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Made available in DSpace on 2022-04-28T19:47:48Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-12-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) Financiadora de Estudos e Projetos Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Structural, optical and photoluminescent properties of Europium-doped potassium germanate glassy materials were investigated in terms of tantalum content and nanoscale crystallization of potassium tantalate K2Ta8O21. For such purpose, an Eu3+-doped germanate glass, Eu3+-doped tantalum germanate glass and Eu3+-doped tantalum germanate glass-ceramics were prepared and characterized by X-ray diffraction, Raman, UV–Vis–NIR and photoluminescence spectroscopies. Eu3+ emission properties were used as a sensitive probe to investigate its symmetry site into the host structure. The chemical microenvironment around Eu3+ ions have changed with tantalum concentration as well as bronze-like tantalum perovskite K2Ta8O21 phase crystallization into the glasses. The ions preferably occupy sites of higher symmetry and lower energy phonons, which attest the ions migration to the tantalum-rich crystalline environment. The correlation between the phonon side band (PSB) spectra and Raman vibrational modes, 5D0 → 7F2/5D0 → 7F1 ratio and experimental Eu3+ 5D0 lifetime support this assumption. The highest photoluminescence intrinsic quantum yield (QEuEu) is calculated for glass-ceramics heat-treated for 20 h by using Judd-Ofelt theory, indicating reduction of nonradiative decay processes due to the lower local phonon energy. The luminescence quenching for longer crystallization times demonstrates the importance of optimizing thermal treatment parameters to ensure proper distance between optically active ions. Accordingly, tantalum germanate glass-ceramics are promising for photonic devices as red laser, solid-state lighting and energy conversion applications, as well as for nonlinear optical applications considering the perovskite bronze-like crystallization. Grupo de Química de Materiais Universidade Federal de Alfenas Campus Poços de Caldas Instituto de Química Universidade Estadual Paulista - UNESP Departamento de Química Faculdade de Filosofia Ciências e Letras de Ribeirão Preto Universidade de São Paulo Instituto de Química Universidade Estadual Paulista - UNESP FAPESP: 2017/11301-2 FAPESP: 2020/01786-1 FAPESP: 2020/05319-9 CNPq: 303110/2019-8

This work presents an economical, technical, and environmentally correct solution for the disposal of long neck bottles (which cannot be bottled more than once), by replacing fine aggregates (sand) with residue of ground glass from long neck bottles in the production of reactive powder concrete (RCP). Using a reference formulation for RCP containing natural sand, this raw material was replaced in 12.5, 25, 50, 75 and 100 wt.% by glass residues, evaluating the physical and mechanical properties in the specimens at the ages of 7, 14, and 28 days. The ground glass was characterized by X-ray Fluorescence and DSC tests, indicating that it is a typical sodo-calcium glass, with a glass transition temperature equals to 560C. Grain size distribution and optical microscopy assays of natural sand and ground glass indicated that the comminution let to the acquisition of glass with granulometry similar to that of natural sand, but with very different geometries and roughness. The replacement of natural sand by 100% of ground glass presented the best results of mechanical properties, reaching 85% of the mechanical strength value of the reference composition, with about 96MPa; this composition also presented the lowest water absorption value (3.94%) and the lowest void index (9.33%) among all compositions. The results indicated that the replacement of sand by powder from long neck bottles is potentially feasible, promoting an environmentally correct destination for this residue in the construction sector, bringing a reduction in environmental impact, and generating concrete within the technical standards required by the norm. Este trabajo presenta una solución económica, técnica y ambientalmente correcta para el desecho de botellas long neck (que no se pueden llenar más de una vez), mediante la sustitución de áridos finos (arena) por residuos de vidrio triturado de botellas long neck en la producción de concretos de polvo reactivo (CPR). A partir de una formulación de referencia para CPR con arena, esta materia prima fue reemplazada en 12.5, 25, 50, 75 y 100% en peso por el residuo, evaluando las propiedades físicas y mecánicas en los especímenes en las edades de curación 7, 14, y 28. El vidrio molido fue caracterizado por Fluorescencia de Rayos X y DSC, indicando un vidrio sodocálcico típico, con una temperatura de transición vítrea de 560C. Ensayos de distribución granulométrica y microscopía óptica para caracterizar y comparar arena y vidrio indicaron que com la trituración se obtenía un vidrio con granulometría similar a la de la arena, pero con diferentes geometrías y rugosidades. La sustitución de arena por vidrio al 100% mostró las mejores propiedades mecánicas, alcanzando 85% del valor de resistencia de la referencia, con 96 MPa; el valor de absorción de agua más bajo (3,94%) y la tasa de vacío más baja (9,33%) entre todas las composiciones. Los resultados indicaron que la sustitución de arena por polvo de botellas es viable, promoviendo un destino ambientalmente correcto para este residuo en la construcción civil, trayendo una reducción del impacto ambiental y generando un concreto dentro de los estándares técnicos exigidos en la norma. Este trabalho apresenta uma solução econômica, técnica e ambientalmente correta para o descarte das garrafas long neck (que não podem ser envasadas mais de uma vez), a partir da substituição de agregados miúdos (areia) por resíduo de vidro moído de garrafas tipo long neck na produção de concreto de pós reativos (CPR). A partir de uma formulação referência para CPR contendo areia natural, esta foi substituída em 12,5, 25, 50, 75 e 100% em peso pelo resíduo de vidro, avaliando-se as propriedades físicas e mecânicas nos corpos de prova nas idades de cura de 7, 14, e 28. O vidro moído foi caracterizado por Fluorescência de Raios X e DSC, indicando que é um vidro sodo-cálcico, com temperatura de transição vítrea de 560C. Ensaios de distribuição granulométrica e microscopia ótica para caracterização e comparação da areia e vidro moído indicaram que com a cominuição obteve-se um vidro com granulometria semelhante à da areia, mas com diferentes geometrias e rugosidades. A substituição da areia por 100% de vidro moído apresentou as melhores propriedades mecânicas, atingindo 85% do valor da composição referência, aproximadamente 96 MPa; também apresentou o mais baixo valor de absorção de água (3,94%) e menor índice de vazios (9,33%) dentre as composições contendo substituição. Os resultados indicaram que a substituição da areia por pó de garrafas do tipo long neck é viável, promovendo uma destinação ambientalmente correta para esse resíduo na construção civil, trazendo redução do impacto ambiental e gerando um concreto dentro dos padrões exigido em norma.

