XANES analysis of phosphate glasses melted with Tb4O7 and SnO: evaluating the impact of valence states on structural, thermal, and luminescent properties.

Barium phosphate glasses were prepared with 0.5 mol% Tb4O7 added alongside SnO up to 5 mol% with the purpose of evaluating the resulting terbium and tin oxidation states and their impact on glass structural, thermal, and luminescent properties. Following material synthesis by melt-quenching, the composition-structure-property investigation was pursued encompassing measurements by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, differential scanning calorimetry (DSC), dilatometry, and photoluminescence (PL) spectroscopy. While XRD confirmed the amorphous nature of the glasses, results from XANES indicated that terbium occurs as terbium(III) with a predisposition for tin to exist as tin(IV) which decreased at high SnO content. The structural as well as the thermal properties appeared to be mostly impacted by the presence of tin(IV). Specifically, glass depolymerization was indicated to be induced by Sn4+ ions, and their concentration was observed to correlate with glass transition and softening temperatures. On the other hand, the tin(II) remnants were observed to exert an impact on the luminescent properties shifting light emission from the green towards the blue-green (cyan). It is indicated that Tb4O7 reacting to produce Tb2O3 supports the oxidation of tin(II) to tin(IV) which in turn dominates the physical properties. However, this was somewhat circumvented at the highest SnO content wherein tin(IV) appeared to be lower.

Nanodiamond-promoted white light emission in Eu, Dy, and Cu-containing phosphate glass: quantitative analysis and colorimetric study.

A thorough analysis of glass containing Eu2 O3 and Dy2 O3 , or Eu2 O3 , Dy2 O3 , and CuO melted together with nanodiamond powder was pursued based on measurements of optical absorption, photoluminescence (PL) emission and excitation spectra, and colorimetry. Nanodiamond facilitated the stabilization of Cu+ and Eu2+ ions with blue-emitting characteristics that, along with yellow-emitting Dy3+ and red-emitting Eu3+ led to the white light-emitting glass. Novel intensity notations implemented in intensity-based spectral ratios, and difference intensity correlation analysis were proposed for the assessment of PL properties. The chromaticity and correlated colour temperature of the emission were ultimately investigated as a two-parametric problem based on: (1) the different ionic components; and (2) the various excitation wavelengths employed. The optical analysis approach adds to the characterization methods to further fundamental understanding and provide helpful analytical tools for designing materials for tunable white light-emitting devices.

Thermodynamic Analysis of Intermediary Metabolic Steps and Nitrous Oxide Production by Ammonium-Oxidizing Bacteria.

Nitrous oxide (N2O) is a greenhouse gas emitted from wastewater treatment, soils, and agriculture largely by ammonium-oxidizing bacteria (AOB). While AOB are characterized by being aerobes that oxidize ammonium (NH4+) to nitrite (NO2-), fundamental studies in microbiology are revealing the importance of metabolic intermediates and reactions that can lead to the production of N2O. These findings about the metabolic pathways for AOB were integrated with thermodynamic electron-equivalents modeling (TEEM) to estimate kinetic and stoichiometric parameters for each of the AOB's nitrogen (N)-oxidation and -reduction reactions. The TEEM analysis shows that hydroxylamine (NH2OH) oxidation to nitroxyl (HNO) is the most energetically efficient means for the AOB to provide electrons for ammonium monooxygenation, while oxidations of HNO to nitric oxide (NO) and NO to NO2- are energetically favorable for respiration and biomass synthesis. The respiratory electron acceptor can be O2 or NO, and both have similar energetics. The TEEM-predicted value for biomass yield, maximum-specific rate of NH4+ utilization, and maximum specific growth rate are consistent with empirical observations. NO reduction to N2O is thermodynamically favorable for respiration and biomass synthesis, but the need for O2 as a reactant in ammonium monooxygenation likely precludes NO reduction to N2O from becoming the major pathway for respiration.

Genome Characterization and Pathogenicity of Two New Hyptis pectinata Viruses Transmitted by Distinct Insect Vectors.

