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.

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.

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.

The Role of Polyethylene Wax on the Thermal Conductivity of Transparent Ultradrawn Polyethylene Films.

Transparency and thermal conductivity of ultradrawn, ultrahigh-molecular-weight polyethylene films containing different contents of low-molecular-weight polyethylene wax (PEwax) are explored from experimental and theoretical viewpoints. It is shown that the addition of PEwax decreases light scattering in all directions, resulting from a reduction of defects while having little effect on crystallinity or chain orientation of ultradrawn films. In general, upon the addition of PEwax, the thermal conductivity of ultradrawn films increases with the highest conductivity being 47 (W m-1 K-1) and subsequently decreases at higher concentrations. The thermal conductivity also depends on draw ratio and number-average molecular weight (Mn) of the films. A model is presented which correlates the thermal conductivity of the films with the draw ratio and Mn, enabling explanation of the experimental results. Hence, the thermal conductivity of ultradrawn polyethylene films can be predicted as a function of Mn and draw ratio.

Ultra-High Actuation Stress Polymer Actuators as Light-Driven Artificial Muscles.

Remotely addressable actuators are of great interest in fields like microrobotics and smart textiles because of their simplicity, integrity, flexibility, and lightweight. However, most of the existing actuator systems are composed of complex assemblies and/or offer a low response rate. Here, the actuation performance of a light-driven, highly oriented film based on ultra-high molecular weight polyethylene (UHMW-PE), containing a photo-responsive additive, 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol (BZT), is reported. The material exhibits a fast (<1 s) and reversible photo-induced thermal response upon exposure to UV light, which results in an exceptionally high actuation stress (∼70 MPa) at a low strain (<0.1%). The proposed actuation mechanism originates from light absorption by BZT and energy transfer into heat, in combination with the intrinsic high stiffness (∼80 GPa) and a negative thermal expansion (NTE) of the oriented polymer films. This unique set of properties of this actuator, in particular the very high specific actuation stress, compared to existing organic and inorganic actuators, and the remote optical actuation, promises impact in fields related to soft robotics, composites, medical devices, optics, prosthetics, and smart textiles.

Direct Laser Writing of Four-Dimensional Structural Color Microactuators Using a Photonic Photoresist.

With the advent of direct laser writing using two-photon polymerization, the generation of high-resolution three-dimensional microstructures has increased dramatically. However, the development of stimuli-responsive photoresists to create four-dimensional (4D) microstructures remains a challenge. Herein, we present a supramolecular cholesteric liquid crystalline photonic photoresist for the fabrication of 4D photonic microactuators, such as pillars, flowers, and butterflies, with submicron resolution. These micron-sized features display structural color and shape changes triggered by a variation of humidity or temperature. These findings serve as a roadmap for the design and creation of high-resolution 4D photonic microactuators.

An Optical Steam Sterilization Sensor Based On a Dual-Responsive Supramolecular Cross-Linked Photonic Polymer.

An optical time-temperature steam sensor is presented based on the loss of structural color in a supramolecularly cross-linked cholesteric liquid crystal photonic coating. A gradual decrease in the selective reflection band is observed upon exposure to temperatures above 105 °C related to the cholesteric to isotropic transition temperature. The linear polymers with carboxylic acid side chains provide physical cross-linking through hydrogen bonding that allows a time-temperature-dependent order loss through the dynamic equilibrium between supramolecular dimer and free monomer states. Steam is accelerating the color loss, and autoclave experiments show that the photonic supramolecular polymer is applicable as a steam sterilization sensor for medical applications.

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.

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.

Transparent, High-Thermal-Conductivity Ultradrawn Polyethylene/Graphene Nanocomposite Films.

Transparent, ultradrawn, ultrahigh molecular weight polyethylene (UHMWPE)/graphene nanocomposite films with a high thermal conductivity are successfully fabricated by solution-casting and solid-state drawing. It is found that the low optical transmittance (<75%) of the ultradrawn UHMWPE/graphene composite films is drastically improved (>90%) by adding 2-(2H-benzontriazol-2-yl)-4,6-ditertpentylphenol (BZT) as a second additive. This high transmission is interpreted in terms of a reduced void content in the composite films and the improved dispersion of graphene both of which decrease light scattering. The high thermal conductivity is attributed to the π-π interaction between BZT and graphene. In addition, a high specific thermal conductivity of ≈75 W m-1 K-1 ρ-1 of the ultradrawn UHMWPE/graphene/BZT composite films is obtained, which is higher than most metals and polymer nanocomposite. These transparent films are potentially excellent candidates for thermal management in various applications due to a combination of low density, ease of processing, and high thermal conductivity.

Rewritable Optical Patterns in Light-Responsive Ultrahigh Molecular Weight Polyethylene.