Er3+-doped and Er3+/Yb3+-codoped GeO2-Nb2O5-K2O glasses were prepared by conventional melt-quenching method. Thermal and spectroscopic analysis were performed. The niobium insertion into the glass structure has decreased the OH groups resulting in a slight increase in the luminescence efficiency as the niobium content. Glass network structure is modified depending on rare earth doping concentration and niobium content. The number of bridge oxygen bonds and nonbridge oxygen bonds is altered and consequently the crystallization composition. The spectroscopic features were discussed in terms of niobium concentration and its influence on the applications as optical devices. The addition of niobium broadens the emission band in the region of 1.5 µm covering C, S and L-telecommunication bands. The gain coefficient has calculated establishing high potentiality to use the niobium germanate glasses for optical amplification. The codoping by Er3+/Yb3+ intensifies the emission in the NIR and visible (upconversion) region in relation to the doped samples and may be interesting for application as visible and near-infrared emitters. In addition, the codoped samples with variable niobium contents have potential as visible tunable phosphors emitting either green or red light. Accordingly, the niobium germanate glasses are interesting matrices for rare earth ions doping and for the development of optical devices, such as visible and NIR laser and optical amplifiers.

International audience; Complex sequential crystallization mechanisms were investigated in the glass composition 70GeO2-10Na2O-20Ta2O5 prepared by melt-quenching. In a first stage, a classical volume-nucleated crystallization of sodium tantalate perovskite Na2Ta8O21 is induced under short time heat-treatments whereas longer annealing treatments promote the formation of surface spherical structures known as spherulites. These singular glass-ceramics were deeply investigated by density measurements, differential scanning calorimetry (DSC), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), Auger Electron Spectroscopy (EDS), correlated Raman and second harmonic generation (SHG) microscopy as well as macro-SHG measurements. These surface spherulites with average size up to 50 µm are richer in tantalum but poorer in germanium than the surrounding material. However, measured SHG signals were found to be related to quartz-like α-GeO2 grown inside the spherulites. Therefore these materials exhibit a second-order non-linear optical response, related to the symmetry of the point group D3 given by the quartz GeO2 grown for the first time in a transparent glass-ceramic.

Transparent fluorotellurite glasses were prepared by melt-quenching in the ternary system TeO2-Nb2O5-PbF2. The synthesis conditions were adjusted to minimize fluorine loss monitored as HF release. It was found that 10 mol% of Nb2O5 is the optimum content for PbF2 incorporation up to 35 mol% in the tellurite matrix without loss of glass forming ability. Such glass compositions exhibit a wide optical window from 380 nm to about 6 &mu, m. Crystallization properties were carefully investigated by thermal analysis and compositions with higher PbF2 contents exhibit preferential precipitation of lead oxyfluoride Pb2OF2 at lower temperatures. The lead oxyfluoride crystallization mechanism is also governed by a volume nucleation, barely reported in tellurite glasses. Eu3+ doping of these glass compositions also promotes a more efficient nucleation step under suitable heat-treatments, resulting in transparent Eu3+-doped glass-ceramics whereas undoped glass-ceramics are translucent. Finally, Eu3+ spectroscopy pointed out a progressive, more symmetric surrounding around the rare earth ions with increasing PbF2 contents as well as higher quantum efficiencies. These new fluorotellurite glass compositions are promising as luminescent hosts working in the middle infrared.

Made available in DSpace on 2020-12-12T01:28:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-11-25 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) Financiadora de Estudos e Projetos Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Transparent Eu3+-doped tantalum phosphate glass-ceramics containing Na2Ta8O21 nanocrystals were successfully obtained by a two-step heat treatment. Structural analyses were performed using X-ray diffraction, Transmission Electron Microscopy, Nuclear Magnetic Resonance and Raman spectroscopy. Due to the high Ta/P ratio (= 2) the glass network is built from a mixed 3D PO4–TaO6 chain in which TaO6-rich regions are inserted and responsible for crystallization of an alkali tantalum oxide phase Na2Ta8O21. Eu3+ and their optical properties was used as a sensitive probe to study it site structure in the host matrix. The radiative properties of Eu3+ emission levels were predicted using the Judd-Ofelt theory. The chemical environment and local phonon energy around the rare-earth ions have been proposed based on phonon side band associated with the 7F0 → 5D2 transition, 5D0 → 7F2/7F1 relative intensity and narrowing of the emission bands. High tantalum content precursor glass exhibits high photoluminescence quantum efficiency due to low phonon energy and high refractive index (1.9461 at 633 nm). A perovskite-like bronze crystalline structure is formed in the glass-ceramic (nucleated at 925 °C for 0.5 h and grown at 940 °C for different times) and is considered promising for nonlinear optical applications and studies. Institute of Chemistry Sao Paulo State University - UNESP Sao Carlos Institute of Chemistry University of Sao Paulo, São Carlos Grupo de Química de Materiais Universidade Federal de Alfenas Campus Poços de Caldas, Poços de Caldas Institute of Chemistry Sao Paulo State University - UNESP CNPq: 156420/2018-0 FAPESP: 2013/07793-6 FAPESP: 2018/16126-7

Made available in DSpace on 2020-12-10T17:34:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-07-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) FINEP Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Alkali niobium germanate glasses were prepared by melt-quenching in the ternary systems 75GeO(2)-15Nb(2)O(5)-10M(2)O with M = Li, Na, K, Rb and Cs. Thermal properties of these glasses and related glass-ceramics are strongly dependent on the alkaline modifier. Structural investigations by Raman allowed to determine that the alkali radius has an influence on the number of non-bridging oxygens and consequently on the average glass network connectivity. Raman spectra of sodium, potassium and rubidium germanate glass-ceramics exhibited slight changes when compared to the pristine glass and the new Raman features can be attributed to a 3D NbO6 network similar to orthorhombic niobium oxide. Characterization of the heat-treated glasses allowed to determine the crystalline phases precipitated in the samples and it has been shown that a single perovskite bronze-like phase of general formula M2Nb5O21 can be obtained in Na, K, and Rb-containing glasses. Luminescent properties of Eu3+-doped glasses pointed out a non-regular tendency where sodium-based glass seems to be the inflexion point of luminescent data with higher asymmetry around Eu3+ ions and higher quantum efficiency. In transparent glass-ceramics, the Eu3+ luminescent properties are clearly modified in the Na- and K-based samples with lower symmetry and quantum efficiency after heat-treatment. Such optical behavior is attributed to Eu3+ migration in the perovskite crystalline phase with highly distorted Eu3+ sites and shorter Eu3+-Eu3+ distances. Univ Fed Alfenas, Grp Quim Mat, Campus Pocos De Caldas, Pocos De Caldas, MG, Brazil Univ Estadual Paulista, Inst Quim, Araraquara, SP, Brazil Univ Estadual Paulista, Inst Quim, Araraquara, SP, Brazil CNPq: 156420/2018-0

