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Nd3+-doped, LaF3-based, transparent oxyfluoride glass-ceramics (GCs) containing Ag nanoparticles (NPs) have been prepared by a melt-quenching method. Different Ag-containing precursors were employed, with AgNO3 as the most suitable for obtaining Ag NPs segregated in the glassy matrix. Transmission electron microscopy and X-ray absorption spectroscopy determined the presence of Ag0 NPs, with higher concentrations in glass-ceramics produced in an inert atmosphere (N2). The spectral features of emission and excitation spectra, in addition to the different lifetimes of the 4 F3/2 state in the co-doped samples with Ag NPs, demonstrate the incorporation of Nd3+ ions into the LaF3 nanocrystals. The relative contribution to the emission from Nd3+ in the nanocrystals depends on the Ag concentration and atmosphere. The glass-ceramic co-doped with 0.2 wt% Ag, thermally treated in N2, exhibits the highest contribution of emissions attributable to Nd3+ ions in the crystalline phase. The crystalline fraction is similar to that of a Ag-free sample synthesized under analogous conditions. This increase of the luminescence is likely attributable to the enhancement of the local electric field in the LaF3 nanocrystals due to the presence of Ag0 NPs.

[EN] The flash phenomenon in flash sintering of ceramic materials is closely related to electrical conductivity of the material. However, our understanding of how particle-to-particle contact of ceramic powders affects this phenomenon and, consequently, the microstructure and electrical properties of flash-sintered materials remains limited. To address this, we utilized “pseudo-in-situ” impedance spectroscopy to investigate the effect of particle-to-particle contact in nanometric powders of ZnO and 8YSZ, both before and after flash sintering. The powders were prepared using two different procedures, either grinding with a binder or employing multiple milling and calcining steps. After compacting into pellets, the samples were characterized before and after flash sintering, either with current-to-voltage control or with the application of current density ramps until the flash event occurred. Pseudo-in-situ impedance was employed to demonstrate that preparing powders using multiple milling and calcining steps improved charge-carrier mobility paths, facilitated homogeneous passage of electric current, reduced thermal gradients, and consequently resulted in better microstructural homogeneity and electrical conductivity. In addition, the use of the electric-current ramp control retained microstructural homogeneity to a greater degree.

In this study, transparent oxyfluoride glass-ceramics (GCs) with NaLaF4 nanocrystals (NCs) were prepared by the sol–gel method for the first time. Three different molar ratios of La(CH3COO)3/Na(CH3COO) were used to obtain the GCs, which were sintered at 450, 550 and 650 °C for 1 min. X-ray diffraction (XRD) was employed to follow the evolution of the xerogel during the heat treatments and to study crystal growth for the three temperatures. In all cases, the LaF3 crystalline phase was present, but crystallization of NaLaF4 was only promoted at 650 °C. Thermogravimetric and thermodifferential analysis (TGA-DTA) and Fourier transform infrared spectroscopy (FTIR) were used to analyze the crystallization process. High-resolution transmission electron microscopy (HRTEM) was employed to confirm NaLaF4 crystallization and determine the size distribution. The incorporation of Nd3+ ion into NaLaF4 and LaF3 nanocrystals was confirmed by site-selective emission and excitation spectra. The Nd3+ emission intensities in both phases depend not only on the NaLaF4/LaF3 ratio but also on their emission efficiencies.

[EN] Glass-ceramics based on the Eu/Dy-doped SrMgSiO phosphor have been obtained from sintering and crystallization of glass powders. Electric and gas furnaces were employed for glass melting. The doped parent glasses show red emission under excitation of UV light whereas the corresponding glass-ceramics show blue emission. The microstructure of the glass-ceramics and the crystals responsible for the blue emission were observed by scanning electron microscopy-cathodoluminescence. The composition of the crystallised phases and the distribution and incorporation of rare-earth (RE) ions into the crystals and remaining glassy phase were determined by X-ray diffraction and energy dispersive X-ray analysis, respectively. Photoluminescence emission spectra showed a main peak at 484 nm assigned to the typical Eu transitions under excitation at 390 nm in the glass-ceramics. The presence of Dy improved persistence in the samples melted in the gas furnace. The glass-ceramics are sensitive to temperature, which modifies both the persistence time and red-blue luminescence.

Protonic ceramic fuel cells (PCFCs) are promising electrochemical devices for the efficient and clean conversion of hydrogen and low hydrocarbons into electrical energy. Their intermediate operation temperature (500–800 °C) proffers advantages in terms of greater component compatibility, unnecessity of expensive noble metals for the electrocatalyst, and no dilution of the fuel electrode due to water formation. Nevertheless, the lower operating temperature, in comparison to classic solid oxide fuel cells, places significant demands on the cathode as the reaction kinetics are slower than those related to fuel oxidation in the anode or ion migration in the electrolyte. Cathode design and composition are therefore of crucial importance for the cell performance at low temperature. The different approaches that have been adopted for cathode materials research can be broadly classified into the categories of protonic–electronic conductors, oxide-ionic–electronic conductors, triple-conducting oxides, and composite electrodes composed of oxides from two of the other categories. Here, we review the relatively short history of PCFC cathode research, discussing trends, highlights, and recent progress. Current understanding of reaction mechanisms is also discussed.