Two newly described viruses belonging to distinct families, Rhabdoviridae and Geminiviridae, were discovered co-infecting Hyptis pectinata from a tropical dry forest of Ecuador. The negative-sense RNA genome of the rhabdovirus, tentatively named Hyptis latent virus (HpLV), comprises 13,765 nucleotides with seven open reading frames separated by the conserved intergenic region 3'-AAUUAUUUUGAU-5'. Sequence analyses showed identities as high as 56% for the polymerase and 38% for the nucleocapsid to members of the genus Cytorhabdovirus. Efficient transmission of HpLV was mediated by the pea aphid (Acyrthosiphon pisum) in a persistent replicative manner. The single-stranded DNA genome of the virus tentatively named Hyptis golden mosaic virus (HpGMV) shared homology with members of the genus Begomovirus with bipartite genomes. The DNA-A component consists of 2,716 nucleotides (nt), whereas the DNA-B component contains 2,666 nt. Pairwise alignments using the complete genomic sequence of DNA-A of HpGMV and closest relatives showed identities below the cutoff (<91% shared nt) established by the ICTV as species demarcation, indicating that HpGMV should be classified in a distinct begomovirus species. Transmission experiments confirmed that the whitefly Bemisia tabaci Middle East-Asia Minor 1 (MEAM1) is a vector of HpGMV.

Announcement Signals and Automatic Braking Using Virtual Balises in Railway Transport Systems.

In rail transport, various automatic protection systems are available to ensure the safe operation of trains and to facilitate automation and optimization tasks. For this purpose, a set of physical balises is used, which are placed at fixed points along the railway track. Based on the information provided by these balises, different information is displayed to the driver, and control actions are generated. The use of physical balises located at fixed points does not allow for automatic protection actions on sections of track where they are not installed. This is a major drawback as in many cases, temporary automatic protection actions are necessary on sections of the railway line without balises due to various circumstances (work on the track, accidents, etc.). To solve this problem, this paper presents a solution called announcement signals and automatic braking using virtual balises (ASAB-VB). This proposal allows the incorporation of virtual balises at points on the track where it is necessary to temporarily perform automatic protection actions. For this purpose, the ASAB-VB system allows obtaining the train position in real-time and storing a digital map of the track that will be made by each train. This digital map includes geographic information about the balises (both physical and virtual ones) located on the track. At the same time, the train position is obtained by merging the information provided by a GNSS, an odometer, and an inertial system (gyro and accelerometers).

Turning Base Transceiver Stations into Scalable and Controllable DC Microgrids Based on a Smart Sensing Strategy.

This paper describes a practical approach to the transformation of Base Transceiver Stations (BTSs) into scalable and controllable DC Microgrids in which an energy management system (EMS) is developed to maximize the economic benefit. The EMS strategy focuses on efficiently managing a Battery Energy Storage System (BESS) along with photovoltaic (PV) energy generation, and non-critical load-shedding. The EMS collects data such as real-time energy consumption and generation, and environmental parameters such as temperature, wind speed and irradiance, using a smart sensing strategy whereby measurements can be recorded and computing can be performed both locally and in the cloud. Within the Spanish electricity market and applying a two-tariff pricing, annual savings per installed battery power of 16.8 euros/kW are achieved. The system has the advantage that it can be applied to both new and existing installations, providing a two-way connection to the electricity grid, PV generation, smart measurement systems and the necessary management software. All these functions are integrated in a flexible and low cost HW/SW architecture. Finally, the whole system is validated through real tests carried out on a pilot plant and under different weather conditions.

Application of Elicitors in Two Ripening Periods of Vitis vinifera L. cv Monastrell: Influence on Anthocyanin Concentration of Grapes and Wines.

