Pr3+-doped YPO4 nanocrystal embedded into an optical fiber.

Optical fiber with YPO4:Pr3+ nanocrystals (NCs) is presented for the first time using the glass powder-NCs doping method. The method's advantage is separate preparation of NCs and glass to preserve luminescent and optical properties of NCs once they are incorporated into optical fiber. The YPO4:Pr3+ nanocrystals were synthesized by the co-precipitation and hydrothermal methods, optimized for size (< 100 nm), shape, Pr3+ ions concentration (0.2 mol%), and emission lifetime. The core glass was selected from the non-silica P2O5-containing system with refractive index (n = 1.788) close to the NCs (no = 1.657, ne = 1.838). Optical fiber was drawn by modified powder-in-tube method after pre-sintering of glass powder-YPO4:Pr3+ (wt 3%) mixture to form optical fiber preform. Luminescent properties of YPO4:Pr3+ and optical fiber showed their excellent agreement, including sharp Pr3+ emission at 600 nm (1D2-3H4) and 1D2 level lifetime (τ = 156 ± 5 µs) under 488 nm excitation. The distribution of the YPO4:Pr3+ NCs in optical fiber were analyzed by TEM-EDS in the core region (FIB-SEM-prepared). The successful usage of glass powder-NCs doping method was discussed in the aspect of promising properties of the first YPO4:Pr3+ doped optical fiber as a new way to develop active materials for lasing applications, among others.

Broadband Profiled Eye-Safe Emission of LMA Silica Fiber Doped with Tm3+/Ho3+ Ions.

LMA (Large Mode Area) optical fibers are presently under active investigation to explore their potential for generating laser action or broadband emission directly within the optical fiber structure. Additionally, a wide mode profile significantly reduces the power distribution density in the fiber cross-section, minimizing the power density, photodegradation, or thermal damage. Multi-stage deposition in the MCVD-CDT system was used to obtain the structural doping profile of the LMA fiber multi-ring core doped with Tm3+ and Tm3+/Ho3+ layer profiles. The low alumina content (Al2O3: 0.03wt%) results in low refractive index modification. The maximum concentrations of the lanthanide oxides were Tm2O3: 0.18wt % and Ho2O3: 0.15wt%. The double-clad construction of optical fiber with emission spectra in the eye-safe spectral range of (1.55-2.10 µm). The calculated LP01 Mode Field Diameter (MFD) was 69.7 µm (@ 2000 nm, and 1/e of maximum intensity), which confirms LMA fundamental mode guiding conditions. The FWHM and λmax vs. fiber length are presented and analyzed as a luminescence profile modification. The proposed structured optical fiber with a ring core can be used in new broadband optical radiation source designs.

Broadband 1.5-2.1 µm emission in gallo-germanate dual-core optical fiber co-doped with Er3+ and Yb3+/Tm3+/Ho3.

The near-infrared emission in fabricated low-phonon energy, gallo-germanate glass, and double-core optical fiber has been investigated. Broadband amplified spontaneous emission (ASE) was obtained in optical fiber with cores doped with: 1st - 0.2Er2O3 and 2nd - 0.5Yb2O3/0.4Tm2O3/0.05Ho2O3 as a result of the superposition of emission bands from both cores corresponding to the Er3+:4I13/2→4I15/2 (1st core) and Tm3+:3F4 → 3H6/Ho3+:5I7 → 5I8 (2nd core) transitions. The effect of fiber length and pump wavelength on the near-infrared amplified spontaneous emission (ASE) properties has been analyzed for 1 m and 5 m optical fiber. The widest emission bandwidth (355 nm - 3 dB level) was obtained for a 5 m length optical fiber pumped by a 940 nm laser.

Tm3+/Ho3+ profiled co-doped core area optical fiber for emission in the range of 1.6-2.1 µm.

