Photomobile Polymer-Piezoelectric Composite for Enhanced Actuation and Energy Generation.

In this study, we present an innovative approach to increase the quantum yield and wavelength sensitivity of photomobile polymer (PMP) films based on azobenzene by doping the polymer matrix with noble metal nanoparticles. These doped PMP films showed faster and more significant bending under both UV as well as visible and near-infrared light regardless of whether it was coherent, incoherent, polarized, or unpolarized irradiation, expanding the potential of PMP-based actuators. To illustrate their practical implications, we created a proof-of-concept model of power generation by coupling it to flexible piezoelectric materials under simulated sunlight. This model has been tested under real operating conditions, thus demonstrating the possibility of generating electricity with variable light exposure. Additionally, our synthetic protocol is solvent-free, which is another benefit of environmental relevance. Our research lays the groundwork for the development of sunlight-sensitive devices, such as photomechanical actuators and advanced photovoltaic modules, which may break ground in the thriving field of smart materials. We are confident that the presented findings will contribute to the ongoing discourse in the field and inspire additional advances in renewable energy applications.

Tungsten disulfide nanotubes enhance flow-induced crystallization and radio-opacity of polylactide without adversely affecting in vitro toxicity.

Treatment of vascular disease, from peripheral ischemia to coronary heart disease (CHD), is poised for transformation with the introduction of transient implants designed to "scaffold" regeneration of blood vessels and ultimately leave nothing behind. Improved materials could expand the use of these devices. Here, we examine one of the leading polymers for bioresorbable scaffolds (BRS), polylactide (PLA), as the matrix of nanocomposites with tungsten disulfide (WS2) nanotubes (WSNT), which may provide mechanical reinforcement and enhance radio-opacity. We evaluate in vitro cytotoxicity using vascular cells, flow-induced crystallization and radio-opacity of PLA-WSNT nanocomposites at low WSNT concentration. A small amount of WSNT (0.1 wt%) can effectively promote oriented crystallization of PLA without compromising molecular weight. And radio-opacity improves significantly: as little as 0.5 to 1 wt% WSNT doubles the radio-opacity of PLA-WSNT relative to PLA at 17 keV. The results suggest that a single component, WSNT, has the potential to increase the strength of BRS to enable thinner devices and increase radio-opacity to improve intraoperative visualization. The in vitro toxicity results indicate that PLA-WSNT nanocomposites are worthy of investigation in vivo. Although substantial further preclinical studies are needed, PLA-WSNT nanocomposites may provide a complement of material properties that may improve BRS and expand the range of lesions that can be treated using transient implants. STATEMENT OF SIGNIFICANCE: Bioresorbable Scaffolds (BRSs) support regeneration of arteries without permanent mechanical constraint. Poly-L-lactide (PLLA) is the structural material of the first approved BRS for coronary heart disease (ABSORB BVS), withdrawn due to adverse events in years 1-3. Here, we examine tungsten disulfide (WS2) nanotubes (WSNT) in PLA to address two contributors to early complications: (1) reinforce PLLA (enable thinner BRS), and (2) increase radiopacity (provide intraoperative visibility). For BRS, it is significant that WSNT disperse, remain dispersed, reduce friction and improve mechanical properties without additional chemicals or surface modifications. Like WS2 nanospheres, bare WSNT and PLA-WSNT nanocomposites show low cytotoxicity in vitro. PLA-WSNT show enhanced flow-induced crystallization relative to PLA, motivating future study of the processing behavior and strength of these materials.

Photo-Responsivity Improvement of Photo-Mobile Polymers Actuators Based on a Novel LCs/Azobenzene Copolymer and ZnO Nanoparticles Network.

The efficiency of photomobile polymers (PMP) in the conversion of light into mechanical work plays a fundamental role in achieving cutting-edge innovation in the development of novel applications ranging from energy harvesting to sensor approaches. Because of their photochromic properties, azobenzene monomers have been shown to be an efficient material for the preparation of PMPs with appropriate photoresponsivity. Upon integration of the azobenzene molecules as moieties into a polymer, they act as an engine, allowing fast movements of up to 50 Hz. In this work we show a promising approach for integrating ZnO nanoparticles into a liquid crystalline polymer network. The addition of such nanoparticles allows the trapping of incoming light, which acts as diffusive points in the polymer matrix. We characterized the achieved nanocomposite material in terms of thermomechanical and optical properties and finally demonstrated that the doped PMP was better performing that the undoped PMP film.