In recent years, it has been demonstrated that the application of elicitors such as methyl-jasmonate (MeJ) and benzothiadiazole (BTH) to wine grapes can increase their phenolic and aromatic compounds if they are treated at the beginning of ripening (veraison). However, the veraison period is short, and it is not always possible to apply the treatments in a few days. Therefore, it would be of great interest to optimize the moment of elicitor application or extend the treatment period. The aim of this paper was to analyze during two consecutive years (2016-2017) the foliar application of MeJ, BTH, and a combination of both, during two different ripening periods of Monastrell grapes (veraison and mid-ripening), and determine the more appropriate moment to increase the concentration of anthocyanins. To carry out this aim, analysis of anthocyanins by HPLC in grapes and wines was mainly performed. The most suitable period for the application of MeJ, BTH, and MeJ + BTH was at mid-ripening, since the grapes showed a greater accumulation of anthocyanins at harvest. However, the MeJ + BTH treatment applied during veraison also obtained similar results, which would allow extending the application period if necessary. However, the increase in the anthocyanin content of grapes was not reflected in all the wines, which may have been due to reinforcement of the skin cell wall as a result of the application of elicitors. Further analysis is needed to improve the maceration process of the Monastrell grapes and the extraction of the anthocyanins that were increased by the treatments applied in the vineyard.

Beachgoer perceptions on health regulations of COVID-19 in two popular beaches on the Brazilian Amazon.

The sandy beaches of the Brazilian Amazon coast have enormous touristic potential and attract thousands of visitors each year, principally in July, at the beginning of the summer vacation period. In 2020, beach going was affected worldwide by the Covid-19 pandemic, but how did the pandemic affect recreational beach use on the Amazon coast in the Brazilian state of Pará? Given this, the objective of this work is to identify public perception in compliance with health safety established by authorities due to COVID-19 pandemic in two popular beaches on the Brazilian Amazon. Recreational patterns on the beaches of this region were analyzed from the user's perspective in July, through semi-structured interviews and direct observations. Recreational activities were prohibited on the beaches located within protected areas. At other locations, however, including Ajuruteua and Atalaia, the beaches were reopened on July 1 st, and both sites received thousands of visitors in July, despite the fact that interviewees believed the pandemic to be dangerous, and considered the situation in Pará state to be at least as bad or worse than in previous months. Agglomerations were verified on both study beaches and social distancing and other protective measures were limited. The increase in the new cases recorded in August was due to the relaxation of restrictions on social, recreational, and economic activities by the local authorities in July 2020, including the reopening of public access to beaches. As Pará state has been hard-hit by the pandemic, prohibitions on recreational beach use should clearly not have been lifted during this period. A number of management measures were presented in this study. These measures should contribute to the prevention of the spread of the virus during the upcoming public holidays, as long as the pandemic continues.

Optical Spectroscopy and Excited-State Dynamics of Eu3+ -Doped Bismuth Borate Glasses Containing CuO.

Bismuth borate glasses containing phosphors and luminescent rare-earths are of interest for applications in light-emitting devices. Herein, the influence of CuO impurities on red-emitting Eu3+ -doped bismuth borate glasses of the 25Bi2 O3 -15BaO-10Li2 O-50B2 O3 type was investigated by various spectroscopic methods. The glasses were prepared by the melt-quench technique and characterized by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, UV/Vis optical absorption (OA), and photoluminescence (PL) spectroscopy including decay kinetics assessment. The XRD data confirmed the amorphous nature of the glasses whereas FT-IR spectra indicated the basic structural features of trigonal BO3 units and BO4 tetrahedra. The OA analysis showed that addition of CuO up to 0.5 mol% results in significant growth of the visible Cu2+ absorption band around 715 nm, with slight decrease in the optical band gap energies assessed through Tauc plots. A drastic PL quenching of Eu3+ ions emission was evidenced concurring with the detrimental effect of Cu2+ . The assessment of the Eu3+ emission decay curves revealed significant lifetime decrease of the 5 D0 emitting state with increasing CuO concentration. An analysis of quenching constants was finally performed comparing results from integrated PL data with the emission decay rates. It is argued that the bismuth borate glass system supports an effective Eu3+ →Cu2+ energy transfer (more so than phosphates) in connection with a strong spectral overlap between Eu3+ emission and Cu2+ absorption.