Double-clad optical fiber with a multi-ring core profile doped with thulium and holmium fabricated by Modified Chemical Vapor Deposition Chelate Doping Technology (MCVD-CDT) is presented. The measured Tm2O3 and Ho2O3 complexes' weight concentrations were 0.5% and 0.2% respectively. Numerical analyses show weakly guiding conditions and 42.2 µm of MFD LP01 at 2000 nm. The low NA numerical aperture (NA = 0.054) was obtained for the 20/250 µm core/cladding ratio optical fiber construction. The emission spectra in the range of 1.6-2.1 µm vs. the fiber length are presented. The full width at half maximum (FWHM) decreases from 318 to 270 nm for fiber lengths from 2 to 10 m. The presented fiber design is of interest for the development of new construction of optical fibers operating in the eye-safe spectral range.

Analysis of Excitation Energy Transfer in LaPO4 Nanophosphors Co-Doped with Eu3+/Nd3+ and Eu3+/Nd3+/Yb3+ Ions.

Nanophosphors are widely used, especially in biological applications in the first and second biological windows. Currently, nanophosphors doped with lanthanide ions (Ln3+) are attracting much attention. However, doping the matrix with lanthanide ions is associated with a narrow luminescence bandwidth. This paper describes the structural and luminescence properties of co-doped LaPO4 nanophosphors, fabricated by the co-precipitation method. X-ray structural analysis, scanning electron microscope measurements with EDS analysis, and luminescence measurements (excitation 395 nm) of LaPO4:Eu3+/Nd3+ and LaPO4:Eu3+/Nd3+/Yb3+ nanophosphors were made and energy transfer between rare-earth ions was investigated. Tests performed confirmed the crystal structure of the produced phosphors and deposition of rare-earth ions in the structure of LaPO4 nanocrystals. In the range of the first biological window (650-950 nm), strong luminescence bands at the wavelengths of 687 nm and 698 nm (5D0 → 7F4:Eu3+) and 867 nm, 873 nm, 889 nm, 896 nm, and 907 nm (4F3/2 → 4I9/2:Nd3+) were observed. At 980 nm, 991 nm, 1033 nm (2F5/2 → 2F7/2:Yb3+) and 1048 nm, 1060 nm, 1073 nm, and 1080 nm (4F3/2 → 4I9/2:Nd3+), strong bands of luminescence were visible in the 950 nm-1100 nm range, demonstrating that energy transfer took place.

Tellurite Glasses from the 70TeO2-5XO-10P2O5-10ZnO-5PbF2(X= Pb, Bi, Ti) System Doped Erbium Ions-The Influence of Erbium on the Structure and Physical Properties.

In this article, we present research on the influence of erbium ions on the structure and magneto-optical properties of 70TeO2-5XO-10P2O5-10ZnO-5PbF2 (X = Pb, Bi, Ti) tellurite glass systems. Structural changes occurring in the glasses during doping with erbium ions were investigated using positron annihilation lifetime spectroscopy (PALS) and Raman spectroscopy. The X-ray diffraction (XRD) method was used to confirm the amorphous structure of the investigated samples. Based on the Faraday effect measurements and calculated values of Verdet constant, the magneto-optical properties of the glasses were determined.

Correction: Highly efficient green up-conversion emission from fluoroindate glass nanoparticles functionalized with a biocompatible polymer.

[This corrects the article DOI: 10.1039/D2RA03171J.].

The Effect of Fluorides (BaF2, MgF2, AlF3) on Structural and Luminescent Properties of Er3+-Doped Gallo-Germanate Glass.

