NIR-vis-UV Light-Responsive High Stress-Generating Polymer Actuators with a Reduced Creep Rate.

Untethered, light-responsive, high-stress-generating actuators based on widely-used commercial polymers are appealing for applications in soft robotics. However, the construction of actuators that are stable and reversibly responsive to low-intensity ultraviolet, visible, and infrared lights remains challenging. Here, transparent, stress-generating actuators are reported based on ultradrawn, ultrahigh molecular weight polyethylene films. The composite films have different draw ratios (30, 70, and 100) and contain a small amount of graphene in combination with ultraviolet and near-infrared-absorbing dyes. The composite actuators respond rapidly (t0.9 < 0.8 s) to different wavelengths of light (i.e., 780, 455, and 365 nm). A maximum photoinduced stress of 35 MPa is achieved at a draw ratio of 70 under near-infrared light irradiation. The photoinduced stress increases linearly with the light intensity, indicating the transfer of light into thermally induced mechanical contraction. Moreover, the addition of additives lead to a reduction in the plastic creep rate of the drawn films compared to their nonmodified counterparts.

Unravelling humidity-gated, temperature responsive bilayer actuators.

By spraying liquid crystal mixtures onto stretched polyamide 6 (PA6) substrates, dual-responsive heat/humidity bilayer actuators are generated. The oriented PA6 guides the self-organization of the liquid crystal monomers into well-aligned, anisotropic liquid crystal networks. The bilayer responds to changes in the environmental relative humidity, resulting in bending of the actuator with the liquid crystal network inside the curvature. In contrast, in conditions of constant high humidity (80%RH), increasing the temperature triggers the liquid crystal network coating to bend the bilayer in the opposing direction. The dual-responsivity to changes in environmental humidity and temperature is examined in detail and discussed theoretically to elucidate the humidity-gated, temperature responsive properties revealing guidelines for fabricating anisotropic bilayer actuators.

Thermoplastic, rubber-like marine antifouling coatings with micro-structures via mechanical embossing.

New processing routes and materials for non-biocidal, antifouling (AF) coatings with an improved performance are currently much sought after for a range of marine applications. Here, the processing, physical properties and marine AF performance of a fluorinated coating based on a thermoplastic (non-crosslinked) fluorinated polymer are reported. It was found that the addition of lubricating oil and hydrodynamic drag reducing microstructures improved the AF properties substantially, i.e. the settlement of a marine biofilm, containing mixed microalgae including diatoms, was reduced to low levels. More importantly, the remaining fouling was removed from the coatings at low hydrodynamic shear rates and promising AF properties were obtained. Moreover, additional potential benefits were revealed originating from the thermoplastic nature of the coating material which might result in significant cost reductions.

Optical Patterns on Drawn Polyethylene by Direct Laser Writing.

Optical patterns are produced on the surface of drawn linear polyethylene containing 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol (BZT), a photothermal dye, by direct laser writing. The photothermal dye absorbs the UV light and dissipates heat in the polyethylene film. This heat locally results in the melting, shrinking, and recrystallization of PE and the loss of the fibrillar crystalline morphology which is typical for these materials. By using this writing method, an optical image can be obtained by controlling the local UV irradiation dose with a pulsed UV laser. The optical image is visible with the naked eye but also between crossed polarizers giving an overt and covert authentication verification that might be interesting for anti-counterfeit applications.

Surface Micropatterning of Uniaxially Oriented Polyethylene Films Using Interference Holography for Strain Sensors.

A new procedure is presented for direct generation of surface micropatterns on uniaxially oriented polyethylene (PE) films using interference holography with a nanosecond pulsed laser. An ultraviolet absorber, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (BZT) is incorporated into PE prior to stretching to generate absorption at the wavelength of the laser. Illumination with an interference pattern in the absorption band of BZT leads to an obvious height variation in the exposed regions and consequently relief gratings are generated. The height in the exposed regions is strongly dependent on the angle between the grating direction and the film orientation direction. This phenomenon is attributed to a combination of events such as melting, entropic contraction, recrystallization, thermal evaporation of BZT, and anisotropic thermal conductivity. It is shown that the relief height increases with increasing BZT concentration and exhibits a linear dependence on the energy dose above a certain threshold. Additionally, the oriented PE films with the surface micropatterns are explored for strain sensors. The results demonstrate that small strains below 10% are monitored accurately in tensile deformation of the micropatterned, oriented PE films which makes these films potentially useful as strain sensors.