High photoluminescence efficiency, unusual NIR broadband and tunable emission are possible in erbium-doped and tantalum germanate glasses and nanostructured glass-ceramics. The chemical microenvironment around erbium ions and their influence on optical properties are dependent on the TaO6 clusters formation and tantalum perovskite-like bronze crystallization, which are strongly related to the tantalum oxide content and annealing. Erbium ions are preferably distributed close to tantalum-rich environment, providing an intense emission with minimized nonradiative processes and inhomogeneous broadband NIR emission with increasing site numbers. A more pronounced broadening in the nanocrystalline samples is due to the multi-sites of the tantalum perovskite-like bronze crystalline structure. Green/red tunable emission from up conversion processes was observed since the erbium ions occupy a chemical environment with low phonon energy in the tantalum germanate glass and with close neighbors in the tantalum germanate glass-ceramics. Accordingly, the highly tantalum germanate glasses and glass ceramics are promising for photonic applications in optical amplification, lighting and lasing, as well as for nonlinear optical applications and studies considering the perovskite-like bronze crystalline samples.

Eu3+-, Er3+-doped and Er3+/Yb3+-codoped niobium alkali germanate glasses, in the compositional host system GeO2-Nb2O5-K2O were synthesized by the conventional melt-quenching technique. Glass-ceramics were manufactured by controlled heat treatment of the precursor glasses. Homogeneous glasses and nanocrystalline glass-ceramics were investigated by DSC, XRD, TEM and spectroscopic analysis. K2Nb14O36 crystals are formed in the prepared glass-ceramics. This crystalline phase has low phonon energy as compared to the precursor glass and a variety of chemical sites for rare-earth ions. In glass-ceramics, the rare-earth ions occupy higher symmetry sites of the K2Nb14O36 nanocrystals resulting in inhomogeneous broadband emissions. Judd-Ofelt parameters were obtained for the Eu3+- and Er3+-doped samples. Glass-ceramics heat-treated for 20 h exhibited the highest photoluminescence quantum efficiency. The increased quantum efficiency is due to the decrease of nonradiative decay processes, that depopulate the excited levels, as well as the decrease in hydroxyl content and overall phonon energy. However, luminescence quenching is verified for samples with longer crystallization times, which emphasizes the importance of optimized heat treatment parameters. The gain coefficient and upconversion data were obtained and corroborate the potential application of these materials as photonic devices, such as visible and NIR laser and optical amplifiers.

The green emissions of the trivalent erbium ions exhibit promising applications in photonics, such as the development of solid-state lasers, optical sensors, and light-emitting diodes (LED). In this work, the intensity of the emissions of two thermally coupled levels 2H11/2 and 4S3/2 excited states of Er3+ ions are studied in Er3+/Yb3+ co-doped tungsten sodium phosphate oxyfluoride glasses. The results demonstrate that an increase in the content of the PbF2 leads to an enhancement in the performance of these samples as optical sensors, and amplifies the relative thermal sensitivity from 0.82% K−1 to 1.15% K−1 for glass samples containing 10 mol% and 50 mol% of PbF2, respectively. Additionally, the effect of PbF2 is discussed in terms of the modifications of the site symmetries around Er3+ ions and changes in the energy gap between the thermally coupled levels, which implied in the improvement of the absolute thermal sensitivity at higher temperatures for high PbF2 contained sample.

Glasses in the binary system KPO3-Ta2O5 were prepared by the melt-quenching technique. Highly modified phosphate glasses with up to 40 mol% Ta2O5 were obtained. The samples were characterized by Differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD) analysis, Ultraviolet–Visible (UV–Vis) and infrared (IR) transmittance, Raman and luminescence spectroscopies. Thermal, structural and optical properties are strongly dependent of the tantalum oxide content. Thermal behavior and Raman data are in agreement with a progressive insertion of tantalum units in the phosphate network through P-O-Ta bonds. These bonds enhance the network connectivity due to TaO6 units cross-linking the linear phosphate chains. In addition, higher Ta2O5 contents in the glass network results in tantalum oxide-rich regions detected as Ta-O-Ta bridging bonds, apparently acting as crystallization nuclei. Emission spectra of Eu3+-doped glasses pointed out a decrease in the symmetry of the Eu3+ sites by increasing Ta2O5 content. A decrease in the excited state lifetimes was also identified due to the progressive Ta-rich environment around Eu3+ ion. Finally, photoluminescence quantum efficiency increases with tantalum insertion due to the reduction of local phonon energy around rare-earth ions. In this sense, high tantalum phosphate glasses are built up from TaOx polyhedra within the phosphate chains. The presence of TaOx clusters allows the improvement of optical and thermal properties and corroborates with the potential application of these materials photonic devices.