The effect of BaF2, MgF2, and AlF3 on the structural and luminescent properties of gallo-germanate glass (BGG) doped with erbium ions was investigated. A detailed analysis of infrared and Raman spectra shows that the local environment of erbium ions in the glass was influenced mainly by [GeO]4 and [GeO]6 units. Moreover, the highest number of non-bridging oxygens was found in the network of the BGG glass modified by MgF2. The 27Al MAS NMR spectrum of BGG glass with AlF3 suggests the presence of aluminum in tetra-, penta-, and octahedral coordination geometry. Therefore, the probability of the 4I13/2→4I15/2 transition of Er3+ ions increases in the BGG + MgF2 glass system. On the other hand, the luminescence spectra showed that the fluoride modifiers lead to an enhancement in the emission of each analyzed transition when different excitation sources are employed (808 nm and 980 nm). The analysis of energy transfer mechanisms shows that the fluoride compounds promote the emission intensity in different channels. These results represent a strong base for designing glasses with unique luminescent properties.

Highly efficient green up-conversion emission from fluoroindate glass nanoparticles functionalized with a biocompatible polymer.

Up-conversion nanoparticles have garnered lots of attention due to their ability to transform low energy light (near-infrared) into high-energy (visible) light, enabling their potential use as remote visible light nano-transducers. However, their low efficiency restricts their full potential. To overcome this disadvantage, fluoroindate glasses (InF3) doped at different molar concentrations of Yb3+ and Er3+ were obtained using the melting-quenching technique, reaching the highest green emission at 1.4Yb and 1.75Er (mol%), which corresponds to the 4S3/2 → 4I15/2 (540-552 nm) transition. The particles possess the amorphous nature of the glass and have a high thermostability, as corroborated by thermogravimetric assay. Furthermore, the spectral decay curve analysis showed efficient energy transfer as the rare-earth ions varied. This was corroborated with the absolute quantum yield (QY) obtained (85%) upon excitation at 385 nm with QYEr = 17% and QYYb = 68%. Additionally, InF3-1.4Yb-1.75Er was milled and functionalized using poly(ethylene glycol) to impart biocompatibility, which is essential for biomedical applications. Such functionalization was verified using FTIR, TG/DSC, and XRD.

Crystallization Mechanism and Optical Properties of Antimony-Germanate-Silicate Glass-Ceramic Doped with Europium Ions.

Glass-ceramic is semi-novel material with many applications, but it is still problematic in obtaining fibers. This paper aims to develop a new glass-ceramic material that is a compromise between crystallization, thermal stability, and optical properties required for optical fiber technology. This compromise is made possible by an alternative method with a controlled crystallization process and a suitable choice of the chemical composition of the core material. In this way, the annealing process is eliminated, and the core material adopts a glass-ceramic character with high transparency directly in the drawing process. In the experiment, low phonon antimony-germanate-silicate glass (SGS) doped with Eu3+ ions and different concentrations of P2O5 were fabricated. The glass material crystallized during the cooling process under conditions similar to the drawing processes'. Thermal stability (DSC), X-ray photo analysis (XRD), and spectroscopic were measured. Eu3+ ions were used as spectral probes to determine the effect of P2O5 on the asymmetry ratio for the selected transitions (5D0 → 7F1 and 5D0 → 7F2). From the measurements, it was observed that the material produced exhibited amorphous or glass-ceramic properties, strongly dependent on the nucleator concentration. In addition, the conducted study confirmed that europium ions co-form the EuPO4 structure during the cooling process from 730 °C to room temperature. Moreover, the asymmetry ratio was changed from over 4 to under 1. The result obtained confirms that the developed material has properties typical of transparent glass-ceramic while maintaining high thermal stability, which will enable the fabrication of fibers with the glass-ceramic core.

TEMPO-oxidized cellulose for in situ synthesis of Pt nanoparticles. Study of catalytic and antimicrobial properties.