Diffractive flat panel solar concentrators of a novel design.

A novel design for a flat panel solar concentrator is presented which is based on a light guide with a grating applied on top that diffracts light into total internal reflection. By combining geometrical and diffractive optics the geometrical concentration ratio is optimized according to the principles of nonimaging optics, while the thickness of the device is minimized due to the use of total internal reflection.

Humidity-responsive liquid crystalline polymer actuators with an asymmetry in the molecular trigger that bend, fold, and curl.

We show a versatile method for the preparation of a variety of humidity-responsive actuators based on a single sheet of a hydrogen-bonded, uniaxially aligned liquid crystal polymer network. In this approach, the asymmetry in the molecular trigger in the anisotropic polymer film plays a dominant role leading to programmed deformation events. The material is locally treated with a potassium hydroxide solution to create the asymmetry in the responsiveness toward humidity, which allows to prepare actuators that bend, fold, or curl.

Thermoresponsive scattering coating for smart white LEDs.

White light emitting diode (LED) systems, capable of lowering the color temperature of emitted light on dimming, have been reported in the literature. These systems all use multiple color LEDs and complex control circuitry. Here we present a novel responsive lighting system based on a single white light emitting LED and a thermoresponsive scattering coating. The coated LED automatically emits light of lower correlated color temperature (CCT) when the power is reduced. We also present results on the use of multiple phosphors in the white light LED allowing for the emission of warm white light in the range between 2900 K and 4150 K, and with a chromaticity complying with the ANSI standards (C78.377). This responsive warm white light LED-system with close-to-ideal emission characteristics is highly interesting for the lighting industry.

Patterned silver nanoparticles embedded in a nanoporous smectic liquid crystalline polymer network.

A nanoporous smectic liquid crystalline polymer network has been exploited to fabricate photo patternable organic-inorganic hybrid materials, wherein, the nanoporous channels control the diameter and orientational order of the silver nanoparticles.

(Photo-)thermally induced formation of dynamic surface topographies in polymer hydrogel networks.

In this Article, we report on our approaches to creating responsive hydrogel coatings with surfaces that can be switched between a close to flat state and a state with a predesigned topographic pattern. The trigger is either temperature or, indirectly, light. The hydrogel coatings are based on the known thermal responsive poly(N-isopropylacrylamide) utilizing its solubility change at its lower critical solution temperature (LCST) at around 32 °C. Using this material in combination with controlled cross-linking, we developed three fabrication strategies. Thermally switching symmetric surface topographies were created by careful and spatial control of the cross-link density. Sensitivity to light was created by patterns of tin oxide converting absorbed light into local heat. And to broaden the application range, we introduced a method based on volumetric effects created by a corrugated substrate. The latter method allows for the formation of asymmetric or slanted surface structures.

Printable optical sensors based on H-bonded supramolecular cholesteric liquid crystal networks.

A printable H-bonded cholesteric liquid crystal (CLC) polymer film has been fabricated that, after conversion to a hygroscopic polymer salt film, responds to temperature and humidity by changing its reflection color. Fast-responding humidity sensors have been made in which the reflection color changes between green and yellow depending on the relative humidity. The change in reflection band is a result of a change in helix pitch in the film due to absorption and desorption of water, resulting in swelling/deswelling of the film material. When the polymer salt was saturated with water, a red-reflecting film was obtained that can potentially act as a time/temperature integrator. Finally, the films were printed on a foil, showing the potential application of supramolecular CLC materials as low-cost, printable, battery-free optical sensors.

Increased efficiency of luminescent solar concentrators after application of organic wavelength selective mirrors.

