This work reports on the first attempt to prepare bioderived polymer films by blending polylactic acid (PLA) and poly(dodecylene furanoate) (PDoF). This blend, containing 10 wt% PDoF, was filled with reduced graphene oxide (rGO) in variable weight fractions (from 0.25 to 2 phr), and the resulting nanocomposites were characterized to assess their microstructural, thermal, mechanical, optical, electrical, and gas barrier properties. The PLA/PDoF blend resulted as immiscible, and the addition of rGO, which preferentially segregated in the PDoF phase, resulted in smaller (from 2.6 to 1.6 µm) and more irregularly shaped PDoF domains and in a higher PLA/PDoF interfacial interaction, which suggests the role of rGO as a blend compatibilizer. rGO also increased PLA crystallinity, and this phenomenon was more pronounced when PDoF was also present, thus evidencing a synergism between PDoF and rGO in accelerating the crystallization kinetics of PLA. Dynamic mechanical thermal analysis (DMTA) showed that the glass transition of PDoF, observed at approx. 5 °C, shifted to a higher temperature upon rGO addition. The addition of 10 wt% PDoF in PLA increased the strain at break from 5.3% to 13.0% (+145%), and the addition of 0.25 phr of rGO increased the tensile strength from 35.6 MPa to 40.2 MPa (+13%), without significantly modifying the strain at break. Moreover, rGO decreased the electrical resistivity of the films, and the relatively high percolation threshold (between 1 and 2 phr) was probably linked to the low aspect ratio of rGO nanosheets and their preferential distribution inside PDoF domains. PDoF and rGO also modified the optical transparency of PLA, resulting in a continuous decrease in transmittance in the visible/NIR range. Finally, rGO strongly modified the gas barrier properties, with a remarkable decrease in diffusivity and permeability to gases such as O₂, N_2, and CO₂. Overall, the presented results highlighted the positive and sometimes synergistic role of PDoF and rGO in tuning the thermomechanical and functional properties of PLA, with simultaneous enhancement of ductility, crystallization kinetics, and gas barrier performance, and these novel polymer nanocomposites could thus be promising for packaging applications.

This study explores the co-deposition of thin polymeric films loaded with nanoparticles for its possible future application as radiation detectors. Thin films containing zinc oxide (ZnO) nanoparticles in plasma polymerized n-hexane (PPH) were deposited on silicon substrates using an atmospheric pressure plasma jet (APPJ). Crystalline ZnO nanoparticles were produced by wet chemistry, characterized, and injected through the plasma with an aerosol buffer. The precursor hydrocarbon was polymerized in atmosphere at room temperature by the plasma, resulting in a highly crosslinked structure chemically stable against common solvents. The polymer structure was characterized by FT-IR, NMR, and thermal analyses. Photoluminescence analysis revealed that ZnO UV excitonic emission is recovered owing to the passivation through polymeric encapsulation, with a remarkable increase in luminescence yield.

Two-dimensional transition metal dichalcogenides (TMDCs) are demonstrated to be appealing semiconductors for optoelectronic applications, thanks to their remarkable properties in the ultraviolet-visible spectral range. Interestingly, TMDCs have not yet been characterized when exposed to x rays, although they would be ideal candidates for optoelectronic applications in this spectral range. They benefit from the high cross section of the constituent heavy atoms, while keeping the absorption very low, due to the ultrathin structure of the film. This encourages the development of photodetectors based on TMDCs for several applications dealing with x rays, such as radioprotection, medical treatments, and diagnosis. Given the atomic thickness of TMDCs, they can be expected to perform well at low dose measurements with minimal perturbation of the radiation beam, which is required for in vivo applications. In this paper, the use of TMDCs as active materials for direct x-ray detection is demonstrated, using a photodetector based on a MoS2 monolayer (1L-MoS2). The detector shows a response to x rays in the range of 101–102 keV, at dose rates as low as fractions of mGy/s. The sensitivity of 1L-MoS2 reaches values in the range of 108–109µC Gy−1 cm−3, overcoming the values reported for most of the organic and inorganic materials. To improve the x-ray photoresponse even further, the 1L-MoS2 was coupled with a polymeric film integrating a scintillator based on terbium-doped gadolinium oxysulfide (Gd2O2S:Tb). The resulting signal was three times larger, enabled by the indirect x ray to visible photoconversion mechanism. This paper might pave the way toward the production of ultrathin real-time dosimeters for in vivo applications.

The aim of this work is to highlight the correlation between treatment conditions, composition, and structure of reduced zinc oxide (ZnO:Zn) with optical and radioluminescence properties for the production of high yield scintillating powders. Purchased zinc oxide (ZnO) powders (≈0.35 ± 0.15 μm) were thermally reduced in Ar/H₂ (3%) atmosphere at temperatures ranging between 600 (≈0.40 ± 0.17 μm) and 1000 °C (≈6.4 ± 1.6 μm), obtaining ZnO:Zn powders. The reduction degree, evaluated through energy dispersive spectroscopy, showed a linear increase from 0% up to 20% (800 °C sample), reaching a plateau condition at about 25% for the highest treatment temperatures (1000 °C sample). Structural analysis highlighted the existence of a threshold temperature, previously reported in the literature, around 800 °C, beyond which (i) the grain size remarkably increases, (ii) the shape changes from hexagonal to round-shaped, and (iii) the intensity of electron spin resonance (ESR)-active defects at g = 1.9596 decreases for a new resonance at g = 2.0105. Additionally, a substantial variation, from 5.63 ± 0.02 down to 5.2 ± 0.1 g/cm³, of the skeletal density and a slight contraction of the optical bandgap are observed. Unlike the structural properties, PL and x-ray radioluminescence showed a continuous increase of the green emission intensity, associated with ESR-active ionized oxygen vacancies and ESR non-active recombination centers, and of the PL defective lifetimes (33 ns < τ_fast < 88 ns, 395 ns < τ_slow < 930 ns).

Organic phase change materials, e.g., paraffins, are attracting increasing attention in thermal energy storage (TES) and thermal management applications. However, they also manifest interesting optical properties such as thermotropism, as they can switch from optically opaque to transparent reversibly and promptly at the melting temperature. This work aims at exploiting this feature to produce flexible silicone-based blends with thermotropic properties for applications in glazed windows or thermal sensors. Blends are produced by adding paraffin (T_m = 44 °C, up to 10 phr) to a silicone bicomponent mixture, and, for the first time, cetyltrimethylammonium bromide (CTAB) is also added to promote paraffin dispersion and avoid its exudation. CTAB is proven effective in preventing paraffin exudation both in the solid and in the liquid state when added in a fraction above 3 phr with respect to paraffin. Rheological results show that paraffin decreases the complex viscosity, but neither paraffin nor CTAB modifies the curing behavior of silicone, which indicates uniform processability across the investigated compositions. On the other hand, paraffin causes a decrease in the stress and strain at break at 60 °C, and this effect is amplified by CTAB, which acts as a defect and stress concentrator. Conversely, at room temperature, solid paraffin only slightly impairs the mechanical properties, while CTAB increases both the elastic modulus and tensile strength, as also highlighted with ANOVA. Finally, optical transmittance results suggest that the maximum transmittance difference below and above the melting temperature (65–70 percentage points) is reached for paraffin amounts of 3 to 5 phr and a CTAB amount of max. 0.15 phr.