Comparison of such different glass systems can be facilitated by using the concept of optical basicity, a system that is based on the quantification of the electron donor power of the glass matrix rather than on a certain composition. The concept of optical basicity works well for inorganic non- metallic oxide glasses and has even be extended to F and N or S containing systems (Duffy 1992, 2011; Ehrt 2018; Möncke et al. 2019). This concept is most useful for optical properties such as refractive index and band gap; however, the extent of ligand field splitting and redox equilibria of polyvalent ions can also be related to the optical basicty.
Table 3. Properties of monomeric and binary sodium glasses of the type Na2O-F2On (with F=B, Si, P, Te, Ge, Sb), as well as of selected multicomponent glasses. Density𝝆𝝆, transition temperature Tg, experimental melting temperature Tm
(or when available in brackets, liquidus melting temperature), coefficient of thermal expansion CTE, refractive index n and Abbe number 𝝂𝝂 (experimental wavelength given as subscript, e=546.1 nm or d=587.1 nm, D=589.3 nm, theoretical optical basicity 𝚲𝚲𝟏𝟏, data in italics are predicted values from SciGlass6.7, calculated with factors from Priven (Mazurin and Priven , Priven 2004)
Glass 𝝆𝝆
g/cm3 Tg
°C Tm*
°C CTE
10-7K-1 n 𝝂𝝂 Egap
eV 𝚲𝚲th Ref.
SiO2 2.20 1203 CVD (1728) 5 1.48e 68e 8.25 0.48 a, b, c
GeO2 3.64 514 1400 (1150) 77 1.61d 42d 5.63 0.70 d, e, f
TeO2 5.62 307 900 - 2.20e 20e 3.37 0.99 g, h
P2O5 2.39 393 1000 77 1.50d 61d - 0.25 i, j
B2O3 1.84 230-40 850-1000 170 1.45e 58e 7.2 0.42 f, k, l
Sb2O3 5.11 250 900 163 2.10d 22? 3.33 1.14 k, l, m, n
Na2O-2SiO2 2.49 460 1600 160 1.51e 55e - 0.60 o
Na2O-2GeO2 3.60 445 - 130 1.63D 41D - 0.71 SciGlass
Na2O-2TeO2 4.20 211 800 - ~1.8d ~22d - 0.97 p, q
Na2O-P2O5 2.48 275 620 250 1.48e 66e - 0.58 r
Na2O-B2O3 2.35 409 800-900 168 1.52D 52D - 0.58 SciGlass
Na2O-Sb2O3 4.72 255 - 180 1.92D 25D - 1.16 SciGlass
ZBLAN 2 4.4 260 470 200 1.50e 78e 5 0.47 s, t
F00 3 3.42 400 1000 - 1.41e 105e 8.25 0.35 s, u
FP10 4 3.54 440 1000 160 1.46e 90e 7.75 0.37 b, s
73Bi2O3-
27B2O3 7.79 340 1000 110 2.30e 15e 2.0 0.98 b
P-laser glass 5 2.59 460 nda 116 1.51d 68.4d - - v
As2S3 3.2 454 850 237 2.41µm 1603-5µm 2.2 1.3 v, w, x
Plexiglas 8N 6 1.19 117 220-260 80050 1.49 59 4 - y, z
47
Notes:
1 Based on recent recommended values as listed by Rodriguez et al. (2011); Na2O=1.11; values for vitreous P2O5
and B2O3 from (1976) for sulfides see Duffy (1992) and for fluorides see Duffy (2011)