Organic wavelength-selective mirrors are used to reduce the loss of emitted photons through the surface of a luminescent solar concentrator (LSC). A theoretical calculation suggests that application of a 400 nm broad reflector on top of an LSC containing BASF Lumogen Red 305 as a luminophore can reflect 91% of all surface emitted photons back into the device. Used in this way, such broad reflectors could increase the edge-emission efficiency of the LSC by up to 66%. Similarly, 175 nm broad reflectors could increase efficiency up to 45%. Measurements demonstrate more limited effectiveness and dependency on the peak absorbance of the LSC. At higher absorbance, the increased number of internal re-absorption events reduces the effectiveness of the reflectors, leading to a maximum increase in LSC efficiency of ~5% for an LSC with a peak absorbance of 1. Reducing re-absorption by reducing dye concentration or the coverage of the luminophore coating results in an increase in LSC efficiency of up to 30% and 27%, respectively.

Molecular machines: nanomotor rotates microscale objects.

Nanomachines of the future will require molecular-scale motors that can perform work and collectively induce controlled motion of much larger objects. We have designed a synthetic, light-driven molecular motor that is embedded in a liquid-crystal film and can rotate objects placed on the film that exceed the size of the motor molecule by a factor of 10,000. The changes in shape of the motor during the rotary steps cause a remarkable rotational reorganization of the liquid-crystal film and its surface relief, which ultimately causes the rotation of submillimetre-sized particles on the film.

Surface-relief and polarization gratings for solar concentrators.

Transmission gratings that combine a large diffraction angle with a high diffraction efficiency and a low angular and wavelength dispersion could be used to collect sunlight in a light guide. In this paper we compare the diffractive properties of polarization gratings and classical surface-relief gratings and explore their possible use in solar concentrators. It is found that polarization gratings and surface-relief gratings have qualitatively comparable diffraction characteristics when their thickness parameters are within the same regime. Relatively large grating periods result in high diffraction efficiencies over a wide range of incident angles. For small grating periods the efficiency and the angular acceptance are decreased. Surface-relief gratings are preferred over polarization gratings as in-couplers for solar concentrators.

Enhanced Thermal Conductivity in Oriented Polyvinyl Alcohol/Graphene Oxide Composites.

Polymer composites have attracted increasing interest as thermal management materials for use in devices owing to their ease of processing and potential lower costs. However, most polymer composites have only modest thermal conductivities, even at high concentrations of additives, resulting in high costs and reduced mechanical properties, which limit their applications. To achieve high thermally conductive polymer materials with a low concentration of additives, anisotropic, solid-state drawn composite films were prepared using water-soluble polyvinyl alcohol (PVA) and dispersible graphene oxide (GO). A co-additive (sodium dodecyl benzenesulfonate) was used to improve both the dispersion of GO and consequently the thermal conductivity. The hydrogen bonding between GO and PVA and the simultaneous alignment of GO and PVA in drawn composite films contribute to an improved thermal conductivity (∼25 W m-1 K-1), which is higher than most reported polymer composites and an approximately 50-fold enhancement over isotropic PVA (0.3-0.5 W m-1 K-1). This work provides a new method for preparing water-processable, drawn polymer composite films with high thermal conductivity, which may be useful for thermal management applications.

Nano-Second Laser Interference Photoembossed Microstructures for Enhanced Cell Alignment.

Photoembossing is a powerful photolithographic technique to prepare surface relief structures relying on polymerization-induced diffusion in a solventless development step. Conveniently, surface patterns are formed by two or more interfering laser beams without the need for a lithographic mask. The use of nanosecond pulsed light-based interference lithography strengthens the pattern resolution through the absence of vibrational line pattern distortions. Typically, a conventional photoembossing protocol consists of an exposure step at room temperature that is followed by a thermal development step at high temperature. In this work, we explore the possibility to perform the pulsed holographic exposure directly at the development temperature. The surface relief structures generated using this modified photoembossing protocol are compared with those generated using the conventional one. Importantly, the enhancement of surface relief height has been observed by exposing the samples directly at the development temperature, reaching approximately double relief heights when compared to samples obtained using the conventional protocol. Advantageously, the light dose needed to reach the optimum height and the amount of photoinitiator can be substantially reduced in this modified protocol, demonstrating it to be a more efficient process for surface relief generation in photopolymers. Kidney epithelial cell alignment studies on substrates with relief-height optimized structures generated using the two described protocols demonstrate improved cell alignment in samples generated with exposure directly at the development temperature, highlighting the relevance of the height enhancement reached by this method. Although cell alignment is well-known to be enhanced by increasing the relief height of the polymeric grating, our work demonstrates nano-second laser interference photoembossing as a powerful tool to easily prepare polymeric gratings with tunable topography in the range of interest for fundamental cell alignment studies.

