liquid-crystalline behavior in the presence of bis(trifluoromethanesulfonyl)imide (HTf2N) and water. We attempted to find an appropriate mixing ratio of S-ZI and G-ZI that satisfied the following two criteria: suitability for the exhibition of bicontinuous cubic (Cubbi) phases and acquisition of self-standing properties and softness. The 25/75 wt% component ratio of S-ZI/G-ZI was found to meet these conditions. By carrying out a polymerization for the mixture in the above mixing ratio in the Cubbi phase, a polymer film with self-standing properties and resistance to bending was successfully obtained. This film showed a high ionic conductivity of 1.27 × 10−2 S cm−1 under a relative humidity of 90%. A gyroid nanostructured soft polymer film was developed by the co-organization of two types of amphiphile zwitterion monomers and a suitable acid into a bicontinuous cubic liquid-crystalline phase and subsequent in situ polymerization. The obtained polymer film showed a high ionic conductivity of 1.27 × 10–2 S cm–1 at a relative humidity of 90%.

Design, development and characterization of polyelectrolyte multilayer membranes for potential filtration applications

Abstract The present work projects to modify the surface of commercially available microfiltration membranes using polyelectrolyte multilayer assembly. This polyelectrolytic modification changes the nature and properties of the membrane such as porosity, absorption capacity, charge etc. which can be used for potential environmental application such as herbicide removal from water. Chitosan (CHI) and polystyrene sulfonate (PSS) were incorporated into nanostructured polymeric films on polyamide membrane using layer-by-layer (LbL) technique. The developed polyelectrolyte multilayer assembly were characterized by using UV–vis spectroscopy, attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy, thermo gravimetric analysis (TGA) and atomic force microscopy (AFM).

Ion-Conductive Nanostructured Polymer Films Formed by Photopolymerization of Lyotropic Columnar Liquid-Crystalline Monomers, Composed of a Zwitterionic Compound and a Protic Ionic Liquid

Here, we report on a new family of columnar nanostructured polymer films forming protic nanochannels that exhibit good ionic conductivities in the order of 10−4–10−3 S cm−1 at ambient temperature. These polymer films were obtained by the in situ photopolymerization of lyotropic columnar liquid crystals, consisting of a polymerizable taper-shaped zwitterionic compound and a protic ionic liquid (imidazolium bis(trifluoromethylsulfonyl)imide), in the presence of 15 wt% water. The composition of the protic ionic liquid in the mixture was changed from 40 to 60 mol%. The ionic conductivities were measured by an alternating current impedance method. The ionic conductivity increased with the increase of the protic ionic liquid. The conductivities of columnar nanostructured polymer films were about 2–3 orders of magnitude higher than those of amorphous polymer films prepared by photopolymerization of the corresponding monomers in an isotropic liquid state. The formation of nanochannels in the polymer matrices significantly enhanced the ion conduction. The present two-component lyotropic liquid-crystalline self-assembly followed by photopolymerization is a promising approach to the development of high ion-conductive polymer membranes.

TransPoly: A theoretical model to quantify the dynamics of water transfer through nanostructured polymer films

Mass transfer of penetrants is among the most important physical properties of polymer films to properly ensure function during service. In the case of interaction between penetrants and polymer, non-Fickian diffusion can be observed. This phenomenon is described by numerous reports and a few models have been proposed. Nevertheless, few of them quantify Fickian and non-Fickian behaviour using parameters with clear physical meaning. The present work develops a new non-Fickian mass transport model: TransPoly (Transfer through Polymers). Based on coupled heat and mass transfer, it accounts for simultaneous Fickian transport and molecular relaxation. This model is applied to data of water vapour mass transfer in nanocomposites of polylactide and cellulose nanocrystals. The contribution of the non-Fickian mass transfer on water vapour sorption is highlighted. TransPoly can be applied to several kinds of polymers and used for prediction purposes once the parameters are determined on a learning database.

Nanostructured polymer films with metal-like thermal conductivity

Due to their unique properties, polymers – typically thermal insulators – can open up opportunities for advanced thermal management when they are transformed into thermal conductors. Recent studies have shown polymers can achieve high thermal conductivity, but the transport mechanisms have yet to be elucidated. Here we report polyethylene films with a high thermal conductivity of 62 Wm−1 K−1, over two orders-of-magnitude greater than that of typical polymers (~0.1 Wm−1 K−1) and exceeding that of many metals and ceramics. Structural studies and thermal modeling reveal that the film consists of nanofibers with crystalline and amorphous regions, and the amorphous region has a remarkably high thermal conductivity, over ~16 Wm−1 K−1. This work lays the foundation for rational design and synthesis of thermally conductive polymers for thermal management, particularly when flexible, lightweight, chemically inert, and electrically insulating thermal conductors are required.