Made available in DSpace on 2018-12-11T16:54:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-10-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) Financiadora de Estudos e Projetos The evolution of research on luminescent phosphors led to research on materials doped with rare earth ions (RE3+), not only because of their photoluminescent properties, but also for their potential applications in photonics. The search for new photoluminescent materials has led to an investigation of the photoluminescence of RE3+ present in an aluminum oxide (Al2O3) matrix. This oxide has a transparent window on the short ultraviolet to near infrared, excellent mechanical properties and good chemical stability. Within this context, this work aims to obtain Al2O3: Er3+/Yb3+. The preparation of Al2O3: Er3+/Yb3+ involved two synthesis processes. For the co-precipitation process, rings of aluminum cans were used as precursors, and for the sol-gel process, the precursor used was tri-sec-butoxide aluminum. From the XRD results, high heat-treatment temperatures were observed to favor the formation of the α-Al2O3 phase and low temperatures were observed to favor the formation the γ-Al2O3 phase. The analysis of the photoluminescence emission spectra when excited at 980 nm, showed the up-conversion phenomenon with an emission in the visible region. The emission spectra also showed emission between 1400 and 1650 nm, with a maximum at about 1530 nm. The materials exhibit efficient energy absorption in the infrared region, with light emission in the visible region. Furthermore, the spectra show an intense emission in the infrared region assigned to the 4I13/2 → 4I15/2 transition of Er3+, demonstrating excellent potential to be used in optical amplifier device at the third telecommunications window. Grupo de Pesquisa em Química de Materiais – (GPQM) Departamento de Ciências Naturais Universidade Federal de São João del-Rei Campus Dom Bosco, Praça Dom Helvécio, 74 Instituto de Química UNESP, P.O. Box 355 Research Group of Materials Chemistry Universidade Federal de Alfenas, Campus de Poços de Caldas Departamento de Química Faculdade de Filosofia Ciências e Letras de Ribeirão Preto USP, Avenida Bandeirantes, 3900 Department of Chemistry and Physics University of Tennessee at Martin Desenvolvimento de Materiais Inorgânicos com Terras Raras - DeMITeR Instituto de Química – (IQ) Universidade Federal de Uberlândia – (UFU), Av. João Naves de Ávila, 2121 – Bairro Santa Mônica Instituto de Química UNESP, P.O. Box 355 FAPEMIG: CEX - RED-00010-14

Made available in DSpace on 2018-11-28T15:26:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-05-01 Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) FINEP (CT-INFRA) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) New glass compositions were investigated in this specific proportion (90-x)TeO2-10GeO(2)-xPbF(2) in order to study the influence of lead fluoride content on the thermal, structural and optical properties. Glass samples with x = 5 to 30% were prepared by melt-quenching method. Thermal characterizations by DSC allowed to identify a clear decrease of the glass transition temperature as well as a very distinct crystallization behavior for higher PbF2 contents. Raman spectroscopy suggests a progressive PbF2 incorporation with conversion of TeO4 to TeO3 units related with the modifier behavior of PbF2 in the glass network. X-ray diffraction patterns of crystallized samples support these results since crystalline TeO2 was detected for lower PbF2 contents whereas lead tellurite Pb2Te3O7 was identified for the most lead fluoride concentrated sample. UV-Vis-MR absorption spectra are in agreement with a progressive increase of the optical bandgap with lead fluoride concentration. Emission spectra of Eu3+ doped samples also pointed out a progressive structural change around Eu3+ ions with more symmetric sites. Finally, experimental lifetimes, Judd-Ofelt parameters and quantum efficiencies were obtained from these samples and exhibited a strong dependency of the lead fluoride contents, suggesting that these new fluorotellurite glasses are interesting hosts for rare earth ions. (C) 2017 Elsevier B.V. All rights reserved. Univ Fed Alfenas, Grp Quim Mat, Campus Pocos de Caldas, Pocos De Caldas, MG, Brazil Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, Av Bandeirantes 3900, BR-14040901 Ribeirao Preto, SP, Brazil Univ Estadual Paulista, Inst Quim, Araraquara, SP, Brazil Univ Estadual Paulista, Inst Quim, Araraquara, SP, Brazil FAPEMIG: CEX-APQ-01410-12 CNPq: 552225/2011-8

In this work, the glass forming ability was studied in potassium phosphate glasses with increasing amounts of TiO2 in order to obtain a glass-ceramic with photocatalytic properties. The first studied series has been the binary system (100-x) KPO3-xTiO2. Homogeneous and transparent glasses could be obtained with x varying from 10 to 30 mole%. Since the photocatalytic anatase phase could not be precipitated in this system, the ternary system KPO3-TiO2-Nb2O5 was investigated in order to incorporate higher TiO2 contents without spontaneous crystallization under cooling. Thermal properties of all glass samples were investigated by DSC and allowed identifying an increase of glass transition temperatures with increasing TiO2. For all compositions, exothermic events related with crystallization were also observed and suitable heat-treatments resulted in specific crystalline phases identified by X-ray diffraction. Selective precipitation of the anatase titanium oxide was successfully obtained from the glass compostion 35KPO3-25Nb2O5-40TiO2 (KN25T40) after heat treatment at 720°C for 2 h, suggesting the possibility of obtaining a glass-ceramic for photocatalytic applications. Structural investigations by Raman were also performed on glasses and glass-ceramics and allowed to point out the glass intermediary behavior of TiO2 in the phosphate vitreous network where TiO4 and TiO6 octahedra are inserted inside the phosphate network with TiO6 clusters identified at higher TiO2 contents. Raman analysis also identified anatase TiO2 in the KN25T40 glass-ceramic.

Niobium alkali germanate glasses were synthesized by the melt-quenching technique. The ternary system (90-x)GeO2-xNb2O5-10K2O forms homogeneous glasses with x ranging from 0 to 20mol%. Samples were investigated by DSC and XRD analysis, FTIR and Raman spectroscopy, and optical absorption. Structural and physical features are discussed in terms of Nb2O5 content. The niobium content increase in the glass network strongly modifies the thermal, structural and optical properties of alkali germanate glasses. DSC, Raman and FTIR analysis suggest niobium addition promotes NbO6 groups insertion close to GeO4 units of the glass network. XRD analysis also pointed out that samples containing high niobium oxide contents exhibit preferential niobium oxide rich phase after crystallization after heat treatment, which is similar to orthorhombic Nb2O5. Absorption spectra revealed high transmission range between 400nm to 6.2μm, added to a considerably decreased hydroxyl group content as the addition of niobium in the alkali germanate network. The niobium oxide rich phase crystallization process was studied and activation energy was determined, as well as nucleation and crystal growth temperatures and time for obtaining transparent glass-ceramics. This article is protected by copyright. All rights reserved.