In this work, platinum nanoparticles (PtNPs) were synthesized by a modified polyol process using TEMPO-oxidized nanocellulose (TOCN) as a stabilizing and co-reducing agent. Different ratios of TOCN nanocellulose to Pt4+ ions were studied to establish the optimum stabilizing effect of PtNPs. The effect of different pH of aqueous TOCN suspensions on the morphology of PtNPs was also examined. It was proved that PtNPs can be obtained solely in the presence of TOCN without the use of an additional reducing agent or ethylene glycol. The morphology and structural properties of the nanocellulose­platinum nanoparticles composites were assessed using spectroscopic, microscopic and diffraction techniques, The catalytic performance in 4-nitrophenol reduction was evaluated. Significant differences in reaction rate constants k were found depending on the pH of the TOCN suspension applied during Pt4+ reduction. The crucial effect of reaction conditions on PtNPs performance was confirmed in tests of antibacterial efficacy against E. coli.

The Utilisation of Solid Fuels Derived from Waste Pistachio Shells in Direct Carbon Solid Oxide Fuel Cells.

The comprehensive results regarding the physicochemical properties of carbonaceous materials that are obtained from pistachio shells support their usage as solid fuels to supply direct carbon solid oxide fuel cells (DC-SOFCs). The influence of preparation conditions on variations in the chemical composition, morphology of the biochar powders, and degree of graphitization of carbonaceous materials were investigated. Based on structural investigations (X-ray diffraction analysis and Raman spectroscopy), it was observed that disordered carbon particles developed during the application of thermal treatments. The use of X-ray fluorescence enabled a comparative analysis of the chemical composition of the inorganic matter in biocarbon-based samples. Additionally, the gasification of carbonaceous-based samples vs. time at a temperature of 850 °C was investigated in a H2O or CO2 gas atmosphere. The analysis demonstrated the conversion rate of biochar obtained from pistachio shells to H2, CH4 and CO during steam gasification. The electrochemical investigations of the DC-SOFCs that were supplied with biochars obtained from pistachio shells were characterized by satisfactory values for the current and power densities at a temperature range of 700-850 °C. However, a higher power output of the DC-SOFCs was observed when CO2 was introduced to the anode chamber. Therefore, the impact of the Boudouard reaction on the performance of DC-SOFCs was confirmed. The chars that were prepared from pistachio shells were adequate for solid fuels for utilization in DC-SOFCs.

Structure and Luminescence Properties of Transparent Germanate Glass-Ceramics Co-Doped with Ni2+/Er3+ for Near-Infrared Optical Fiber Application.

An investigation of the structural and luminescent properties of the transparent germanate glass-ceramics co-doped with Ni2+/Er3+ for near-infrared optical fiber applications was presented. Modification of germanate glasses with 10-20 ZnO (mol.%) was focused to propose the additional heat treatment process controlled at 650 °C to obtain transparent glass-ceramics. The formation of 11 nm ZnGa2O4 nanocrystals was confirmed by the X-ray diffraction (XRD) method. It followed the glass network changes analyzed in detail (MIR-Mid Infrared spectroscopy) with an increasing heating time of precursor glass. The broadband 1000-1650 nm luminescence (λexc = 808 nm) was obtained as a result of Ni2+: 3T2(3F) → 3A2(3F) octahedral Ni2+ ions and Er3+: 4I13/2 → 4I15/2 radiative transitions and energy transfer from Ni2+ to Er3+ with the efficiency of 19%. Elaborated glass-nanocrystalline material is a very promising candidate for use as a core of broadband luminescence optical fibers.

Dehydroxylation of Perlite and Vermiculite: Impact on Improving the Knock-Out Properties of Moulding and Core Sand with an Inorganic Binder.

The article presents the results of research aimed at examining the type of swelling material introduced into moulding or core sand to improve their knock-out properties. Tests on Slovak perlite ore (three grain sizes), Hungarian perlite ore and ground vermiculite (South Africa) were carried out. For this purpose, thermal and structural analyses (FTIR-Fourier Transform Infrared Spectroscopy), a chemical composition test (XRF-X-Ray Fluorescence), phase analysis (XRD-X-Ray Diffraction), and scanning electron microscopy (SEM-Scanning Electron Microscope) as well as final strength tests of moulding sands with the addition of perlite ore and vermiculite were carried out. The results of thermal studies were related to IR (Infrared Spectroscopy) spectra and XRD diffractograms. It has been shown that the water content in the pearlite ore is almost three times lower than in vermiculite, but the process of its removal is different. Moreover, the chemical composition of the perlite ore, in particular the alkali content and its grain size, may influence its structure. The phenomena of expansion (perlite) and peeling (vermiculite) have a positive effect on the reduction of the final sand strength and eliminate technological inconveniences (poor knocking out) that significantly limit the wide use of moulding sands with inorganic binders.