Modification of block copolymer lithography masks by O2/Ar plasma treatment: insights from lift-off experiments, nanopore etching and free membranes

Block copolymer lithography allows for the large-area patterning of surfaces with self-assembled nanoscale features. The created nanostructured polymer films can be applied as masks in common lithography processing steps, such as lift-off and etching for pattern replication and transfer. In this work, we discuss an approach to improve the pattern replication efficiency by modification of the polymer mask prior to lithographical use by means of an O2/Ar plasma treatment. We present a much better quality of pattern replication without loss of features, along with a precise tunability of feature sizes, that can be achieved by short mask treatment. We point out a correlation between nanopore position within the ordered arrays, expressed by its coordination number, the nanopore shape and the replication efficiency. Our experimental strategy to explain these correlations combines the indirect investigation of patterns replicated from the modified polymer masks and direct investigation of the mask top and bottom. Pattern replication is performed either in the form of gold nanodot arrays created via lift-off or nanopores transferred into a SiO2 substrate by reactive ion etching. The direct analysis of free polymer membranes released from the substrate reveals the nanopore shape at the mask top and bottom surfaces.

Nanoporous Organic Network Coating of Nanostructured Polymer Films with Enhanced Adsorption Performance toward Particulate Matter.

This work shows that the surface properties of polyurethane acrylate (PUA) films can be controlled by the coating of nanoporous organic networks (NONs). By the NON coating, the hydrophilic nature of nanostructured PUA (N-PUA) film was converted to superhydrophobic surface. The NON-coated N-PUA films (N-PUA-NONs) were applied as stationary adsorbents for the capture of particulate matter (PM) in air. Compared with the original PUA films, the N-PUA-NON films showed much enhanced capture performance toward PM and recyclability through water washing, indicating the potential of outdoor application as stationary self-cleaning adsorbents under natural surroundings.

Homeotropic Self-Alignment of Discotic Liquid Crystals for Nanoporous Polymer Films.

Nanostructured polymer films with continuous, membrane-spanning pores from polymerizable hexagonal columnar discotic liquid crystals (LCs) were fabricated. A robust alignment method was developed to obtain homeotropic alignment of columns between glass surfaces by adding a small amount of a tri(ethylene glycol) modified analogue of the mesogen as a dopant that preferentially wets glass. The homeotropic LC alignment was fixated via a photoinitiated free radical copolymerization of a high-temperature tolerant trisallyl mesogen with a divinyl ester. Removal of the hydrogen-bonded template from the aligned columns afforded a nanoporous network with pores of nearly 1 nm in diameter perpendicular to the surface, and without noticeable collapse of the nanopores. The effect of pore orientation was demonstrated by an adsorption experiment in which homeotropic film showed a threefold increase in the initial uptake rate of methylene blue compared to planarly aligned films.

Effect of the surface wettability changes on nanostructured polymer film for heat exchanger applications

Polymer heat exchangers have drawn attention due to their special characteristics such as flexibility, low weight, corrosion, and bio-fouling resistance, as well as their ease of manufacturing. However, since their thermal conductivity is low, they require a way to increase their heat transfer rate. We investigated the effect of modifying the surface wettability of polymer films on the heat transfer rate during the condensation process, both theoretically and experimentally. Condensed water formation on the film surface depends on the surface wettability control, and thus, hydrophilic or hydrophobic surfaces can induce film-wise or drop-wise condensation, respectively. Generally, the polymer surface shows a hydrophobic property due to the intrinsic C-C and C-H bonding of polymer frames. Here, we used four different types of polymer films, which have different thermal conductivity and controlled wettability properties, including polyimide film, polyimide film containing aluminum nanoparticles, and both films with super-hydrophobic treatment. The results show that nanostructured polymers with hydrophobic treatment have a 25% lower wetted area fraction than those without hydrophobic treatment, independent of the thermal conductivity of the polymer films. To compare the heat transfer rates, we designed a thermal resistance model considering vapor convection, vapor-water interfaces and curvatures, and conductions of the droplet, nanostructure, and polymer. We found that the convective thermal resistance dominantly affects the heat transfer rate and treated polymers showed over 200% higher total heat transfer than bare polymer.

Granular Nanostructure: A Facile Biomimetic Strategy for the Design of Supertough Polymeric Materials with High Ductility and Strength.