Made available in DSpace on 2019-10-04T13:15:57Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-10-01 Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) FINEP Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Niobium alkali germanate glasses doped with Er3+ up to 4.0 mol% were synthesized by the melt-quenching technique. Glass-ceramics were obtained by controlled heat treatment of the pristine glass. Thermal and optical properties were investigated and are shown to depend on the erbium content. The main radiative parameters were obtained based on the Judd-Ofelt theory. The change of radiation energy processes and modification of the environment of the earth-rare ion occurs in samples with high erbium concentrations. In general, strong enhancement of upconversion emission occurs due to the efficient process of excited-state absorption for the high erbium content samples. Visible tunable phosphors emitting either red-to-green light depends on the erbium content and heat treatment. In addition, these glasses and glass-ceramics samples have high thermal stability and wide transmission window. For these reasons, Er3+-doped niobium germanate glasses and glass-ceramics may be suitable for photonic device applications, especially as visible laser. Univ Fed Alfenas, Grp Quim Mat, Campus Pocos Caldas, Pocos De Caldas, MG, Brazil Univ Sao Paulo, Fac Filosofia, Dept Quim Ciencias & Letras Ribeirao Preto, Ribeirao Preto, SP, Brazil Univ Sao Paulo, Inst Fis Sao Carlos, Sao Carlos, SP, Brazil Univ Sao Paulo, Inst Quim Sao Carlos, Sao Carlos, SP, Brazil Univ Estadual Paulista, Inst Quim, Araraquara, SP, Brazil Univ Estadual Paulista, Inst Quim, Araraquara, SP, Brazil FAPESP: 2013/07793-6

The main objective of this work has been to prepare and characterize the thermal and structural properties of glasses in the pseudo binary system TeO 2 –Pb(PO 3 ) 2 with respect to the composition. Homogeneous and transparent glass samples were obtained by the melt-quenching method in a large glass forming range in the pseudo binary system (100 − x )TeO 2 – x Pb(PO 3 ) 2 with x varying from 5 to 100. Thermal properties investigated by DSC pointed out an increase of the glass transition temperature from x = 5 to x = 40 and further decrease of Tg for higher Pb(PO 3 ) 2 concentrations. A similar tendency has been observed for the thermal stability against devitrification measured using the stability parameter Tx–Tg. FTIR together with Raman spectroscopies allowed building a structural model for these glasses with the contribution of distinct phosphate and tellurite units depending on the composition. Identification of crystalline phases obtained after the glasses heat-treatments obtained by X-ray diffraction support the structural evolution suggested by vibrational spectroscopies. These data suggest that incorporation of TeO 2 in the lead metaphosphate glass results in tellurium conversion from TeO 4 seesaw geometry to TeO 3 trigonal pyramids and consequent conversion of well-known metaphosphate units Q 2 to modified pyrophosphate units Q 2 1Te in which the phosphorus PO 4 tetrahedron is linked to another PO 4 unit and one TeO 3 pyramid. These tellurite trigonal units cross-link the modified metaphosphate chains with a resulting increase of the glass network connectivity. For high TeO 2 concentrations, all Q 2 were converted to Q 2 1Te and the additional tellurium atoms are incorporated in the glass network as TeO 4 seesaw units with a glass network built from a tridimensional network of TeO 3 , TeO 4 and Q 2 1Te . Finally, this work pointed out the possibility to use this pseudo-binary system for the preparation of phosphate glass-ceramics containing a TeO 2 crystalline phase or tellurite glass-ceramics containing a pyrophosphate or metaphosphate crystalline phase.

Made available in DSpace on 2018-11-28T01:36:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-12-01 Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) FINEP Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) In this work the novel glass system TeO2-Sb2O3-GeO2 was investigated and promising glass compositions were selected for further specific studies. Glass samples in the (80-0.8x)TeO2-(20-0.2x)Sb2O3-xGeO(2) molar composition were prepared by the melt-quenching method with a glass-forming domain from x = 10 to x = 90. Samples were investigated by XRD, DSC, FTIR, Raman spectroscopy and UV-visible absorption. The XRD and DSC results bring informations about the non-crystalline state and thermal properties of these materials. It has been observed that higher GeO2 contents lead to higher glass transition temperatures and thermal stabilities against crystallization. FTIR and Raman spectroscopies suggest a progressive incorporation of GeO2 in the covalent network of TeO2 with conversion of structural units TeO4 to TeO3. Absorption spectra revealed the high visible transparency of these samples and an increase of the optical band gap with GeO2 addition, in agreement with a decreasing polarizability of the glass network. Er3+ doped and Er3+/Yb3+ codoped samples were also studied with respect to their infrared emission properties and higher GeO2 contents lead to an increase in IR emission intensity at 1,5 mu m as well as longer radiative lifetimes. Finally, upconversion emission in the visible were also recorded and were shown to be strongly dependent of the composition. (C) 2016 Elsevier B.V. All rights reserved. Univ Fed Alfenas, Grp Quim Mat, Campus Pocos Caldas, Pocos De Caldas, MG, Brazil Univ Sao Paulo, Dept Quim, Fac Filosofia Ciencias & Letras Ribeirao Preto, Av Bandeirantes, BR-14040901 Ribeirao Preto, SP, Brazil Univ Estdual Paulista Julio Mesquita Filho, Inst Quim, Araraquara, SP, Brazil Univ Estdual Paulista Julio Mesquita Filho, Inst Quim, Araraquara, SP, Brazil

Crystalline lead–pyrophosphate precursor was prepared in aqueous solution from lead nitrate and phosphoric acid and characterized by X-ray diffraction, thermogravimetry and Raman scattering. This crystalline lead–phosphate was then used to prepare glass samples in the binary system Pb 2 P 2 O 7 –WO 3 . Dependence of WO 3 content on thermal, structural and optical properties were investigated by thermal analysis (DSC), Raman spectroscopy, UV–visible and near-infrared absorption and M-Line technique to access refractive index values. Incorporation of WO 3 in the lead–pyrophosphate matrix enhances the glass transition temperature and thermal stability against devitrification, favors formation of P O W bonds and WO 6 clusters. In addition, optical properties are strongly modified with a redshift of the optical bandgap with WO 3 incorporation as well as an increase of the refractive index from 1.89 to 2.05 in the visible.

