Exploration of glassy state in Prussian blue analogues

Prussian blue analogues (PBAs), a class of microporous crystalline coordination frameworks, are long known for their diverse properties in porosity, magnetic, charge transport, catalysis, optics, and more. Versatile structural composition and the ability to control defect ordering through synthetic conditions offer opportunities to manipulate the functionality in the crystalline state. However, developments in Prussian blue analogues (PBAs) have primarily revolved around the ordered crystalline state, and the glassy state of PBAs has not yet been explored. Here we report the discovery of a disordered glassy state of the PBA via mechanically induced crystal–glass transformation. We found the preservation of metal–ligand–metal connectivity, confirming the short-range order and semiconductor behaviour, exhibiting an electronic conductivity value of 0.31 mS cm−1 at 50 ˚C. Mechanical-induced glass transformation also triggers changes in electronic states, where electroneutrality is compensated by introducing unconventional CN− vacancies. Partial disorders and ligand vacancies in recrystallized PBA give rise to an enhanced porosity, inaccessible in the crystalline parent. The present work also established a correlation between the mechanical stress required to initiate crystal–glass transformation and intrinsic mechanical properties, which are controlled by the vacancy/defect content, the presence of interstitial water, and the overall composition of PBAs.

Structural, Thermal and Optical Properties of Rare Earth Doped Lead-Tellurite Oxide Glasses

Structural, thermal and optical properties of lead-tellurite oxide glasses consisting TeO2 – PbO – Bi2O3 – Er2O3, synthesized by high temperature melt-quenching-thermal annealing method were investigated in this study. The role of rare-earth element, erbium ion as dopant into the host glass has affected physically, thermally and optically of the glasses. The amorphous nature of the glasses was confirmed by XRD (x-ray diffraction). Thermal exo-endothermic event profiles clarify its glass transformation temperature Tg, crystallization temperature Tx, and melting temperature Tm are exist. Both UV-Vis-NIR optical absorption and Raman spectroscopy have revealed optical energy gap changes due to the structural deformation by the erbium ions. Related obtained glass parameters such as polarizability, refractive indices and metallization criterion were also explained further in this study.

Geochemistry of bentonite clays from the Eastern Rhodopes (SE Bulgaria): preliminary results

In this work we report data from LA-ICP-MS analyses of 7 bentonite samples from the Eastern Rhodopes as three of the samples come from two bentonite deposits – Zlatna Livada and Propast-Dobrovolets. The obtained results show no significant accumulation of trace elements in the studied samples. Their overall chemical composition is strongly influenced by the volcanic glass chemistry, the presence and abundance of magmatic minerals and lithic clasts and to lesser extent by secondary authigenic mineral associations. Respectively, their trace element signature is similar to that of the unaltered extension-related orogenic volcanic rocks in the Eastern Rhodopes. No correlation between any of the trace elements measured and the relative montmorillonite abundance (in samples A-ZL and I-PD) have been established. Nevertheless, these data complete the knowledge of bentonite clays from the Eastern Rhodopes; they can shed more light on the connection between volcanic precursors and alteration products and can provide deeper insight into the process of glass transformation.

A New Strategy to Produce Hemp Fibers through a Waterglass-Based Ecofriendly Process

Natural fibers such as kenaf, hemp, flax, jute, and sisal have become the subject of much research as potential green or eco-friendly reinforcement composites, since they assure the reduction of weight, cost, and CO2 release with less reliance on oil sources. Herein, an inexpensive and eco-friendly waterglass treatment is proposed, allowing the production of silica-coated fibers that can be easily obtained in micro/nano fibrils through a low power mixer. The silica coating has been exploited to improve the chemical compatibility between fibers and the polymer matrix through the reaction of silanol groups with suitable coupling agents. In particular, silica-coated fibers easily functionalized with (3-Aminopropyl) triethoxysilane (APTS) were used as a filler in the manufacturing of epoxy-based composites. Morphological investigation of the composites through Scanning Electron Microscopy (SEM) demonstrated that the filler has a tendency to produce a web-like structure, formed by continuously interconnected fibrils and microfibrils, from which particularly effective mechanical properties may be obtained. Dynamic Mechanical Analysis (DMA) shows that the functionalized fibers, in a concentration of 5 wt%, strongly affect the glass transformation temperature (10 °C increase) and the storage modulus of the pristine resin. Taking into account the large number of organosilicon compounds (in particular the alkoxide ones) available on the market, the new process appears to pave the way for the cleaner and cheaper production of biocomposites with different polymeric matrices and well-tailored interfaces.

Thermal properties of Na2O–P2O5–Fe2O3 polyphosphate glasses

Iron phosphate glasses are materials that can have many applications like durable matrixes in waste immobilization techniques, biomaterials, optoelectronic devices, etc. Their possible usage is related to their glass network and thermal properties. The influence of Na2O content on thermal properties and crystallization ability of iron phosphate glass of base composition 30 Fe2O3–70 P2O5 mol% were studied. Increasing the content of Na2O causes a decrease in transformation temperature and increase in ΔCp. Characteristic temperatures, thermal stability and crystallizing phases were determined. Increasing content of sodium causes depolarization of iron phosphate glass network which causes a continuous change in ΔCp and glass transformation temperature. Discontinuous change in some glass properties suggests structure rebuilding about 30 mol% of Na2O.