Temperature Dependent Spectroscopic Properties of Cu+ and Dy3+ Co-Doped Phosphate Glass: Band Gap Analysis and Cu Nanocluster-Enhanced Dy3+ Luminescence.

This paper reports on the effects of temperature on light absorption and emission in Cu+ and Dy3+ co-doped phosphate glass, which is of interest for photonic applications. First, the temperature dependence of the absorption edge of the glass in connection with Cu+ ions absorption was assessed. A thermally-induced red shift attributed to Cu+ ion-lattice interactions was observed and analyzed through optical band gap determinations in the context of indirect-allowed transitions. Application of the Varshni model for the dependence of the energy gaps with temperature allowed to estimate the 0 K energy gap at 2.87 (±0.01) eV. Furthermore, Dy3+ photoluminescence (PL) along with Cu nanoparticles (NPs) absorption was monitored in real-time during an isothermal treatment by the in situ concurrent PL and absorption microspectroscopy technique. Periods of enhancement and quenching of Dy3+ emission linked to bidirectional energy transfer processes involving non-plasmonic Cu clusters and plasmonic Cu NPs were revealed. The formation of Cu NPs was promoted by tin(II) used as reductant. It is the first time to the author's knowledge that the 0 K energy gap is estimated for a highly Cu+ -doped glass and that the enhancement of Dy3+ PL by Cu clusters is exposed.

Modelling gas-liquid mass transfer in wastewater treatment: when current knowledge needs to encounter engineering practice and vice versa.

Gas-liquid mass transfer in wastewater treatment processes has received considerable attention over the last decades from both academia and industry. Indeed, improvements in modelling gas-liquid mass transfer can bring huge benefits in terms of reaction rates, plant energy expenditure, acid-base equilibria and greenhouse gas emissions. Despite these efforts, there is still no universally valid correlation between the design and operating parameters of a wastewater treatment plant and the gas-liquid mass transfer coefficients. That is why the current practice for oxygen mass transfer modelling is to apply overly simplified models, which come with multiple assumptions that are not valid for most applications. To deal with these complexities, correction factors were introduced over time. The most uncertain of them is the α-factor. To build fundamental gas-liquid mass transfer knowledge more advanced modelling paradigms have been applied more recently. Yet these come with a high level of complexity making them impractical for rapid process design and optimisation in an industrial setting. However, the knowledge gained from these more advanced models can help in improving the way the α-factor and thus gas-liquid mass transfer coefficient should be applied. That is why the presented work aims at clarifying the current state-of-the-art in gas-liquid mass transfer modelling of oxygen and other gases, but also to direct academic research efforts towards the needs of the industrial practitioners.

Optimal Use of Transient Elastography and Acoustic Radiation Force Impulse to Stage Liver Fibrosis in HIV/HCV-Coinfected Patients in Clinical Practice.

OBJECTIVES: Liver fibrosis (LF) is crucial for the individualized management of patients with hepatitis C virus (HCV). We evaluated the concordance between two noninvasive methods for staging LF, transient elastography (TE) and acoustic radiation force impulse (ARFI), in patients coinfected with human immunodeficiency virus and HCV. We propose an algorithm for optimal use of both techniques in routine clinical practice. METHODS: A total of 89 human immunodeficiency virus/HCV-coinfected patients underwent TE and ARFI on the same day. The kappa index was used to assess concordance between the techniques. An algorithm combining ARFI and TE was proposed based on the independent factors associated with a kappa index greater than or equal to 0.70, obtained from a multiple regression analysis. We performed a cost-effectiveness analysis. The study was approved by our institutional review board and all patients signed the informed consent. RESULTS: Concordance between TE and ARFI for F2, F3, and F4 was 0.55, 0.59, and 0.69, respectively. Ultrasound normal spleen size (odds ratio [OR], 0.20; 95% confidence interval [CI], 0.05-0.91) and high viral load (OR, 0.36; 95% CI, 0.17-0.77) reduced the probability of agreement between TE and ARFI, whereas ultrasound normal left liver lobe size (OR, 3.32; 95% CI, 1.21-9.10) increased this probability. The algorithm revealed that LF was adequately assessed in 74.16%, with 25.84% of patients misclassified. The incremental cost-effectiveness ratio of TE compared with ARFI to increase concordance by 1% was €8.86. CONCLUSIONS: Concordance between TE and ARFI was moderate. In the algorithm we proposed, ARFI was cost-effective as a first technique for the staging of LF in the study population.

