The main interests of the group in phosphate glasses deal with their applications in optics and energy fields. On the one hand, neodymium doped phosphate glasses are currently the best solution as hosts for high energy and high power lasers, though the production of big and homogeneous specimens requires of very special conditions. Furthermore, small amounts of retained water conduct to important deteriorating effects from the quenching of the Nd luminescence. We have recently demonstrated that a very efficient dehydroxylation method of the phosphate glasses may be obtained by re-melting the glass under a reducing or inert atmosphere [Muñoz, Int. J. App. Glass Sci. (2019)]. This new processing technique allows to obtain glasses with high optical homogeneity and absorption coefficients of hydroxyl ions below 2 cm-1. The luminescence behaviour of Nd3+ ions has shown optimal results for their application as high power laser glasses, and the thermal and mechanical properties of the currently studied alumina-containing glasses have comparable values to those of commercial laser glasses, proving that the employed method of dehydroxylation may be a promising alternative for their production.
On the other hand, phosphate glasses are well known for their high dissolution rates in aqueous media though, nevertheless, they have found relevant technological applications as low temperature sealing glasses, matrices for the immobilization of radioactive wastes or as laser hosts as mentioned above. Another way to improve their durability is through nitridation, where part of the oxygen is substituted by nitrogen atoms by means of thermal ammonolysis reactions under NH3 flow. As a consequence, the dissolution rate can be decreased by orders of magnitude at the same time that other properties are improved, such as hardness, thermal and mechanical resistance and ionic conductivity [Muñoz et al., Solid State Ionics 179 (2008) 574], having found application as solid electrolytes in lithium secondary batteries when processed as thin-films as the so-called LiPON electrolytes [Yu, J. Electrochem. Soc., 144(2) (1997) 524].
Finally, great attention is also paid to the study of the relationships between the properties of the glasses and their atomic structure and thermodynamics, conducting basic research onto a range of topics such as the viscous behaviour, glass-forming ability and the prediction of their properties [Dagupati et al. Mat. Chem. Phys., 258 (2021) 123941].
Nd-doped phosphate laser glasses
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F. Muñoz, R. Balda, A highly efficient method of dehydroxylation and fining of Nd phosphate laser glasses, Int. J. App. Glass Sci. https://onlinelibrary.wiley.com/doi/full/10.1111/ijag.12974
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F. Muñoz, L. Sánchez-Muñoz, The glass-forming ability explained from local structural differences by NMR between glasses and crystals in alkali metaphosphates, J. Non-Cryst. Solids, 503-504 (2019) 94-97. https://www.sciencedirect.com/science/article/pii/S0022309318305532
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P. Hockicko, J. Mizeráková, F. Muñoz, The internal friction of lithium and sodium borophosphate glasses, J. Non-Cryst. Solids, 498 (2018) 194-198. https://www.sciencedirect.com/science/article/pii/S0022309318303752
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Laura G. Paraschiv, Francisco Muñoz, Lars R. Jensen, Raino Mikael Larsen, Yuanzheng Yue, Morten M. Smedskjaer, Structural impact of nitrogen incorporation in alkali germanophosphate oxynitride glasses, J. Am. Ceram. Soc. 101 (2018) 5004-5019. https://onlinelibrary.wiley.com/doi/full/10.1111/jace.15747
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A. Dias, F. Muñoz, A. Alvarez, P. Moreno, J. Atienzar, A. Urbieta, P. Fernandez, M. García, R. Serna, J. Solis, Fs-laser writing of photonic devices in borate glasses compositionally designed to be laser writable, Optics Letters 43(11) (2018) 2523-2526. https://www.osapublishing.org/ol/abstract.cfm?uri=ol-43-11-2523
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Laura G. Paraschiv, Francisco Muñoz, Lars Jensen, Yuanzheng Yue, Morten M. Smedskjaer, Structural stability of NaPON glass upon heating in air and nitrogen, J. Non-Cryst. Solids 482 (2018) 137-146. https://www.sciencedirect.com/science/article/pii/S0022309317306944
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Xin Wang, Francisco Muñoz, Dongbing He, Yajun Ding, Jinjun Ren, Wei Chen, Hong Li, Lili Hu, Effect of SiO2 on properties and structure of P2O5-Al2O3-Li2O-MgO-Sb2O3 glass, J. Alloys and Compounds 729 (2017) 1038-1045. https://www.sciencedirect.com/science/article/pii/S0925838817331316
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Jana Mizeráková, Peter Hockicko, Francisco Muñoz, Dielectric study of Lithium and Sodium Borophosphate Glasses, Communications 19 (2017) 46-50.