Spiropyran is used as a photochromic dye to create colored patterns in highly drawn ultrahigh molecular weight polyethylene (UHMW PE) films. The dye is incorporated in highly crystalline, drawn UHMW PE tapes and fibers and isomerizes to its merocyanine state upon UV light irradiation, resulting in a color change from transparent to purple. The isomerization from merocyanine to spiropyran to erase the color can be simply induced by using heat or a green LED light. The combination of the use of a mask and the reversibility of the isomerization results in colored patterns that can be written, erased, and rewritten using UV light and heat or green LED light.

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.

Degradation and biocompatibility of photoembossed PLGA-acrylate blend for improved cell adhesion.

We have shown previously that PMMA-acrylate photopolymers are biocomopatible and can exhibit improved cell adhesion compared to PMMA, due to an increase in negative surface charge caused by UV radiation PLGA has been used widely in soft tissue regeneration due to its high biocompatibility and cell adhesion. This polymer is also biodegradable and can be utilised in the field of vascular regeneration. In this study, PLGA is blended with a triacrylate monomer (TPETA) to create a degradable photopolymer blend. Surface relief structures are formed on this PLGA-TPETA by photoembossing. An optimum height of 950 nm was achieved for a 10 µm pitch with the height of these relief structures being controlled by changing UV intensity, processing temperature and time. Degradation studies of this blend revealed a bulk degradation mechanism with PLGA-TPETA degrading slower compared to pure PLGA. We also evaluated the adhesion of human umbilical vein endothelial cells (HUVECs) on both smooth and textured PLGA-TPETA films. Embossed PLGA-TPETA films showed improved cell adhesion compared to smooth substrates. Furthermore, HUVECs proliferated faster on the embossed surface compared to their smooth counterparts. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 163-171, 2018.

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.

Photonic Shape Memory Polymer with Stable Multiple Colors.

A photonic shape memory polymer film that shows large color response (∼155 nm) in a wide temperature range has been fabricated from a semi-interpenetrating network of a cholesteric polymer and poly(benzyl acrylate). The large color response is achieved by mechanical embossing of the photonic film above its broad glass transition temperature. The embossed film, as it recovers to its original shape on heating through the broad thermal transition, exhibits multiple structural colors ranging from blue to orange. The relaxation behavior of the embossed film can be fully described using a Kelvin-Voigt model, which reveals that the influence of temperature on the generation of colors is much stronger than that of time, thereby producing stable multiple colors.

Responses of Vascular Endothelial Cells to Photoembossed Topographies on Poly(Methyl Methacrylate) Films.

Failures of vascular grafts are normally caused by the lack of a durable and adherent endothelium covering the graft which leads to thrombus and neointima formation. A promising approach to overcome these issues is to create a functional, quiescent monolayer of endothelial cells on the surface of implants. The present study reports for the first time on the use of photoembossing as a technique to create polymer films with different topographical features for improved cell interaction in biomedical applications. For this, a photopolymer is created by mixing poly(methyl methacrylate) (PMMA) and trimethylolpropane ethoxylate triacrylate (TPETA) at a 1:1 ratio. This photopolymer demonstrated an improvement in biocompatibility over PMMA which is already known to be biocompatible and has been extensively used in the biomedical field. Additionally, photoembossed films showed significantly improved cell attachment and proliferation compared to their non-embossed counterparts. Surface texturing consisted of grooves of different pitches (6, 10, and 20 µm) and heights (1 µm and 2.5 µm). The 20 µm pitch photoembossed films significantly accelerated cell migration in a wound-healing assay, while films with a 6 µm pitch inhibited cells from detaching. Additionally, the relief structure obtained by photoembossing also changed the surface wettability of the substrates. Photoembossed PMMA-TPETA systems benefited from this change as it improved their water contact angle to around 70°, making it well suited for cell adhesion.

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.

Improving the Transparency of Ultra-Drawn Melt-Crystallized Polyethylenes: Toward High-Modulus/High-Strength Window Application.

Highly transparent, ultradrawn high-density polyethylene (HDPE) films were successfully prepared using compression molding and solid-state drawing techniques. The low optical transmittance (<50%) of the pure drawn HDPE films can be drastically improved (>90%) by incorporating a small amount (>1 wt %/wt) of specific additives to HDPE materials prior to drawing. It is shown that additives with relatively high refractive index result in an increased optical transmittance in the visible light wavelength which illustrates that the improvement in optical characteristics probably originates from refractive index matching between the crystalline and noncrystalline regions in the drawn films. Moreover, the optically transparent drawn HDPE films containing additives maintain their physical and mechanical properties, especially their high modulus and high strength, which make these films potentially useful in a variety of applications, such as high-impact windows.

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.