Absorption Spectroscopy Analysis of Calcium-Phosphate Glasses Highly Doped with Monovalent Copper.

CaO-P2 O5 glasses with high concentrations of monovalent copper ions were prepared by a simple melt-quench method through CuO and SnO co-doping. Spectroscopic characterization was carried out by optical absorption with the aim of analyzing the effects of Cu(+) ions on the optical band-gap energies, which were estimated on the basis of indirect-allowed transitions. The copper(I) content is estimated in the CuO/SnO-containing glasses after the assessment of the concentration dependence of Cu(2+) absorption in the visible region for CuO singly doped glasses. An exponential dependence of the change in optical band gaps (relative to the host) with Cu(+) concentration is inferred up to about 10 mol %. However, the entire range is divided into two distinct linear regions that are characterized by different rates of change with respect to concentration: 1) below 5 mol %, where the linear dependence presents a relatively high magnitude of the slope; and 2) from 5-10 mol %, where a lower magnitude of the slope is manifested. With increasing concentration, the mean Cu(+) -Cu(+) interionic distance decreases, thereby decreasing the sensitivity of monovalent copper for light absorption. The decrease in optical band-gap energies is ultimately shown to follow a linear dependence with the interionic distance, suggesting the potential of the approach to gauge the concentration of monovalent copper straightforwardly in amorphous hosts.

Long-term intake of white tea prevents oxidative damage caused by adriamycin in kidney of rats.

BACKGROUND: White tea infusion (Camelia sinensis) has antioxidants properties. The infusion contains polyphenols that have been proposed to induce antioxidant response element (ARE) response via nuclear factor E2-related factor 2 (NRF2). Adriamycin (ADR) has antitumour properties and oxidative effects. Oxidative stress is related to a variety of kidney diseases. Prevention of the oxidative stress through long-term intake of white tea and the study of the molecular mechanisms involved in protection could be of great interest. Rats were given distilled water, 0.015 or 0.045 g of solid white tea extract kg(-1) body weight for 12 months. Animals received an injection of ADR. In kidney, oxidative stress parameters were measured, the expressions of nuclear factor E2-related factor 2 gene (Nrf2), and detoxifying and antioxidants genes were analysed, and the activities of catalase (CAT), superoxide dismutase (SOD) and glutathione reductase (GR) were measured. RESULTS: ADR administration increased oxidative parameters and decreased the antioxidant activity; significantly increased the expression of analysed genes and the activity of CAT and SOD and decreased GR activity. The highest white tea dose protected redox status and inhibited ARE response. CONCLUSION: Long-term intake of white tea protected kidney against the oxidative stress. ADR activated the ARE response but in animals treated with the highest dose of white tea, this response was inhibited, probably for antioxidant protection. © 2015 Society of Chemical Industry.

UV Emission of Gd³âº in the Presence of Cu²âº : Towards Luminescence Quenching through Quantum Cutting?

The first investigation into the ultraviolet (UV) photoluminescence of gadolinium(III) in the presence of copper(II) is reported. A melt-quenched barium phosphate glass was used as a model matrix. The optical spectroscopy assessment shows that with increasing CuO concentration the Cu(2+) absorption band grows steadily, whereas the UV emission from Gd(3+) ions is progressively quenched. The data, thus, suggests the existence of a Gd(3+) →Cu(2+) energy-transfer process ocurring through quantum cutting. A downconversion/cross-relaxation pathway proceeding through a virtual state in Gd(3+) is proposed. These findings suggest gadolinium(III) could potentially be used in the optical sensing of copper(II).

Kinetics of copper nanoparticle precipitation in phosphate glass: an isothermal plasmonic approach.

