Novel Physical Vapor Deposition Approach to Hybrid Perovskites: Growth of MAPbI3 Thin Films by RF-Magnetron Sputtering

Solution-based methods represent the most widespread approach used to deposit hybrid organic-inorganic perovskite films for low-cost but efficient solar cells. However, solution-process techniques offer limited control over film morphology and crystallinity, and most importantly do not allow sequential film deposition to produce perovskite-perovskite heterostructures. Here the successful deposition of CH3NH3PbI3 (MAPI) thin films by RF-magnetron sputtering is reported, an industry-tested method to grow large area devices with precisely controlled stoichiometry. MAPI films are grown starting from a single-target made of CH3NH3I (MAI) and PbI2. Films are single-phase, with a barely detectable content of unreacted PbI2, full surface coverage and thickness ranging from less than 200 nm to more than 3 {\mu}m. Light absorption and emission properties of the deposited films are comparable to as-grown solution-processed MAPI films. The development of vapor-phase deposition methods is of interest to advance perovskite photovoltaic devices with the possibility of fabricating perovskite multijunction solar cells or multicolor bright light-emitting devices in the whole visible spectrum

Photocuring of Epoxidized Cardanol for Biobased Composites with Microfibrillated Cellulose

Cardanol is a natural alkylphenolic compound derived from Cashew NutShell Liquid (CNSL), a non-food annually renewable raw material extracted from cashew nutshells. In the quest for sustainable materials, the curing of biobased monomers and prepolymers with environmentally friendly processes attracts increasing interest. Photopolymerization is considered a green technology owing to low energy requirements, room temperature operation with high reaction rates, and absence of solvents. In this work we study the photocuring of a commercially available epoxidized cardanol, and explore its use in combination with microfibrillated cellulose (MFC) for the fabrication of fully biobased composites. Wet MFC mats were prepared by filtration, and then impregnated with the resin. The impregnated mats were then irradiated with UV light. Fourier Transform InfraRed (FTIR) spectroscopy was used to investigate the photocuring of the epoxidized cardanol, and of the composites. The thermomechanical properties of the composites were assessed by thermogravimetric analysis, differential scanning calorimetry and dynamic mechanical analysis. We confirmed that fully cured composites could be obtained, although a high photoinitiator concentration was needed, possibly due to a side reaction of the photoinitiator with MFC

Photoinduced Processes as a Way to Sustainable Polymers and Innovation in Polymeric Materials

Photoinduced processes have gained considerable attention in polymer science and have greatly implemented the technological developments of new products. Therefore, a large amount of research work is currently developed in this area: in this paper we illustrate the advantages of a chemistry driven by light, the present perspectives of the technology, and summarize some of our recent research works, honoring the memory of Prof. Aldo Priola who passed away in March 2021 and was one of the first scientists in Italy to contribute to the field

Enhancing properties and water resistance of PEO-based electrospun nanofibrous membranes by photo-crosslinking

Abstract In this study, modified fibrous mats of poly(ethylene oxide) (PEO) were fabricated through the versatile technique of electrospinning. Acrylic monomers were added to PEO with different composition ratios, and the mats were irradiated. The kinetics of photo-cross-linking reaction in the presence of the acrylic cross-linkers, as well as the structural, thermal and mechanical properties of the nanofibers, were studied. The morphology of the fibrous membranes before and after water treatment was monitored, and the insoluble fraction of the fibers was measured. As a result, by tuning the photo-cross-linking reaction, the control over fibers properties was feasible. The photo-cured PEO-based nanofibrous mats showed the solubility resistance needed to use them as membranes and to apply them in aqueous environments, as in water treatment processes and biomedical applications. Graphical Abstrac

Suspension electrospinning of SBR latex combined with photo-induced crosslinking: control of nanofiber composition, morphology, and properties

Suspension electrospinning of a styrene-butadiene rubber (SBR) latex coupled with photo-induced crosslinking in ambient conditions is proposed as a rapid method to prepare ultrafine shape-stable rubber fibrous membranes. Polyethylene oxide (PEO) is used as template polymer and can eventually be removed from the nanostructured membrane by a simple water treatment. A multifunctional thiol crosslinker and an appropriate photo-initiating system are added to the latex to allow the fast and efficient photo-induced crosslinking of the nanofibers, based on thiol addition to the SBR double bonds, as demonstrated by real-time Infrared spectroscopy analyses. It is proved that by varying the PEO template polymer and the thiol crosslinker content, a fine control of the chemical composition, morphology, water solubility, and thermal properties of the nanofibrous membranes is ensured. Moreover, comparable mechanical properties to those of fibrous membranes produced by conventional electrospinning of organic solvent-based solutions are obtained, clearly showing the attractiveness of the present method, especially in terms of process sustainability

Compositionally Graded Hydrophobic UV-Cured Coatings for the Prevention of Glass Stress Corrosion