Interaction of Poly L-Lactide and Tungsten Disulfide Nanotubes Studied by in Situ X-ray Scattering during Expansion of PLLA/WS2NT Nanocomposite Tubes.

In situ synchrotron X-ray scattering was used to reveal the transient microstructure of poly(L-lactide) (PLLA)/tungsten disulfide inorganic nanotubes (WS2NTs) nanocomposites. This microstructure is formed during the blow molding process ("tube expansion") of an extruded polymer tube, an important step in the manufacturing of PLLA-based bioresorbable vascular scaffolds (BVS). A fundamental understanding of how such a microstructure develops during processing is relevant to two unmet needs in PLLA-based BVS: increasing strength to enable thinner devices and improving radiopacity to enable imaging during implantation. Here, we focus on how the flow generated during tube expansion affects the orientation of the WS2NTs and the formation of polymer crystals by comparing neat PLLA and nanocomposite tubes under different expansion conditions. Surprisingly, the WS2NTs remain oriented along the extrusion direction despite significant strain in the transverse direction while the PLLA crystals (c-axis) form along the circumferential direction of the tube. Although WS2NTs promote the nucleation of PLLA crystals in nanocomposite tubes, crystallization proceeds with largely the same orientation as in neat PLLA tubes. We suggest that the reason for the unusual independence of the orientations of the nanotubes and polymer crystals stems from the favorable interaction between PLLA and WS2NTs. This favorable interaction leads WS2NTs to disperse well in PLLA and strongly orient along the axis of the PLLA tube during extrusion. As a consequence, the nanotubes are aligned orthogonally to the circumferential stretching direction, which appears to decouple the orientations of PLLA crystals and WS2NTs.

Low-Temperature Growth of ZnO Nanowires from Gravure-Printed ZnO Nanoparticle Seed Layers for Flexible Piezoelectric Devices.

Zinc oxide (ZnO) nanowires (NWs) are excellent candidates for the fabrication of energy harvesters, mechanical sensors, and piezotronic and piezophototronic devices. In order to integrate ZnO NWs into flexible devices, low-temperature fabrication methods are required that do not damage the plastic substrate. To date, the deposition of patterned ceramic thin films on flexible substrates is a difficult task to perform under vacuum-free conditions. Printing methods to deposit functional thin films offer many advantages, such as a low cost, low temperature, high throughput, and patterning at the same stage of deposition. Among printing techniques, gravure-based techniques are among the most attractive due to their ability to produce high quality results at high speeds and perform deposition over a large area. In this paper, we explore gravure printing as a cost-effective high-quality method to deposit thin ZnO seed layers on flexible polymer substrates. For the first time, we show that by following a chemical bath deposition (CBD) process, ZnO nanowires may be grown over gravure-printed ZnO nanoparticle seed layers. Piezo-response force microscopy (PFM) reveals the presence of a homogeneous distribution of Zn-polar domains in the NWs, and, by use of the data, the piezoelectric coefficient is estimated to be close to 4 pm/V. The overall results demonstrate that gravure printing is an appropriate method to deposit seed layers at a low temperature and to undertake the direct fabrication of flexible piezoelectric transducers that are based on ZnO nanowires. This work opens the possibility of manufacturing completely vacuum-free solution-based flexible piezoelectric devices.

Dual-step method to manufacture a polymeric GRIN lens with a high refractive index range.

We introduce a new method to obtain gradient index (GRIN) lenses by dual-step process based on interdiffusion of two different polymeric solutions and gelation of the final mixture. The aim of the study was investigated as a simple process to produce a gel characterized by a continuous axial concentration gradient starting from two thermoplastic polymers [poly(vinyl alcohol) and poly(acrylic acid)] having different refractive indexes. We also introduced a laser scanning system that is conveniently implemented to analyze the refractive index variation in the samples.