2 53ZrF4-20BaF2-4LaF3-3AlF3-20NaF
339AlF3-10MgF2-28CaF2-23SrF2
4 10Sr(PO3)2-35AlF3-30CaF2-15SrF2-10MgF2
5 Laser glass, LG-770 from Schott, a neodynium containing alumophosphate based glass (Musgraves, Hu et al.
2019)
6 Plexiglass – polymethylmethacrylate (PMMA), commercial product References:
a Lithosil data sheet (SCHOTT Lithotec AG 2006);b Heraeus Quarzglas GmbH & Co. KG (2016); c Ehrt et al. (2000);
d Dennis and Laubengayer (1926); e Walker et al. (2015); f Shelby (1974); g Kim et al. (1993); h Tagiara et al. (2017);
i Hudgens (1994); j Kordes et al. (1953); k Terashima et al. (1996); l Kordes (1939); m Doweidar (2015); n Bednarik and Neely (1982); o Ehrt and Keding (2009); p Kavaklıoğlu et al. (2015); q nd and 𝜈𝜈d for 40Na2O-60TeO2 Vogel (1992);
r Möncke et al. (2018); s Möncke et al. (2004, 2005); t Poulain et al. (1992); u Ehrt (2015); v Musgraves et al. (2019);
w Glaze et al. (1957); x Fekeshgazi et al. (2005); y Evonik Industries AG (2019); z Amine et al. (2018).
Actually, the concept was originally developed for the assessment of slags and the redox state of polyvalent ions therein. Importantly, it should be noted that many apparent correlations, e.g.
when comparing the optical basicty with thermal properties, is infact a corrleation with the increased number of non-bridging oxygen ions created by adding modifier oxides of higher basicity compared to the network former (B, Si or P) and not a direct causation to a higher electron donor power of the glass matrix. This becomes apparent when comparing e.g. the absorption spectra of transition metal ions in a high basicity, highly polymerized tellurite or antimonite glass with a highly modified silicate glass of lower optical basicity. Probe ions like Co2+ or Ni2+ are indicators of non-bridging oxygen atoms, and change their coordination from octahedral sites in low basicty borate, phosphate or silicate rich glasses, to tetrahedral coordination as the optical basicty increases with the addition of modifier oxides. In high basicty tellurite or antimonite rich glasses the octahedral coordinations dominated whileaddition of Na2O decreases actually the optical basicity but still supports the tetrahedral coordination of these probe ions as they link to the non-bridging oxygen atomsthat are generated by modifier oxide addition, that is preferential bonding sites of high microbasicity (Soltani et al. 2016)
CONCLUDING REMARKS
Many materials can form a glass when quenched fast enough, organic polymers as well as metals or, oxides, which are the largest group in inorganic non-metallic glasses. All glasses have two characteristic properties: one is the lack of a long-range order and the other is that they all exhibit a glass transition temperature. One big advantage of glasses over many other materials is their formability, due to a viscosity behavior that exhibits a broad softening interval, which allows molding (form pressing, form blowing), fiber drawing or the preparation of large bulk pieces or large planes of float glass. The lack of long-range order allows for an almost unlimited number of compositional variations that do not need to consider stoichiometric compositions as is often found for mixed crystals. Thus, the structure and properties of glasses can be adjusted and fine-tuned on different scales.
48 The variability of glass compositions cannot be fully honored in such a short book chapter.
However, we hope the interested reader got a general idea and will find the given - but by no means exhaustive-references helpful. With applications ranging from everyday materials such as architecture and container glass which are mostly based on silicates, to specialty glasses used in optics and photonics, in biomedicine, or metallic glasses golf clubs. Even the piece of amber you found at the beach might constitute a very different type of glass.
ACKNOWLEDGEMENTS
The authors want to thank Doris Ehrt and Dominique de Ligny for proof reading and valuable hints and discussions. Doris answered many of our questions to properties by tireless searched in the SciGlass data base. We also want to acknowledge the presenters at the 13 Ecole thématique
"Structural Role of Elements in Glasses from Classical Concept to a Reflexion over broad Composition Range" - Cargèse, France, 27-31 Mars 2017. Especially for the non-conventional glass former, such as: Invert Glasses and Aluminate Glasses, L. Hennet, Borate Glasses, G. Lelong, Phosphates and Vanadates glasses, F. Munoz & L. Montagne, Metallic glasses, L. Greer, Chalcogenide glasses: structure vs. compositions, A. Pradel, Chalcogenide glasses: properties vs.
structure, B. Bureau, Chalcogenide glasses: properties vs. structure, E. Byschkov, Organic glasses, C. Alba Simionesco, Hybrid glasses, N. Greaves, Borates, Silicates and Tellurites glasses, A.
Hannon, Tellurite glasses, P. Thomas. Their presentation and slides provided us with valuable references, examples and summaries of the respective fields.
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