The kinetics of copper nanoparticle (NP) precipitation in melt-quenched barium-phosphate glass has been studied by in situ isothermal optical micro-spectroscopy. A spectroscopically based approximation technique is proposed to obtain information about the activation energies of nucleation and growth in a narrow temperature range (530-570 °C). Pre-plasmonic and plasmonic NP precipitation stages are identified separated in time. The process as a whole is discussed employing classical nucleation/growth theory and the Kolmogorov-Johnson-Mehl-Avrami phase change model. Activation energies of 3.9(7) eV and 2.6(5) eV have been estimated for the pre-plasmonic and plasmonic spectroscopically assessed stages, respectively. High resolution transmission electron microscopy, differential scanning calorimetry, and Raman spectroscopy were used as complementary techniques for studying the nanoparticulate phase and glass host structure. An empirical linear dependence of the diffusion activation energy on the glass transition temperature with broad applicability is suggested.

[Effect of hydrogymnastics physical exercise on serum level of immunoglobulin A in elderly women]. / Efecto del ejercicio físico de hidrogimnasia sobre la concentración sérica de inmunoglobulina A en mujeres adultas mayores.

BACKGROUND: Decreases in function of the immune system with age contribute to the increase the risk of infectious diseases especially the upper respiratory tract. On the other hand, physical activity has been widely recommended for health. However, more studies are needed to support the benefit effect of exercise on immune system in elderly. AIM: To evaluate the effect of the hydrogymnastics on the serum level of immunoglobulin A (IgA) in elderly women. METHODS: Twenty-six participants were randomly assigned to an experimental (n: 16) or a control group (n: 10). IgA concentrations were determined by nephelometry (BN2 Analyzer, Dade Behring). The hydrogymnastics training protocol was performed 5 times a week during 12 weeks. The intensity of the aerobic exercise was 50-60% of the maximum heart rate monitored by telemetry (Polar-FT7). RESULTS: No significant differences (p: 0.797) resulted by ANOVA on serum IgA levels; the percentage of change in experimental group was Δ% = -6.7 mg/dL compared to the control group, Δ%= -7.4 mg/dL. CONCLUSION: After three months of hydrogymnastics the IgA level did not show significant change on elderly women; However, positive improvement in percentage of change Δ% was found.

Primary central neurocytoma of the mesencephalic tectum in a pediatric patient.

PURPOSE: Neurocytomas are tumors or neuronal differentiation, typically located within the supratentorial ventricular system. The extraventricular location is uncommon. A limited number of cases involving the brainstem have been reported and may be misdiagnosed as brainstem gliomas. Furthermore, midbrain neurocytomas are extremely rare, and no similar cases in pediatric patients have been reported in the literature to date. Brainstem location of neurocytomas often precludes gross total removal of the lesion, and in these cases, adjuvant therapies may be helpful. METHODS: We report a case of a 16-year-old child who presented with signs and symptoms of increased intracranial pressure. The magnetic resonance imaging study demonstrated the presence of a primary mesencephalic tectum lesion causing obstructive hydrocephalus. The patient underwent emergent ventriculoperitoneal shunt implantation, resolving the hydrocephalus and the clinical symptoms. The lesion was partially removed through a suboccipital craniotomy and supracerebellar infratentorial approach to the mesencephalic tectum, without intraoperative complications. RESULTS: Histological examination of the lesion was consistent with the diagnosis of extraventricular neurocytoma. The patient was referred to the oncology department for additional treatment with Gamma Knife radiosurgery. CONCLUSIONS: Although brainstem neurocytoma is rare, this case demonstrates that it should be included in the differential diagnosis of brainstem gliomas. Because of brainstem tumor location, complete surgical removal may be challenging or not possible, with a high risk of postoperative neurological deficits. Adjuvant therapies may prevent local tumor growth in cases of tumor remnants or recurrences following microsurgery in selected cases.

Holistic Assessment of NIR-Emitting Nd3+-Activated Phosphate Glasses: A Structure-Property Relationship Study.

