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.

Reduction of Lead and Antimony Ions from the Crystal Glass Wastewaters Utilising Adsorption

The presented research examined five adsorbents, i.e., zeolite 4A, a mixture of three zeolites (4A, 13X, and ZSM-5), natural zeolite (tuff), activated carbon, and peat, and their potential capability for removal of exceeded ions of lead (Pb), antimony (Sb), sulphates (SO42−), and fluorides (F−) from real wastewater generated in the crystal glass industry, which was previously treated in-situ by flocculation, with the aim to attain the statutory values for discharge into watercourses or possible recycling. The screening experiment evidenced that the tuff was the most suitable adsorbent for the reduction of Pb (93.8%) and F− (98.1%). It also lowered wastewater’s pH sufficiently from 9.6 to 7.8, although it was less appropriate for the reduction of Sb (66.7%) as compared to activated carbon (96.7%) or peat (99.9%). By adjusting the pH of the initial wastewater to pH 5, its adsorption capacity even enlarged. Results from the tuff-filled column experiment revealed reduction of Pb up to 97%, Sb up to 80%, and F− up to 96%, depending on the velocity flow, and thus it could be used for post-treatment (and recycling) of wastewaters from the crystal glass industry. Moreover, the system showed an explicit buffering capacity, but negligible reduction of the SO42−.

Corrosion of Longquan celadons in the marine environment: study on the celadons from the Dalian Island shipwreck of the Yuan Dynasty

The Dalian ("Image missing") Island shipwreck of the Yuan Dynasty (1271–1368 CE) was located in the sea area of Pingtan ("Image missing"), Fujian ("Image missing") Province, China. A total of 603 Longquan ("Image missing") celadon wares were excavated, some of which have been severely corroded. In this study, two celadon specimens with severe corrosion were selected to investigate the corrosion mechanism in the marine environment. Optical microscopy (OM), scanning electron microscopy equipped with energy dispersive X-ray spectrometry (SEM–EDS), X-ray diffraction analysis (XRD), Micro-Raman spectroscopy, and thermal expansion analysis were applied to analyze the microstructure of the glaze, corrosion morphology, and composition of corrosion products, and the corrosion mechanism was discussed in depth. The results showed that these two celadon wares are opaque matt glaze, in which the anorthite crystallization-phase separation structure with low chemical stability was found, which was more likely to be corroded. There are three possible stages in the corrosion process of the glaze. The first stage is mainly the long-term cation exchange reaction. Then, because of the corrosion of the CaO-rich droplet phase and the crystal-glass phase interface layer, the porous structure and many microcracks may be formed, promoting the corrosion process. Finally, many corrosion craters, caused by the shedding of anorthite crystals, may appear on the glaze surface. The quintinite group minerals in the glaze were probably formed during the corrosion process, which may be related to the marine buried environment and the corrosion of the glaze. This study discussed the influencing factors of the corrosion process of celadon wares in the marine environment from the perspective of microstructure for the first time, which is of great significance to the study of the corrosion mechanism of ancient ceramics.

The Possibility of a Non-Lagrangian Theory of Gravity

General Relativity resembles a very elegant crystal glass: If we touch its principles, that is, its Lagrangian, there is a risk of breaking everything. Or, if we will, it is like a short blanket: Curing some problems creates new problems. This paper is devoted to bring to light the reasons why we pursue the possibility of a non-Lagrangian theory of gravity under the hypothesis of an extension of the original general relativity with an ansatz inspired in the fundamental principles of classical and quantum physics.

Thermal Expansion of Metal–Organic Framework Crystal–Glass Composites

<a>Metal-organic framework crystal-glass composites (MOF CGCs) are a class of materials comprising a crystalline framework embedded within a MOF glass matrix. Here, we investigate the thermal expansion behavior of three MOF CGCs, incorporating two flexible (MIL-53(Al) and MIL-118) and one rigid (UL-MOF-1) MOF within a ZIF-62 glass matrix. Specifically, variable-temperature powder X-ray diffraction data and thermo-mechanical analysis show the suppression of thermal expansivity in each of these three crystalline MOFs when suspended within a ZIF-62 glass matrix. In particular, for the two flexible frameworks, the average volumetric thermal expansion (<i>β</i>) was found to be near-zero in the crystal-glass composite.</a> These results provide a route to engineering thermal expansivity in stimuli-responsive MOF glass composites.

Thermal Expansion of Metal–Organic Framework Crystal–Glass Composites

<a>Metal-organic framework crystal-glass composites (MOF CGCs) are a class of materials comprising a crystalline framework embedded within a MOF glass matrix. Here, we investigate the thermal expansion behavior of three MOF CGCs, incorporating two flexible (MIL-53(Al) and MIL-118) and one rigid (UL-MOF-1) MOF within a ZIF-62 glass matrix. Specifically, variable-temperature powder X-ray diffraction data and thermo-mechanical analysis show the suppression of thermal expansivity in each of these three crystalline MOFs when suspended within a ZIF-62 glass matrix. In particular, for the two flexible frameworks, the average volumetric thermal expansion (<i>β</i>) was found to be near-zero in the crystal-glass composite.</a> These results provide a route to engineering thermal expansivity in stimuli-responsive MOF glass composites.