The possibility to assess diffusion coefficients of small molecules in packaging polymer films directly on the shelf, or even along the fabrication line, without the use laboratory equipment commonly employed for gravimetric methods would represent a paradigm changer in the evaluation of barrier properties and byproduct formation in goods packaging and device encapsulation. In this work, we demonstrate a simple, effective and versatile method for the determination of the molecular diffusion coefficients that exploits simple UV-Vis spectroscopy and is suitable for any polymer film. This simple method also allows the direct identification of the intercalating molecule without the need for chemical targeting or of complex laboratory equipment. For this purpose, we report on the assessment of diffusion coefficients of both polar and non-polar molecules including water, ammonia, methanol, ethanol, toluene, and even hexafluorobenzene into polyvinyl chloride wrap commercialized for food packaging.
A holistic detection system, in principle sensitive to any molecular species in the vapor phase is proposed. The sensor consists of a polymeric multilayered distributed Bragg reflector made of a perfluorinated polar polymer, Aquivion, and a nonpolar polymer, poly(N‐vinylcarbazole). Alternated layers of the two polymers provide a characteristic optical response that depends on the chemical species intercalating within the structure. Such differences arise from Flory–Huggins polymer–solvent interactions. Then, the presence of polar, nonpolar, and perfluorinated moieties in the structures, potentially, allows sensitivity to any molecular species, providing a detection system with no need for any additional chemical receptors. As a proof of concept, the study demonstrates the sensitivity of the sensor to very diverse classes of molecules in the vapor phase including perfluorinated, nonpolar hydrophobic, and hydrophilic species and the capability to distinguish them, even in binary mixtures. Additionally, a connection between the dynamic temporal response of the sensors and the chemical–physical properties of the analytes, their concentration, and effective diffusion coefficient within the polymer structure is revealed.
Historically, photonic crystals have been made of inorganic high refractive index materials coupled to air voids to maximize the dielectric contrast and in turn the light confinement. However, these systems are complex, costly, and time-demanding, and the fabrication processes are difficult to scale. Polymer structures promise to tackle this issue thanks to their easy solution and melt processing. Unfortunately, their low dielectric contrast limits their performance. In this work, we propose a concise but exhaustive review of the common polymers employed in the fabrication of planar 1D photonic crystals and new approaches to the enhancement of their dielectric contrast. Transfer matrix method modeling will be employed to quantify the effect of this parameter in standardized structures and to propose a new polymer structure for applications dealing with light management.
Solution processing of highly performing photonic crystals has been a towering ambition for making them technologically relevant in applications requiring mass and large-area production. It would indeed represent a paradigm changer for the fabrication of sensors and for light management nanostructures meant for photonics and advanced photocatalytic systems. On the other hand, solution-processed structures often suffer from low dielectric contrast and poor optical quality or require complex deposition procedures due to the intrinsic properties of components treatable from solution. This work reports on a low-temperature sol–gel route between the alkoxides of Si and Ti and poly(acrylic acid), leading to stable polymer–inorganic hybrid materials with tunable refractive index and, in the case of titania hybrid, photoactive properties. Alternating thin films of the two hybrids allows planar photonic crystals with high optical quality and dielectric contrast as large as 0.64. Moreover, low-temperature treatments also allow coupling the titania hybrids with several temperature-sensitive materials including dielectric and semiconducting polymers to fabricate photonic structures. These findings open new perspectives in several fields; preliminary results demonstrate that the hybrid structures are suitable for sensing and the enhancement of the catalytic activity of photoactive media and light emission control.
Multilayered photonic sensors that rely on polymer‐solvent Flory–Huggins interactions are drawing increasing interest owing to their broad‐band selectivity, even among mixtures, without the need for chemical targeting. Moreover, these sensors provide simple colorimetric responses, and easy, quick fabrication both on laboratory and industrial scales. However, complex optical responses and slow response times are limiting their development. In this work, the behavior of different photonic sensor architectures is analyzed to speed up response time and define a strategy to simplify their spectral behavior. To this end, the effect of interfaces, materials order, and thickness on the diffusion kinetics of a single reference analyte in the multilayered sensors is studied to design the optimal structure.
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