In this study, transparent oxyfluoride glass-ceramics (GCs) with NaLaF4 nanocrystals (NCs) were prepared by the sol–gel method for the first time. Three different molar ratios of La(CH3COO)3/Na(CH3COO) were used to obtain the GCs, which were sintered at 450, 550 and 650 °C for 1 min. X-ray diffraction (XRD) was employed to follow the evolution of the xerogel during the heat treatments and to study crystal growth for the three temperatures. In all cases, the LaF3 crystalline phase was present, but crystallization of NaLaF4 was only promoted at 650 °C. Thermogravimetric and thermodifferential analysis (TGA-DTA) and Fourier transform infrared spectroscopy (FTIR) were used to analyze the crystallization process. High-resolution transmission electron microscopy (HRTEM) was employed to confirm NaLaF4 crystallization and determine the size distribution. The incorporation of Nd3+ ion into NaLaF4 and LaF3 nanocrystals was confirmed by site-selective emission and excitation spectra. The Nd3+ emission intensities in both phases depend not only on the NaLaF4/LaF3 ratio but also on their emission efficiencies.

[EN] Glass-ceramics based on the Eu 2 O 3 /Dy 2 O 3 -doped Sr 2 MgSi 2 O 7 phosphor have been obtained from sinter- ing and crystallization of glass powders. The doped parent glasses show red emission under excitation of UV light. After thermal treatment, the corresponding glass-ceramics show persistent blue emission which emanates from Eu 2 + incorporated in the crystals; red emission also occurs from Eu 3 + in the residual vitreous phase. The aim of this work is to investigate the structure of defects such as oxygen and strontium vacancies in the Sr 2 MgSi 2 O 7 crystals and the environment, oxidation state and coordination of the Eu and Dy ions in the glass-ceramics, their partitioning between crystalline and glassy phase and their influence on lu- minescence properties, employing X-ray absorption spectroscopy (XAS) and neutron diffraction (ND) as investigative structural tools. We suggest that the luminescence mechanism involves the presence of shal- low electron traps that are abruptly emptied for temperatures above 100 K. The most persistent lumines- cence is likely due to an effective concentration of Eu 2 + in the dendritic-shaped crystals in one of the particular compositions, and with a suitable level of Sr vacancies, even though Sr vacancies are most likely formed in all the investigated samples.

Glass-ceramic materials with composition 0.9Nd(3+)-80SiO(2)-20LaF(3) were successfully obtained and further heat-treated at 450 degrees C for 6 h. Stable and homogeneous LaF3 nanoparticle suspensions with and without Nd3+ were first prepared by a chemical route, incorporating polyvinylpyrrolidone (PVP) as dispersant. The suspensions were then concentrated and characterised by XRD, HRTEM and zeta potential, confirming that LaF3 crystallises as the only phase, with particle size around 16 nm. The suspensions were incorporated in a silica sol to obtain a 0.9Nd(3+)-20LaF(3)-80SiO(2) particulate sol, xerogel and glass-ceramic. HRTEM confirmed the homogeneous incorporation of the doped nanocrystals into the SiO2 matrix without modification of the nanoparticle structure. Rietveld refinement was used to determine the crystallinity and quantity of LaF3 nanoparticles present in the glass-ceramic after treatment of the particulate sol at 450 degrees C for 6 h. Luminescence measurements of near infrared Nd3+ ion emissions in the lanthanum fluoride nanoparticles and SiO2-LaF3 glass-ceramic showed well-structured emission spectra with lifetimes similar to those of theoretical Nd+3 in LaF3 crystals

Glass-ceramic materials with composition 0.9Nd3+–80SiO2–20LaF3 were successfully obtained and further heat-treated at 450 °C for 6 h. Stable and homogeneous LaF3 nanoparticle suspensions with and without Nd3+ were first prepared by a chemical route, incorporating polyvinylpyrrolidone (PVP) as dispersant. The suspensions were then concentrated and characterised by XRD, HRTEM and zeta potential, confirming that LaF3 crystallises as the only phase, with particle size around 16 nm. The suspensions were incorporated in a silica sol to obtain a 0.9Nd3+–20LaF3–80SiO2 particulate sol, xerogel and glass-ceramic. HRTEM confirmed the homogeneous incorporation of the doped nanocrystals into the SiO2 matrix without modification of the nanoparticle structure. Rietveld refinement was used to determine the crystallinity and quantity of LaF3 nanoparticles present in the glass-ceramic after treatment of the particulate sol at 450 °C for 6 h. Luminescence measurements of near infrared Nd3+ ion emissions in the lanthanum fluoride nanoparticles and SiO2–LaF3 glass-ceramic showed well-structured emission spectra with lifetimes similar to those of theoretical Nd+3 in LaF3 crystals.