The use of glass in architecture is growing and is moving towards structural applications. However, the tensile strength of glass cannot be fully exploited because of stress corrosion. This is a corrosion triggered by stress applied to the material and dependent on environmental factors such as humidity and temperature. To protect glass from stress corrosion, we developed a UV-cured coating, characterized by hydrophobicity, barrier to water vapor properties, and good adhesion to glass, thanks to a compositional profile. The coating was obtained by combining a cycloaliphatic diacrylate resin with a very low amount of a perfluoropolyether methacrylate co-monomer, which migrated to the free surface, creating a compositionally graded coating. The adhesion to glass was improved, using as a primer an acrylated silane able to co-react with the resins. With a mechanical load test using the coaxial double ring set-up, we proved that the coating is effective in the inhibition of stress corrosion of glass plates, with an increase of 76% of tensile strength

Structure of Starch-Sepiolite Bio-Nanocomposites: Effect of Processing and Matrix-Filler Interactions

Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of applications, such as packaging. Herein, the effect of the processing (i.e., starch gelatinization, addition of glycerol as plasticizer, casting to obtain films) and of the sepiolite filler amount on the microstructure of starch-based nanocomposites was investigated by SS-NMR (solid-state nuclear magnetic resonance), XRD (X-ray diffraction) and FTIR (Fourier-transform infrared) spectroscopy. Morphology, transparency and thermal stability were then assessed by SEM (scanning electron microscope), TGA (thermogravimetric analysis) and UV-visible spectroscopy. It was demonstrated that the processing method allowed to disrupt the rigid lattice structure of semicrystalline starch and thus obtain amorphous flexible films, with high transparency and good thermal resistance. Moreover, the microstructure of the bio-nanocomposites was found to intrinsically depend on complex interactions among sepiolite, glycerol and starch chains, which are also supposed to affect the final properties of the starch-sepiolite composite materials

SiO2/Ladder-Like Polysilsesquioxanes Nanocomposite Coatings: Playing with the Hybrid Interface for Tuning Thermal Properties and Wettability

The present study explores the exploitation of ladder-like polysilsesquioxanes (PSQs) bearing reactive functional groups in conjunction with SiO2 nanoparticles (NPs) to produce UV-curable nanocomposite coatings with increased hydrophobicity and good thermal resistance. In detail, a medium degree regular ladder-like structured poly (methacryloxypropyl) silsesquioxane (LPMASQ) and silica NPs, either naked or functionalized with a methacrylsilane (SiO2@TMMS), were blended and then irradiated in the form of a film. Material characterization evidenced significant modifications of the structural organization of the LPMASQ backbone and, in particular, a rearrangement of the silsesquioxane chains at the interface upon introduction of the functionalized silica NPs. This leads to remarkable thermal resistance and enhanced hydrophobic features in the final nanocomposite. The results suggest that the adopted strategy, in comparison with mostly difficult and expensive surface modification and structuring protocols, may provide tailored functional properties without modifying the surface roughness or the functionalities of silsesquioxanes, but simply tuning their interactions at the hybrid interface with silica fillers

Differential vaginal expression of interleukin-1 system cytokines in the presence of Mycoplasma hominis and Ureaplasma urealyticum in pregnant women.

OBJECTIVE: The genital mycoplasmas, Ureaplasma urealyticum and Mycoplasma hominis, are commonly identified in the vagina of healthy pregnant women. However, these microorganisms are the most common isolates from the amniotic fluids of women in preterm labor. The mechanisms responsible for vaginal colonization and ascent to the uterus remain undetermined. We evaluated the association between U. urealyticum and M. hominis vaginal colonization and the presence of pro-inflammatory and anti-inflammatory interleukin-1 system components in asymptomatic pregnant women of different ethnicities. METHODS: Vaginal specimens, obtained from 224 first trimester pregnant women, were assayed for interleukin-1beta (IL-1beta) and IL-1 receptor antagonist (IL-1ra) concentrations by ELISA. U. urealyticum and M. hominis vaginal colonization were identified by polymerase chain reaction (PCR). RESULTS: Vaginal colonization with M. hominis was identified in 37 (16.5%) women, and was more prevalent in black (18.9%) and Hispanic (20.9%) than in white (4.2%) women (p = 0.01). U. urealyticum was present in 84 (37.5%) women and there was no ethnic disparity in its detection. M. hominis colonization was associated with elevated median vaginal IL-1beta concentrations in both black women (p = 0.02) and Hispanic women (p = 0.04), and was unrelated to vaginal IL-1ra concentrations. In marked contrast, U. urealyticum colonization was associated with elevations in vaginal IL-1ra levels, but not with IL-1beta concentrations, in black women (p = 0.02) and Hispanic women (p < 0.0001) and marginally in white women (p = 0.06). CONCLUSION: M. hominis colonization in healthy pregnant women is associated with localized pro-inflammatory immune activation, while U. urealyticum colonization is associated with immune suppression