Application of Statistical Methods in Predicting the Properties of Glass-Ceramic Materials Obtained from Inorganic Solid Waste.

This paper uses mathematical methods as the basic tool at the stage of experiment planning. The importance of research programming applications was shown using the theory of experiments and the STATISTICA software. The method of experiment planning used in the case of studying the properties of a mixture, depending on its composition, features considerable complexity. The aim of the statistical analysis was to determine the influence of variable chemical composition of waste materials on selected properties of glass-ceramic materials. A statistical approach to multicomponent systems, such as ceramic sets, enables the selection of appropriate amounts of raw materials through the application of 'a plan for mixtures'. To utilize the raw waste materials, e.g., slags from a solid waste incinerator, fly or bottom ashes, in the modeling of new materials, a mathematical relationship was developed, which enables estimating, based on the waste chemical composition, selected technological and practical properties of the glass so as to obtain a material featuring the required technological-practical parameters. For the obtained glasses, a comparative analysis of the experimentally and computationally determined properties was carried out: transformation temperature, liquidus temperature, density, and thermal expansion coefficient. The obtained high theoretical approximation (at the level of determination correlation coefficient R2 > 0.8) confirms the suitability of the polynomial model for mixtures for applications in the design of new glass-ceramic products.

Fluoroindate Glass Co-Doped with Yb3+/Ho3+ as a 2.85 µm Luminescent Source for MID-IR Sensing.

This work reports on the fabrication and analysis of near-infrared and mid-infrared luminescence spectra and their decays in fluoroindate glasses co-doped with Yb3+/Ho3+. The attention has been paid to the analysis of the Yb3+→ Ho3+ energy transfer processed ions in fluoroindate glasses pumped by 976 nm laser diode. The most effective sensitization for 2 µm luminescence has been obtained in glass co-doped with 0.8YbF3/1.6HoF3. Further study in the mid-infrared spectral range (2.85 µm) showed that the maximum emission intensity has been obtained in fluoroindate glass co-doped with 0.1YbF3/1.4HoF3. The obtained efficiency of Yb3+→ Ho3+ energy transfer was calculated to be up to 61% (0.8YbF3/1.6HoF3), which confirms the possibility of obtaining an efficient glass or glass fiber infrared source for a MID-infrared (MID-IR) sensing application.

Luminescence Sensing Method for Degradation Analysis of Bioactive Glass Fibers.

The effects of Sm3+ content on the optical properties and bioactivity of 13-93 bioactive glass were presented. Sm3+ doped glass fibers drawn from bioactive glass were analyzed in simulated body fluid (SBF) for the determination of ion release. Optical analysis of the Sm3+ ions in bioactive glass fibers was used for degradation monitoring. While the fibers were immersed in SBF solution, changes in their luminescence spectra under 405 nm laser excitation were measured continuously for 48 h. The morphology of the fibers after the immersion process was determined by SEM/EDS. It was shown that the proposed approach to the analysis of changes in Sm3+ ion luminescence is a sensitive method for the monitoring of degradation processes and the formation of hydroxycarbonate-apatite (HCA) layers on glass fiber surfaces. SEM/EDS measurements showed a significant deterioration on the surface of the fibers and the formation of HCA on 13-93_02Sm bioactive glass. The optical analysis of the time constant indicated that bioactive glass fibers doped with 2 %mol Sm3+ degrade at a rate almost five times slower than 13-93_02Sm.

