Structure, gas-barrier properties and overall migration of poly(lactic acid) films coated with hydrogenated amorphous carbon layers

Hydrogenated amorphous carbon (a-C:H) films were grown on a poly(lactic acid) (PLA) substrate by means of a radiofrequency plasma-enhanced chemical vapour deposition (rf-PECVD) technique with different deposition times (5, 20 and 40 min). The main goal of this treatment was to increase the barrier properties of PLA, maintaining its original transparency and colour as well as controlling interactions with food simulants for packaging applications. Morphological, chemical, and mechanical properties of PLA/a-C:H systems were evaluated while permeability and overall migration tests were performed in order to determine the effect of the plasma treatment on the gas-barrier properties of PLA films and their application in food packaging. Morphological results suggested a good adhesion of the deposited layers onto the polymer surface and the samples treated for 5 and 20 min only slightly darkened the PLA film. X-ray photoelectron spectroscopy revealed that the structural properties of the carbon layer deposited onto the PLA film depend on the exposure time. PLA/a-C:H system treated for 5 min showed the highest barrier properties, while none of the studied samples exceeded the migration limit established by the current legislation, suggesting the suitability of these materials in packaging applications.

Growth of Carbon Nanotubes on Surfaces: The Effects of Catalyst and Substrate

We report a study of synthesising air-stable, nearly monodispersed bimetallic colloids of Co/Pd and Fe/Mo of varying compositions as active catalysts for the growth of carbon nanotubes. Using these catalysts we have investigated the effects of catalyst and substrate on the carbon nanostructures formed in a plasma-enhanced chemical vapour deposition (PECVD) process. We will show how it is possible to assess the influence of both the catalyst and the support on the controlled growth of carbon nanotube and nanofiber arrays. The importance of the composition of the catalytic nuclei will be put into perspective with other results from the literature. Furthermore, the influence of other synthetic parameters such as the nature of the nanoparticle catalysts will also be analysed and discussed in detail.

Oxygen evolution at ultrathin nanostructured Ni(OH)2 layers deposited on conducting glass

Ultrathin and transparent nanostructured Ni(OH)2 films were deposited on conducting glass (F:SnO2) by a urea-based chemical bath deposition method. By controlling the deposition time, the amount of deposited Ni(OH)2 was varied over 7 orders of magnitude. The turnover number for O2 generation, defined as the number of O2 molecules generated per catalytic site (Ni atom) and per second, increases drastically as the electrocatalyst amount decreases. The electrocatalytic activity of the studied samples (measured as the current density at a certain potential) increases with the amount of deposited Ni(OH)2 until a saturation value is already obtained for a thin film of around 1 nm in thickness, composed of Ni(OH)2 nanoplatelets lying flat on the conductive support. The deposition of additional amounts of catalyst generates a porous honeycomb structure that does not improve (only maintains) the electrocatalytic activity. The optimized ultrathin electrodes show a remarkable stability, which indicates that the preparation of highly transparent electrodes, efficient for oxygen evolution, with a minimum amount of nickel is possible.

Improving the Photoelectrochemical Response of TiO2 Nanotubes upon Decoration with Quantum-Sized Anatase Nanowires

TiO2 nanotubes (NTs) have been widely used for a number of applications including solar cells, photo(electro)chromic devices, and photocatalysis. Their quasi-one-dimensional morphology has the advantage of a fast electron transport although they have a relatively reduced interfacial area compared with nanoparticulate films. In this study, vertically oriented, smooth TiO2 NT arrays fabricated by anodization are decorated with ultrathin anatase nanowires (NWs). This facile modification, performed by chemical bath deposition, allows to create an advantageous self-organized structure that exhibits remarkable properties. On one hand, the huge increase in the electroactive interfacial area induces an improvement by 1 order of magnitude in the charge accumulation capacity. On the other hand, the modified NT arrays display larger photocurrents for water and oxalic acid oxidation than bare NTs. Their particular morphology enables a fast transfer of photogenerated holes but also efficient mass and electron transport. The importance of a proper band energy alignment for electron transfer from the NWs to the NTs is evidenced by comparing the behavior of these electrodes with that of NTs modified with rutile NWs. The NT-NW self-organized architecture allows for a precise design and control of the interfacial surface area, providing a material with particularly attractive properties for the applications mentioned above.

Potentiostatic Reversible Photoelectrochromism: An Effect Appearing in Nanoporous TiO2/Ni(OH)2 Thin Films

In the field of energy saving, finding composite materials with the ability of coloring upon both illumination and change of the applied electrode potential keeps on being an important goal. In this context, chemical bath deposition of Ni(OH)2 into nanoporous TiO2 thin films supported on conducting glass leads to electrodes showing both conventional electrochromic behavior (from colorless to dark brown and vice versa) together with photochromism at constant applied potential. The latter phenomenon, reported here for the first time, is characterized by fast and reversible coloration upon UV illumination. The bleaching kinetics shows first order behavior with respect to the NiIII centers in the film, and an order 1.2 with respect to electrons in the TiO2 film. From a more applied point of view, this study opens up the possibility of having two-mode smart windows showing not only conventional electrochromism but also reversible darkening upon illumination.