The potential of interactive layers of mixed-conducting oxides for improving the performance of air electrodes of solid oxide cells in the intermediate-temperature range is demonstrated. Active layers of CeGdO (CGO), CePrO (CPO), and SrFeMoO (SFM) with thickness in the range 200-400 nm are deposited on CGO-based electrolyte by spray pyrolysis, followed by deposition of a SFM/CGO composite air electrode by painting. The morphologies and phase composition of the active layers are examined by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy microanalysis. The electrochemical performance of the electrolyte-electrode assemblies is determined by impedance spectroscopy in the range 600-800 °C. Significant improvements in the performance of the electrode process and the geometrically normalized ohmic conductance are observed for the assembly with a CPO active layer with mixed-oxide-ionic-electronic conductivity, especially in the low-temperature range, attributable to extension of the surface path of the electrochemical reactions. The CGO intermediate layer also improves performance but to a lesser degree, most likely due to better ionic-current collection in comparison to the assemblies with either SFM as the active layer or no active layer.

Transparent oxyfluoride glass-ceramic films and self-supported layers with composition 80SiO₂-20LaF₃ doped with Er3+ have been successfully synthesized by sol-gel process for the first time. Crack-free films and self-supported layer with a maximum thickness up to 1.4 m were obtained after heat treatment at the low temperature of 550 °C for 1 min, resulting in a LaF₃ crystal fraction of 18 wt%, as confirmed by quantitative Rietveld refinement. This is the highest value reported up to now for transparent oxyfluoride glass-ceramics prepared by sol-gel. This work provides a new synthesis strategy and opens the way to a wide range of potential applications of oxyfluoride glass-ceramics. The characterization by a wide range of techniques revealed the homogeneous precipitation of LaF₃ nanocrystals into the glass matrix. X-ray absorption spectroscopy and electron paramagnetic resonance confirmed that the Er3+ ions are preferentially embedded in the low phonon-energy LaF₃ nanocrystals. Moreover, photoluminescence (PL) measurements confirmed the incorporation of dopants in the LaF₃ nanocrystals. The effective concentration of rare-earth ions in the LaF₃ nanocrystals is also estimated by X-ray absorption spectroscopy.

[EN] Exploring the reasons for the initiation of Al-O-Al bond formation in alkali-earth alumino silicate glasses is a key topic in the glass-science community. Evidence for the formation of Al-O-Al and Al-NBO bonds in the glass composition 38.7CaO-9.7MgO-12.9AlO-38.7SiO (CMAS, mol%) has been provided based on Molecular Dynamics (MD) simulations. Analyses in the short-range order confirm that silicon and the majority of aluminium cations form regular tetrahedra. Well-separated homonuclear (Si-O-Si) and heteronuclear (Si-O-Al) cluster regions have been identified. In addition, a channel region (C-Region), separated from the network region, enriched with both NBO and non-framework modifier cations, has also been identified. These findings are in support of the previously proposed extended modified random network (EMRN) model for aluminosilicate glasses. A detailed analysis of the structural distributions revealed that a majority of Al, 51.6%, is found in Si-O-Al links. Although the formation of Al-O-Al and Al-NBO bonds is energetically less favourable, a significant amount of Al is found in Al-O-Al links (33.5%), violating Lowenstein's rule, and the remainder is bonded with non-bridging oxygen (NBO) in the form of Al-NBO (Al-O-(Ca, Mg)). The conditions necessary for the formation of less favourable bonds are attributed to the presence of a high amount of modifier cations in current CMAS glass and their preferable coordination.

Transparent oxyfluoride glass-ceramic films and self-supported layers with composition 80SiO2-20LaF3 doped with Er3+ have been successfully synthesized by sol-gel process for the first time. Crack-free films and self-supported layer with a maximum thickness up to 1.4 µm were obtained after heat treatment at the low temperature of 550 °C for 1 min, resulting in a LaF3 crystal fraction of 18 wt%, as confirmed by quantitative Rietveld refinement. This is the highest value reported up to now for transparent oxyfluoride glass-ceramics prepared by sol-gel. This work provides a new synthesis strategy and opens the way to a wide range of potential applications of oxyfluoride glass-ceramics. The characterization by a wide range of techniques revealed the homogeneous precipitation of LaF3 nanocrystals into the glass matrix. X-ray absorption spectroscopy and electron paramagnetic resonance confirmed that the Er3+ ions are preferentially embedded in the low phonon-energy LaF3 nanocrystals. Moreover, photoluminescence (PL) measurements confirmed the incorporation of dopants in the LaF3 nanocrystals. The effective concentration of rare-earth ions in the LaF3 nanocrystals is also estimated by X-ray absorption spectroscopy.