Glasses were prepared by the melt-quenching method in the ternary system Pb(PO 3 ) 2 -WO 3 -PbF 2 and doped with Er 3+ in order to prepare luminescent transparent glass-ceramics. This work focused on thermal and structural characterization of tungsten lead-phosphate glasses and crystallization study for preparing transparent glass-ceramics. Thermal properties such as thermal stability and crystallization behavior upon heating were investigated by DSC in function of PbF 2 content. For low PbF 2 concentrations, only one crystallization peak due to Pb 3 (PO 4 ) 2 is observed whereas samples containing more than 15% of PbF 2 present another exothermic event at lower temperatures related with precipitation of PbF 2 , Pb 2 P 2 O 7 and Pb 2 OF 2 . Structural investigations by Raman spectroscopy suggest that PbF 2 modifies the tungsten-phosphate network through the formation of P―F and P―O―Pb bonds but the average network connectivity remains almost constant. A crystallization study has been performed by DSC to investigate the dominant crystallization mechanisms in these glasses and it has been established that Pb 3 (PO 4 ) 2 is nucleated on the surface whereas PbF 2 , Pb 2 P 2 O 7 and Pb 2 OF 2 crystallize dominantly from the glassy bulk. Transparent glass-ceramics containing nanosized PbF 2 crystallites were also prepared by suitable heat-treatment on the glass sample containing 20% of PbF 2 and Raman microscopy of these glass-ceramics supports the crystallization mechanisms determined by DSC.

Glasses were prepared in the binary system (100 − x )NaPO 3 – x MoO 3 with x varying from 0 to 50 mol%. An increase in the MoO 3 concentration promotes a strong absorption in the visible and near infrared attributed to Mo reduction during glass synthesis. X-ray absorption measurements were performed at the Mo K and L 3 edges to investigate both the coordination number and oxidation state of Mo in these glasses. The evolution of the pre-peak observed at the K edge suggests that Mo atoms are six-fold coordinated in these glasses. This hypothesis was confirmed by data obtained at the Mo–L 3 -absorption edge. Since the final electronic states at the L 3 -absorption edge are mostly orbitals of d-character which are splitted by the ligand field, the amplitude of the d-orbital splitting could be estimated and the related coordination number of Mo obtained. Finally, the oxidation state of Mo could be related with a change of the white line intensity at the Mo–L 3 edge. These results confirm that the optical absorption in the visible is due to Mo reduction and that transparent samples prepared by slow cooling contain less reduced Mo species.

Vitreous samples were prepared in the binary system NaPO 3 –MoO 3 and their characteristic temperatures were determined by Differential Scanning Calorimetry. Glasses with high amounts of MoO 3 (>45 mol%) exhibit an intense crystallization peak and the composition 50 NaPO 3 –50 MoO 3 was chosen for the crystallization study. Two different methods based on thermal analyzes were used to determine the mechanism of crystallization in these molybdenum–phosphate glasses. In the first procedure, thermal analyses by DTA were performed on samples with different grain sizes and the crystallization tendency deduced in function of superficial area. The second method used the classical non-isothermal crystallization study: DSC measurements were performed under several heating rates to access activation energy for crystallization and Avrami parameter n . Critical cooling rate was calculated and compared with experimental data obtained from DTA analysis upon cooling.

In this paper we investigate the energy transfer processes in Tm 3+ /Er 3+ doped telluride glass pumped at the commercial diode laser pump wavelength ∼800 nm. Tailoring the rare-earths content in the glass matrix, seven main energy transfer channels within the doping range considered were identified. A 6-fold enhancement of the Er 3+ visible frequency upconversion fluorescence at ∼660 nm is observed due to the inclusion of Tm 3+ ions. This is evidence of the relevant contribution of the route Er 1 ( 4 I 11/2 ) + Er 2 ( 4 I 13/2 ) → Er 1 ( 4 I 15/2 ) + Er 2 ( 4 F 9/2 ) to the process. Energy migration among pumped 4 I 9/2 level reducing the efficiency of the upconversion emission rate ( 3 H 11/2 , 4 S 3/2 , and 4 F 9/2 ) is observed for Er 3+ above 1.5 wt%. The rate equations regarding the observed energy transfer routes are determined and a qualitative analysis of the observed processes is reported.

The glass forming ability was investigated in the codoped Er3+/Yb3+ ternary system NaPO3-WO3-PbF2 with increasing amounts of PbF2. It has been found that glass samples can be obtained for PbF2 contents ranging from 0 mole% to 50 mole% for the codoped samples and an undoped sample containing 60% of lead fluoride could also be vitrified. Thermal properties of the most PbF2 concentrated glasses exhibit strong dependence of the composition with a decrease of the glass transition temperatures and thermal stabilities against devitrification with increasing the lead fluoride content. These glass samples were heat-treated near the crystallization peaks and the X-ray diffraction measurements pointed out that the dominant phase which precipitates from the glass samples containing 40% and 50% of PbF2 is the lead fluorophosphate phase Pb5F(PO4)3 whereas the sample containing 60% of PbF2 exhibits a preferential bulk crystallization of cubic lead fluoride β-PbF2.

In this work, new glass compositions were prepared in the ternary system GeO2–K2O–Ta2O5. Potassium oxide was added to reach the complete melt of the starting mixture and two composition series were investigated: the first one with a constant K2O molar content of 10% in the ternary system (90–x)GeO2–10K2O–xTa2O5 and the second one with the same molar content of K2O and Ta2O5 in the ternary system (100–2x)GeO2–xK2O–xTa2O5. Homogeneous and transparent glasses could be obtained between x = 0 and 20. X-ray diffraction analyzes of samples with x = 25 identified orthorhombic Ta2O5 in the first series and an isostructure of K3.8Ge3Nb5O20.4 in the second series where it is assumed that Ta5+ ions are inserted in the Nb5+ sites. As one of our goal with these materials is related with the preparation of glass-ceramics containing Ta2O5 nanocrystals, the first series has been selected for further characterizations. An increase in glass-transition temperatures with increasing Ta2O5 content as well as an increase of the thermal stability from x = 0 to 10 has been identified by differential scanning calorimetry. For higher contents, crystallization events were identified. Fourier transform infrared and Raman spectroscopic characterizations allowed to point out the intermediary behavior of Ta2O5 in the vitreous network where TaO6 octahedra are inserted inside the germanate network with TaO6 clusters identified at higher Ta2O5 contents. Heat-treated samples with high tantalum contents (x = 15 and 20) exhibit preferential precipitation of orthorhombic Ta2O5 with nanometric size, suggesting the possibility of obtaining transparent glass-ceramics for optical applications.