The realization of high strength, large ductility, and great toughness for polymeric materials is a vital factor for practical applications in industry. Unfortunately, until now this remains a huge challenge due to the common opposing trends that exist when promoting improvements in these properties using materials design strategies. In the natural world, the cuticle of mussel byssus exhibits a breaking strain as high as 100%, which is revealed to arise from an architectural granular microphase-separated structure within the protein matrix. Herein, a facile biomimetic designed granular nanostructured polymer film is reported. Such biomimetic nanostructured polymer films show a world-record toughness of 122 (± 6.1) J g-1 as compared with other polyvinyl alcohol films, with a breaking strain as high as 205% and a high tensile strength of 91.2 MPa, which is much superior to those of most engineering plastics. This portfolio of outstanding properties can be attributed to the unique nanoscale granular phase-separated structure of this material. These biomimetic designed polymer films are expected to find promising applications in tissue engineering and biomaterials fields, such as artificial skin and tendon, which opens up an innovative methodology for the design of robust polymer materials for a range of innovative future applications.

A facile electrochemical strategy for synthesis of 3D nanodimensional polypyrrole structures using self-assembled layers of pyrrole monomers

Abstract The formation of nanodimensional conductive polymers is one of the major challenges of scientists. They show enhanced performance compared to the bulk structures, because of their higher surface area to volume ratio. However, most of synthesis strategies are chemical, template-assisted techniques with difficult controlling factors. The electrochemical routes have been considered in recent years, since they are more simple and controllable than chemical methods. The present work, reports a simple electrochemical method for synthesis of 3D nanostructured polypyrrole films. The idea was that pretreatment of electrode with pyrrole monomers may lead to their adsorption on metal surface. Then, a very thin polymer film is formed by applying a constant current in a monomer-free solution to the pretreated electrodes; the morphology of this film was expected to be different from the morphology of commonly electrosynthesized bulk polymer films. Scanning electron microscopic studies showed that the nanodimensional slates of polypyrrole have been formed during this procedure. Atomic force microscopy images verified the formation of nanostructured polymer film. The effect of monomer concentration, immersion time and substrate properties on the morphology of the nanostructures was evaluated. Cyclic voltammetry tests were performed and the results showed significant enhancement in surface area of the polypyrrole films.

Label-free and sensitive impedimetric nanosensor for the detection of cocaine based on a supramolecular complexation with β-cyclodextrin, immobilized on a nanostructured polymer film

Cocaine, a powerful addictive stimulant drug, has a variety of adverse effects on the body, thus its sensitive detection is very important. Here, we report on a simple, label-free, and sensitive impedimetric sensor for determination of cocaine based on its affinity to form an inclusion complex with β-cyclodextrin (β-CD). First, we prepared nanostructured poly N-acetylaniline film via electropolymerization of its monomer on a glassy carbon electrode (PNAANI/GC), subsequently overoxidized it, and conjugated β-CD to the polymer backbone. The designed and synthesized nanostructured PNAANI film serves a dual function in the sensor: on one hand, it maintains a high effective surface area on a geometrically small electrode that significantly enhances the number of β-CD molecules immobilized on the electrode; on the other hand, it provides an upright-oriented β-CD conjugation to the polymer backbone, thus all the β-CD receptors are actively involved in responding to the target. Sensitivity of the sensor was further enhanced by preconcentration of cocaine on the modified electrode surface. We attributed the changes in the interfacial charge transfer resistance (R ct) of the electrode to cocaine concentration. Under optimized condition (pH 7.4, 5-min accumulation at an open circuit voltage), the sensor responded to cocaine concentration in the range of 100 nM–1.0 mM with a detection limit of 50 nM. Selectivity of the sensor for cocaine relative to some potential inferring compounds was also investigated, and the results were promising. The proposed approach exhibited an extended dynamic range, low detection limit, good sensitivity, and a desirable selectivity, which provides an efficient application prospect for on-field cocaine sensing.

Design and fabrication of zwitter-wettable nanostructured films.

Manipulating surface properties using chemistry and roughness has led to the development of advanced multifunctional surfaces. Here, in a nanostructured polymer film consisting of a hydrophilic reservoir of chitosan/carboxymethyl cellulose capped with various hydrophobic layers, we demonstrate the role of a third design factor, water permeation rate. We use this additional design criterion to produce antifogging coatings that readily absorb water vapor while simultaneously exhibiting hydrophobic character to liquid water. These zwitter-wettable films, produced via aqueous layer-by-layer assembly, consist of a nanoscale thin hydrophobic capping layer (chitosan/Nafion) that enables water vapor to diffuse rapidly into the underlying hydrophilic reservoir rather than nucleating drops of liquid water on the surface. We characterize these novel films using a quartz crystal microbalance with dissipation monitoring (QCM-D) and via depth-profiling X-ray photoelectron spectroscopy (XPS) in addition to extensive testing for fogging/antifogging performance.