Near-infrared (NIR)-emitting phosphate glasses containing Nd3+ ions are attractive for applications in laser materials and solar spectral converters. The composition-structure-property relation in this type of glass system is thus of interest from fundamental and applied perspectives. In this work, Nd3+-containing glasses were made by melting with 50P2O5-(50 - x)BaO-xNd2O3 (x = 0, 0.5, 1.0, 2.0, 3.0, 4.0 mol %) nominal compositions and studied comprehensively by density and related physical properties, X-ray diffraction (XRD), Raman spectroscopy, O 1s X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), dilatometry, ultraviolet-visible (UV-vis)-NIR optical absorption, and photoluminescence (PL) spectroscopy with decay dynamics assessment. The densities and molar volumes of the Nd3+-containing glasses generally increased with Nd2O3 concentration also resulting in shorter Nd3+-Nd3+ distances. XRD supported the amorphous nature of the glasses, whereas the Raman spectra evolution was indicative of glass depolymerization being induced by Nd3+ ions. Oxygen (1s) and phosphorus (2p) analysis by XPS for the glass with 4.0 mol % Nd2O3 agreed with the increase in nonbridging oxygens relative to the undoped host. DSC results showed that the glass transition temperatures increased with Nd3+ concentration, with the glasses also displaying a decreased tendency toward crystallization. Dilatometry showed trends of increasing softening temperatures and decreasing thermal expansion coefficients with increasing Nd2O3 content. A glass strengthening/tightening effect was then indicated to be induced by Nd3+ with higher field strength compared to Ba2+ ions. The UV-vis-NIR absorption by Nd3+ ions increased consistently with Nd3+ concentration. The UV-vis absorption edges of the Nd-containing glasses were also analyzed via Tauc and Urbach plots for comparison with the undoped host. Concerning the PL behavior, the Nd3+ NIR emission intensity was highest for 1.0 mol % Nd2O3 and decreased thereafter. The decay kinetics of the 4F3/2 emitting state in Nd3+ ions analyzed revealed decreasing lifetimes where the decay rate analysis pointed to the prevalence of ion-ion excitation migration leading to PL quenching at high Nd3+ concentrations.

Impact of Lanthanide (Nd3+, Gd3+, and Yb3+) Ionic Field Strength on the Structure and Thermal Expansion of Phosphate Glasses.

Phosphate glasses containing Nd3+, Gd3+, and Yb3+ as lanthanide ions are attractive for applications in laser materials, phototherapy lamps, and solar spectral converters. The composition-structure-property relation in this type of glass system is thus of interest from fundamental and applied perspectives. In this work, the impact of the differing ionic radius of Nd3+, Gd3+, and Yb3+ and consequent field strength on the physical properties of phosphate glasses is investigated, focusing ultimately on thermal expansion effects. The glasses were made by melting with a fixed concentration of the lanthanide ions having 50P2O5-46BaO-4Ln2O3 nominal compositions (mol %) with Ln = Nd, Gd, and Yb. The investigation encompassed measurements by X-ray diffraction (XRD), optical spectroscopy, density, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and dilatometry. XRD supported the amorphous nature of the glasses, whereas absorption and photoluminescence spectra showed the optical features of the Nd3+, Gd3+, and Yb3+ ions in the glasses. Oxygen speciation by XPS indicated an increase in nonbridging oxygens for the larger radii Nd3+ and Gd3+ ions relative to the host, contrasting with Yb3+. Phosphorus XPS analysis further supported the hypothesis that the P 2p binding energies of the glasses increased with the cation field strength of the lanthanides. The Raman spectra were interpreted based on glass depolymerization effects and the impact of Ln3+ ions with high field strength. Particularly, the band position of the symmetric out-of-chain nonbridging oxygen stretch, νs(PO2-), shifted to higher frequencies correlating with the Ln3+ field strength. Dilatometry ultimately revealed a steady decrease in the coefficient of thermal expansion for the glasses, which correlated linearly with Ln3+ field strengths and thus indicated to sustain increased glass rigidities. The various analyses performed thus illuminated the structural foundation of the thermomechanical behavior of the glasses connected with changes in the Ln3+ field strengths.