X-ray absorption spectroscopy was used to study the local environment of tungsten atoms in NaPO 3 –BaF 2 –WO 3 glasses and the results were compared with crystalline references Na 2 WO 4 and WO 3 . XANES measurements at the W-L 1 edge allowed to determine a distorted octahedral environment of tungsten atoms in these glasses similar to the local order of tungsten in monoclinic WO 3 . Extended X-ray absorption fine structure (EXAFS) has been used as a local probe to monitor the effect of WO 3 concentration on the tungsten environment. Based on an analysis of the EXAFS data, we proposed a three-shell model of oxygen atoms around tungsten as in monoclinic WO 3 . With increasing WO 3 concentration, it was found that R 2 decreases from 1.96 to 1.92 A whereas R 3 increases from 2.07 to 2.12 A.

Diode-pumped Yb-doped glass lasers have received considerable attention for applications such as high-power beam production or femtosecond pulses generation. In this paper, we evaluate the laser potential of three different glass families doped with Yb3+: alkali lead fluorborate (PbO–PbF2–B2O3), heavy metal oxide (Bi2O3–PbO–Ga2O3) and niobium tellurite (TeO2–Nb2O5–K2O–Li2O). Spectroscopic properties were studied for the samples and calculations of the minimum laser pump intensity (Imin), saturation fluence (Usat) and the theoretical limit of peak power (Pmax) are also presented. A comparison of laser properties of these three different glasses and their importance is shown and analyzed.

Infrared-to-visible frequency upconversion through cooperative energy-transfer and thermal effects in Tb 3+ /Yb 3+ -codoped tellurite glasses excited at 1.064 μm is investigated. Bright luminescence emission around 485, 550, 590, 625 and 655 nm, identified as due to the 5 D 4 → 7 F J ( J =6, 5, 4, 3, and 2) transitions of the terbium ions, respectively, was recorded. The excitation of the 5 D 4 emitting level of the Tb 3+ ions is assigned to cooperative energy-transfer from pairs of ytterbium ions. The effect of temperature on the upconversion process was examined and the results revealed a fourfold upconversion enhancement in the 300–500 K interval. The enhancement of the upconversion process is due to the temperature dependence of the Yb 3+ -sensitizer absorption cross-section under anti-Stokes excitation. A rate-equation model using multiphonon-assisted absorption for the ytterbium excitation combined with the energy migration effect between Yb–Yb pair and Tb 3+ ground-state depopulation via multiphonon excitation of the 7 F J excited states describes quite well the experimental results.

Temperature investigation of infrared-to-visible frequency upconversion in erbium-doped tellurite glasses excited by CW laser radiation at 1540 nm and under cryogenic temperatures is reported. Intense upconversion emission signals around 530, 550 and 660 nm corresponding to the 2H11/2, 4S3/2, and 4F9/2 transitions to the 4I15/2 ground state were generated and studied as a function of the laser intensity and temperature. The upconversion excitation mechanism of the Er3+ ions emitting energy levels was accomplished via stepwise multiphoton absorption. The green upconversion luminescence exhibited a fivefold intensity enhancement when the temperature of the sample was varied in the range between 5 and 300 K. A maximum green upconversion intensity was attained around 120 K and a steady decreasing behavior for higher temperatures up to 300 K was observed. A model based upon conventional rate equations was used to model the observed temperature evolution of the upconversion luminescence.

Optical spectroscopic properties of Tm3+-doped 60TeO2−10GeO2−10K2O−10Li2O−10Nb2O5 glass are reported. The absorption spectra were obtained and radiative parameters were determined using the Judd–Ofelt theory. Characteristics of excited states were studied in two sets of experiments. Excitation at 360 nm originates a relatively narrow band emission at 450 nm attributed to transition 1D2→3F4 of the Tm3+ ion with photon energy larger than the band-gap energy of the glass matrix. Excitation at 655 nm originates a frequency upconverted emission at 450 nm (1D2→3F4) and emission at 790 nm (3H4→3H6). The radiative lifetimes of levels 1D2 and 3H4 were measured and the differences between their experimental values and the theoretical predictions are understood as due to the contribution of energy transfer among Tm3+ ions.

Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm 3+ and Er 3+ excited at 1.064 μm is investigated. The Tm 3+ /Er 3+ -codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the 1 G 4 → 3 H 6 transition of the Tm 3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 530, 550 nm green and 660 nm red upconversion luminescences were identified as originating from the 2 H 11/2 , 4 S 3/2 → 4 I 15/2 and 4 F 9/2 → 4 I 15/2 transitions of the Er 3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined.

Upconversion luminescence and thermal effects in Pr3+/Yb3+- and Er3+/Yb3+-codoped 60TeO2–10GeO2–10K2O–10Li2O–10Nb2O5 tellurite glasses excited by CW infrared radiation at 1.064 μm is reported. Generation of intense green and red fluorescence emission in Er3+/Yb3+-codoped samples and appreciable upconversion luminescence in the wavelength region of 450–680 nm in Pr3+/Yb3+-codoped samples is observed. Temperature-induced enhancement of ×12 in the upconversion efficiency in Er3+/Yb3+- and ×10 in the Pr3+/Yb3+-doped samples is demonstrated.

Glass samples with the composition (mol%) 80TeO2–10Nb2O5–5K2O–5Li2O, stable against crystallization, were prepared containing Yb3+, Tm3+ and Ho3+. The energy transfer and energy back transfer mechanisms in samples containing 5% Yb 3+ –5% Tm 3+ and 5% Yb 3+ –5% Tm 3+ –0.5% Ho 3+ were estimated by measuring the absorption and fluorescence spectra together with the time dependence of the Yb 3+ 2 F 5/2 excited state. A good fit for the luminescence time evolution was obtained with the Yokota–Tanimoto's diffusion-limited model. The up-conversion fluorescence was also studied in 5% Yb–5% Tm, 5% Yb–0.5% Ho and 5% Yb–5% Tm–0.5% Ho tellurite glasses under laser excitation at 975 nm. Strong emission was observed from 1 G 4 and 3 F 2 Tm 3+ energy levels in all samples. The 5 S 2 Ho 3+ emission was observed only in Yb3+Ho3+ samples being completely quenched in Yb3+/Tm3+/Tm3+ samples.