All-inkjet-printed thin-film transistors: manufacturing process reliability by root cause analysis.

We report on the detailed electrical investigation of all-inkjet-printed thin-film transistor (TFT) arrays focusing on TFT failures and their origins. The TFT arrays were manufactured on flexible polymer substrates in ambient condition without the need for cleanroom environment or inert atmosphere and at a maximum temperature of 150 °C. Alternative manufacturing processes for electronic devices such as inkjet printing suffer from lower accuracy compared to traditional microelectronic manufacturing methods. Furthermore, usually printing methods do not allow the manufacturing of electronic devices with high yield (high number of functional devices). In general, the manufacturing yield is much lower compared to the established conventional manufacturing methods based on lithography. Thus, the focus of this contribution is set on a comprehensive analysis of defective TFTs printed by inkjet technology. Based on root cause analysis, we present the defects by developing failure categories and discuss the reasons for the defects. This procedure identifies failure origins and allows the optimization of the manufacturing resulting finally to a yield improvement.

Plasma functionalization procedure for antibody immobilization for SU-8 based sensor.

In this paper, we report the study on a new protocol for the immobilization process of antigen/antibody assay on SU-8 layers by oxygen plasma treatment. Plasma treatments, at different plasma powers and for different duration times, are performed and their effects on immobilization efficiency are studied. The chemical properties and the surface morphology of SU-8 before and after the functionalization and immobilization of (IgG) are then verified by Raman spectroscopy and atomic force microscopy (AFM). An increase of the surface roughness of SU-8 layers is observed after the oxygen plasma treatment and an intensity variation of functional groups is also evidenced. To demonstrate the validity of the process the distribution of IgG immobilized on SU-8 surfaces is detected by fluorescence microscopy measurement after incubation with fluorescein isothiocyanate (FITC)-tagged anti-human IgG. An increase of the amount of the adsorbed protein of about 20% and a good repeatability on antigen/antibody distribution on the surface are detected for IgG on plasma treated substrates. Finally, label free measurements are performed by SU-8 optical ring resonators reaching detection limits of 0.86ngcm(-2). The proposed approach offers a smart protocol for IgG immobilization on SU-8 substrate that can be easily extended to different antigen/antibody assay and polymeric materials for the realization of high performance immunosensors.

Modelling of organic field effect transistors with inkjet printed poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) electrodes: study of the annealing effects.

In the present work, the transport mechanism of organic transistors with bottom-gate/top-contact structure, manufactured by employing traditional and inkjet printing techniques, was studied. Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) conductive polymer was used for realizing printed source, drain and gate electrodes. The influence of the printing parameters (substrate temperature, drop overlapping degree, drop emission frequency) on the uniformity and morphology of the PEDOT:PSS layer was investigated. Polymethyl methacrylate (PMMA) was used as organic dielectric and pentacene, deposited by thermal evaporation, was employed as p-type semiconductor. Organic field effect transistors (OFETs) were fabricated and electrically characterized before and after the thermal annealing process at 120 degrees C for 1 h in nitrogen ambient. The effect of the annealing on the performances of the OFETs was investigated by modelling the measured electrical characteristics and analyzing them in terms of mobility, characteristic temperature and energy distribution of the density of localized states (DOS). In addition, the OFET working under electrical stress in ambient conditions was observed and discussed.

Study of the interference effects in an optical cavity for organic light-emitting diode applications.

The interference effects generated in a bottom-emitting electroluminescent device fabricated on a polymer underlayer introduced with the aim of improving the anode roughness have been studied. The analysis of the interference fringes at different detection angles and the spatial coherence demonstrates that this phenomenon is due to multiple internal reflections that propagate in the polymer layer. This effect can be eliminated by modifying the polymer thickness and the incidence angle of the electromagnetic radiation at the anode-polymer interface. Inkjet etching technology is adopted for microcavities-shaped polymer structuring to destroy the resonator effect of the optical cavity.