Optical monitoring of gases with cholesteric liquid crystals.

A new approach to optical monitors for gases is introduced using cholesteric liquid crystals doped with reactive chiral compounds. The approach is based on cholesteric pitch length changes caused by a change in helical twisting power (HTP) of the chiral dopants upon reaction with the analyte. The concept is demonstrated for monitoring carbon dioxide via reversible carbamate formation and for oxygen using the irreversible oxidation of a chiral dithiol to a disulfide. Monitoring of CO(2) was achieved by doping a commercial cholesteric liquid crystalline mixture (E7) with 1.6% mol of the 1:1 complex of an optically pure diamine with a TADDOL derivative. Upon exposure to carbon dioxide, the reflection band of a thin film of the mixture shifted from 637 to 495 nm as a consequence of dissociation of the complex after carbamate formation of the diamine. An O(2) monitor was obtained by doping E7 with a chiral binaphthyl dithiol derivative and a nonresponsive codopant. The reflection band of the oxygen monitor film changed from 542 to 600 nm, due to the conformational change accompanying oxidation of the dithiol to disulfide. These monitoring mechanisms hold promise for application in smart packaging, where carbon dioxide and oxygen are of special interest because of their roles in food preservation.

Printed artificial cilia from liquid-crystal network actuators modularly driven by light.

Polymeric microactuators are potentially useful in micromechanical systems and lab-on-a-chip systems. However, manufacturing of miniature polymeric actuators has been complicated owing to the necessity of including electrodes for actuation or using lithographic techniques for patterning. Here, we demonstrate that all-polymer microdevices can be fabricated using inkjet printing technology in combination with self-organizing liquid-crystal network actuators. We exploit the self-assembling properties of the liquid crystal to create large strain gradients, and light-driven actuation is chosen to allow simple and remote addressing. By using multiple inks, microactuators with different subunits are created that can be selectively addressed by changing the wavelength of the light. The actuators mimic the motion of natural cilia. These artificial cilia have the potential to create flow and mixing in wet environments such as lab-on-a-chip applications. The process is easily adapted for roll-to-roll fabrication, allowing for large-scale and low-cost production of miniaturized active polymer systems.

Fully reversible transition from Wenzel to Cassie-Baxter states on corrugated superhydrophobic surfaces.

Liquid drops on textured surfaces show different dynamical behaviors depending on their wetting states. They are extremely mobile when they are supported by composite solid-liquid-air interfaces (Cassie-Baxter state) and immobile when they fully wet the textured surfaces (Wenzel state). By reversibly switching between these two states, it will be possible to achieve control over the fluid dynamics. Unfortunately, these wetting transitions are usually prevented by surface energy barriers. We demonstrate here a new, simple design paradigm consisting of parallel grooves with an appropriate aspect ratio that allows for the controlled, barrierless, reversible switching of the wetting states upon application of electrowetting. We report a direct observation of the barrierless dynamical pathway for the reversible transitions between the Wenzel (collapsed) and Cassie-Baxter (suspended) states and present a theory that accounts for these transitions, including detailed lattice Boltzmann simulations.

Effect on the output of a luminescent solar concentrator on application of organic wavelength-selective mirrors.

To reduce surface loss in luminescent solar concentrators (LSCs), we systematically apply organic wavelength-selective mirrors, chiral nematic (cholesteric) liquid crystals, onto the LSCs with an air gap and determine their effect on waveguide output. The highest output is achieved using a scattering background and cholesteric mirror with a reflection band significantly redshifted (approximately 150 nm) from the emission peak of the fluorescent dye. The use of an air gap results in light bending away from the waveguide surface normal and, consequently, a redshift of the cholesteric mirrors is required. Up to 35% more dye-emitted light energy exits the waveguide edge after application of the cholesteric, and an increase in absolute edge power of 12% was found for a waveguide using a separate scatterer.