Investigation of the TeO2/GeO2 Ratio on the Spectroscopic Properties of Eu3+-Doped Oxide Glasses for Optical Fiber Application.

This study presented an analysis of the TeO2/GeO2 molar ratio in an oxide glass system. A family of melt-quenched glasses with the range of 0-35 mol% of GeO2 has been characterized by using DSC, Raman, MIR, refractive index, PLE, PL spectra, and time-resolved spectral measurements. The increase in the content of germanium oxide caused an increase in the transition temperature but a decrease in the refractive index. The photoluminescence spectra of europium ions were examined under the excitation of 465 nm, corresponding to 7F0 → 5D2 transition. The PSB (phonon sidebands) analysis was carried out to determine the phonon energy of the glass hosts. It was reported that the red (5D0 → 7F2) to orange (5D0 → 7F1) fluorescence intensity ratio for Eu3+ ions decreased from 4.49 (Te0Ge) to 3.33 (Te15Ge) and showed a constant increase from 4.58 (Te20Ge) to 4.88 (Te35Ge). These optical features were explained in structural studies, especially changes in the coordination of [4]Ge to [6]Ge. The most extended lifetime was reported for the Eu3+ doped glass with the highest content of GeO2. This glass was successfully used for the drawing of optical fiber.

Synthesis and Influence of 3-Amino Benzoxaboroles Structure on Their Activity against Candida albicans.

Benzoxaboroles emerged recently as molecules of high medicinal potential with Kerydin® (Tavaborole) and Eucrisa® (Crisaborole) currently in clinical practice as antifungal and anti-inflammatory drugs, respectively. Over a dozen of 3-amino benzoxaboroles, including Tavaborole's derivatives, have been synthetized and characterized in terms of their activity against Candida albicans as a model pathogenic fungus. The studied compounds broaden considerably the structural diversity of reported benzoxaboroles, enabling determination of the influence of the introduction of a heterocyclic amine, a fluorine substituent as well as the formyl group on antifungal activity of those compounds. The determined zones of the growth inhibition of examined microorganism indicate high diffusion of majority of the studied compounds within the applied media as well as their reasonable activity. The Minimum Inhibitory Concentration (MIC) values show that the introduction of an amine substituent in position "3" of the benzoxaborole heterocyclic ring results in a considerable drop in activity in comparison with Tavaborole (AN2690) as well as unsubstituted benzoxaborole (AN2679). In all studied cases the presence of a fluorine substituent at position para to the boron atom results in lower MIC values (higher activity). Interestingly, introduction of a fluorine substituent in the more distant piperazine phenyl ring does not influence MIC values. As determined by X-ray studies, introduction of a formyl group in proximity of the boron atom results in a considerable change of the boronic group geometry. The presence of a formyl group next to the benzoxaborole unit is also detrimental for activity against Candida albicans.

Fluoroindate glasses co-doped with Pr3+/Er3+ for near-infrared luminescence applications.

Fluoroindate glasses co-doped with Pr3+/Er3+ ions were synthesized and their near-infrared luminescence properties have been examined under selective excitation wavelengths. For the Pr3+/Er3+ co-doped glass samples several radiative and nonradiative relaxation channels and their mechanisms are proposed under direct excitation of Pr3+ and/or Er3+. The energy transfer processes between Pr3+ and Er3+ ions in fluoroindate glasses were identified. In particular, broadband near-infrared luminescence (FWHM = 278 nm) associated to the 1G4 → 3H5 (Pr3+), 1D2 → 1G4 (Pr3+) and 4I13/2 → 4I15/2 (Er3+) transitions of rare earth ions in fluoroindate glass is successfully observed under direct excitation at 483 nm. Near-infrared luminescence spectra and their decays for glass samples co-doped with Pr3+/Er3+ are compared to the experimental results obtained for fluoroindate glasses singly doped with rare earth ions.