Alkali niobium tellurite glasses have been prepared and some of their properties measured by differential scanning calorimetry and Raman scattering. The vitreous domain was established in the pseudo ternary phases diagram for the system TeO2–Nb2O5–(0.5K2O–0.5Li2O). Raman scattering shows that for samples in the TeO2 rich part of the phase diagram the vitreous structure is composed essentially of (TeO4) units connected by the vertices, as in the α-TeO2 crystal. The addition of alkali and niobium oxides causes depolymerization to occur with structures composed essentially of (TeO3) and (NbO6) units. Samples with the composition (mol%) 80TeO2–10Nb2O5–5K2O–5Li2O, stable against crystallization, were prepared containing up to 10% mol Nd3+. The addition of this oxide increases the rigidity of the vitreous network shifting characteristic temperatures to higher temperatures. For the 10% Nd3+ sample amorphous phase separation is assumed to exist from the observation of two glass transition temperatures. Spectroscopic properties such as Judd–Ofelt Ωλ intensity parameters, radiative emission probabilities, and induced emission cross sections were calculated. From these results and also from the emission quenching observed as a function of Nd3+ concentration, we suggest that these glasses could be utilized in optical amplifying devices.

We investigated near-infrared-to-blue upconversion from thulium (Tm3+) doped in tellurite glasses upon continuous wave excitation near 800 nm. We observed an enhancement of over two orders of magnitude of the upconverted emission at ∼480 nm when neodymium (Nd3+) ions were codoped with Tm3+ ions. For comparison, using a Tm3+:Nd3+ codoped fluorozirconate glass as a reference material we observed a 40-fold enhancement of the blue emission. Analysis of the blue emission for samples with different doping levels of Nd3+ ions showed that energy transfer between Nd3+ and Tm3+ is the mechanism responsible for the enhancement in upconversion.

Infrared-to-visible upconversion luminescence emission in Nd 3+ -doped 60TeO 2 –10GeO 2 –10K 2 O–10Li 2 O–10Nb 2 O 5 tellurite glasses under cw excitation around 800 nm is investigated. Blue (430, and 475 nm), green (530 nm) and yellow-orange (590 nm) energy upconversion emission owing to the 2 P 1/2 → 4 I j ( j =9/2, 11/2, 13/2 and 15/2) transitions of the Nd 3+ ions, respectively, was recorded. The dependence of the upconversion intensity upon the excitation wavelength and pump power is also studied. The upconversion excitation mechanism responsible for the observed emission signals is attributed to stepwise multiphoton absorption.

Frequency upconversion emission (UC) in visible region from Er3+-doped materials have been intensively investigated in the last decades and employed in the development of photonic devices such as temperature sensors [1–3]. Among the multitude of potential hosts, phosphate glasses are promising materials for this purpose due to their physical properties such as large thermal expansion coefficient, low melting temperatures, high transparency in the UV range and efficient infrared-to-visible UC [4]. In this work, we investigate the use of Er3+-doped tungsten-lead and sodium-lead-metaphosphate glasses as temperature sensors, based on the fluorescence intensity ratio technique [1].

Efficient energy upconversion of cw radiation at 1.064 μm into blue, red, and near infrared emission in Tm3+-doped Yb3+-sensitized 60TeO2-10GeO2-10K2O-10Li2O-10Nb2O5 glasses is reported. Intense blue upconversion luminescence at 485 nm corresponding to the Tm3+ 1G4→3H6 transition with a measured absolute power of 0.1 μW for 800 mW excitation power at room temperature is observed. The experimental results also revealed a sevenfold enhancement in the upconversion efficiency when the sample was heated from room temperature to 235 °C yielding 0.7 μW of blue absolute fluorescence power for 800 mW pump power. High brightness emission around 800 nm (3F4→3H6) in addition to a less intense 655 nm (1G4→3H4 and 3F2,3→3H6) fluorescence is also recorded. The energy upconversion excitation mechanism for thulium emitting levels is assigned to multiphonon-assisted anti-Stokes excitation of the ytterbium-sensitizer followed by multiphonon-assisted sequential energy-transfer processes.

In this work, bright visible upconversion emission excited through cooperative energy-transfer and thermal effects in Tb/sup 3+//Yb/sup 3+/-codoped 60TeO/sub 2/-10GeO/sub 2/-10K/sub 2/O-10Li/sub 2/O-10Nb/sub 2/O/sub 5/glasses excited at 1.064 /spl mu/m is investigated. Bright upconversion luminescence around 485, 550, 590, 625 and 655 nm, identified as due to the /sup 5/D/sub 4//spl rarr//sup 7/F/sub J/(J= 6, 5, 4, 3, and 2) transitions of the terbium-ions, respectively, was generated.

In this work, tantalum alkali-phosphate glasses were prepared in the ternary system 0.9[(100 − x)NaPO3 − xTa2O5] − 0.1K2O with x varying from 0 to 20. The thermal properties as a function of Ta2O5 content were investigated by Differential Scanning Calorimetry and Differential Thermal Analysis in order to understand the influence of composition on glass transition temperatures and crystallization behaviors. Increasing Ta2O5 content leads to a drastic and linear increase of glass transition temperatures in agreement with the increasing viscosity of the melt observed during the synthesis. In addition, Ta2O5 incorporation results in high thermal stability against devitrification, suggesting the intermediary role of tantalum in the alkali-phosphate network. Comparison of powder and bulk thermal analyzes also pointed out a dominant surface crystallization mechanism for these glass samples. UV–visible absorption measurements proved the high visible transparency of the samples and a decrease of the optical bandgap energy with tantalum addition, suggesting an increase of the glass network covalency. Finally, vibrational spectroscopies performed by FTIR and Raman support the hypothesis of tantalum insertion inside the phosphate tetrahedral network with TaO6 units cross-linking the metaphosphate and pyrophosphate units. Thus, the intermediary behavior of tantalum increases the network connectivity with higher rigidity, glass transition temperatures and thermal stabilities against devitrification.