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Francisco Muñoz, Akira Saitoh, Rafael Jiménez-Riobóo, Rolindes Balda, Synthesis and properties of Nd-doped oxynitride phosphate laser glasses, J. Non-Cryst. Solids 473C (2017) 125-131. https://www.sciencedirect.com/science/article/pii/S0022309317303976
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Francisco Muñoz, Pedro Moreno-Zárate, Javier Solís, Influence of melting conditions on the water content and structure of K2O-La2O3-Al2O3-P2O5 glasses, J. Non-Cryst. Solids 473C (2017) 114-119. https://www.sciencedirect.com/science/article/pii/S0022309317303939
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Laura Muñoz-Senovilla, Gregory Tricot, Francisco Muñoz, Kinetic fragility and structure of lithium borophosphate glasses analysed by solid state NMR, Phys. Chem. Chem. Phys. 19 (2017) 22777-22784. https://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04171C#!divAbstract
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Francisco Muñoz, Laura Muñoz-Senovilla, A model for the construction of the network in phosphate glasses through viscosity-structure relationships, J. Non-Cryst. Solids 471 (2017) 142-145. https://www.sciencedirect.com/science/article/pii/S0022309317302776
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L. Muñoz-Senovilla, F. Muñoz, G. Tricot, I. Ahmed, A. J. Parsons, Structure-properties relationships in fibre drawing of bioactive phosphate glasses, J. Mat. Sci. 52 (2017) 9166-9178. https://link.springer.com/article/10.1007/s10853-017-0773-7
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Georgiana Laura Paraschiv, Francisco Muñoz, Gregory Tricot, Nerea Mascaraque, Lars R. Jensen, Yuanzheng Yue, Morten M. Smedskjaer, Mixed alkali silicophophate oxynitride glasses: Structure-Property relations, J. Non-Cryst. Solids 462 (2017) 51-64. https://www.sciencedirect.com/science/article/pii/S0022309317300819
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Mouritz N. Svenson, G. Laura Paraschiv, Francisco Muñoz, Yuanzheng Yue, Sylwester J. Rzoska, Michal Bockowski, Lars R. Jensen, Morten M. Smedskjaer, Pressure-induced structural transformations in phosphorus oxynitride glasses, J. Non-Cryst. Solids 452 (2016) 153-160. https://www.sciencedirect.com/science/article/pii/S0022309316303726
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P. Mezeix, F. Célarié, P. Houizot, Y. Gueguen, F. Muñoz, and T. Rouxel, ¬¬Elasticity and viscosity of BaO-TiO2-SiO2 glasses in the 0.9 to 1.2Tg temperature interval, J. Non-Cryst. Solids 445-446 (2016) 45-52. https://www.sciencedirect.com/science/article/pii/S0022309316301624
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Georgiana Laura Paraschiv, Francisco Muñoz, Lars R. Jensen, Yuanzheng Yue, Morten M. Smedskjaer, Impact of Nitridation of Metaphosphate Glasses on their Liquid Fragility, J. Non-Cryst. Solids 441 (2016) 22-28. https://www.sciencedirect.com/science/article/pii/S0022309316300588
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Laura Muñoz-Senovilla, Jana Bírešová, Peter Hockicko, Francisco Muñoz, Investigation of the relationships between acoustic attenuation and ionic conduction in metaphosphate glasses, J. Non-Cryst. Solids 440 (2016) 26-30. https://www.sciencedirect.com/science/article/pii/S0022309316300485
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N. Mascaraque, G. Tricot, A. Durán, F. Muñoz, Structural features of LiPON glasses determined by 1D and 2D 31P MAS NMR, Int. J. App. Glass. Sci. 7(1) (2016) 69-79. https://onlinelibrary.wiley.com/doi/full/10.1111/ijag.12120
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Yaqoot Shahrayar, Eric Wein, Jung-Ju Kim, Randall E. Youngman, Francisco Muñoz, Hae-Won Kim, Antonio Tilocca, Ashutosh Goel, Structure-solubility relationships in fluoride-containing phosphate based bioactive glasses, J. Mat. Chem. B. 3 (2015) 9360-9373. https://pubs.rsc.org/en/Content/ArticleLanding/2015/TB/C5TB01494H#!divAbstract
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L. Muñoz-Senovilla, S. Venkatachalam, F. Muñoz, L. Van Wüllen, Relationships between fragility and structure through viscosity and high temperature NMR measurements in Li2O-ZnO-P2O5 phosphate glasses, J. Non-Cryst. Solids 428 (2015) 54-61. https://www.sciencedirect.com/science/article/pii/S0022309315301435
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Nerea Mascaraque, José Luis G. Fierro, Francisco Muñoz, Alicia Durán, Yusuke Ito, Yoshiaki Hibi, Ryo Harada, Atsutaka Kato, Akitoshi Hayashi, Misahiro Tatsumisago, Thio-oxynitride phosphate glass electrolytes prepared by mechanical milling, J. Mat. Res. 30 (2015) 1-9. https://www.cambridge.org/core/journals/journal-of-materials-research/article/thiooxynitride-phosphate-glass-electrolytes-prepared-by-mechanical-milling/084DD480F9D937E7055D154D5A5FD585
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Peter Hockicko, Jozef Kudelcik, Francisco Muñoz, Laura Muñoz-Senovilla, Structural and electrical properties of LiPO3 glasses, Advances in Electrical and Electronic Engineering 13(2) (2015) 198-205.
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N. Mascaraque, A. Durán, F. Muñoz, Effect of nitrogen and fluorine on the chemical properties of lithium phosphate glasses, J. Non-Cryst. Solids 417-418 (2015) 60-65. https://www.sciencedirect.com/science/article/pii/S0022309315001180