Zinc borate glasses: properties, structure and modelling of the composition-dependence of borate speciation

Topper, Brian; Möncke, Doris; Yougman, Randall; Valvi, C.; Kamitsos, E. I.; Varsamis, Christos Platon P.E.

doi:10.1039/d2cp05517a

Cited by 28 publications

(34 citation statements)

References 94 publications

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“…The spectrum of Nb 2 O 5 -free glass ( Figure 3 , spectrum x = 0) agreed well with what has been reported by other authors for similar compositions [ 15 , 16 , 17 ]. The most prominent band at 877 cm −1 in the base binary glass x = 0 was assigned to the symmetric stretching of pyroborate dimers, [B 2 O 5 ] 4− [ 15 , 16 , 17 ].…”

Section: Resultssupporting

confidence: 91%

“…The most prominent band at 877 cm −1 in the base binary glass x = 0 was assigned to the symmetric stretching of pyroborate dimers, [B 2 O 5 ] 4− [ 15 , 16 , 17 ]. The two shoulders observed at 800 cm −1 and 770 cm −1 are due to the ring breathing of the boroxol rings and of the six-membered borate rings with one BO 4 tetrahedron (tri-, tetra- and pentaborate rings), respectively [ 15 ]. The broad shoulder at about 705 cm −1 contains contributions of at least four borate arrangements: metaborate chains [BØ 2 O − ] n (deformation modes; Ø = bridging oxygen, O − = nonbridging oxygen), in-plane and out-of-plane bending modes of both polymerized (BØ 0 ) species and isolated orthoborate units (BO 3 ) 3− , and bending of the B-O-B connection in the pyroborate dimers, [B 2 O 5 ] 4− [ 15 , 16 , 17 ].…”

Section: Resultsmentioning

confidence: 99%

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Structure and Luminescent Properties of Niobium-Modified ZnO-B2O3:Eu3+ Glass

Iordanova,

Milanova,

Yordanova

et al. 2024

Materials

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The effect of the addition of Nb2O5 (up to 5 mol%) on the structure and luminescent properties of ZnO-B2O3 glass doped with 0.5 mol% (1.32 × 1022) Eu2O3 was investigated by applying infrared (IR), Raman and photoluminescence (PL) spectroscopy. Through differential thermal analysis and density measurements, various physical properties such as molar volume, oxygen packing density and glass transition temperature were determined. IR and Raman spectra revealed that niobium ions enter into the base zinc borate glass structure as NbO4 tetrahedra and NbO6 octahedra. A strong red emission from the 5D0 level of Eu3+ ions was registered under near UV (392 nm) excitation using the 7F0 → 5L6 transition of Eu3+. The integrated fluorescence intensity ratio R (5D0 → 7F2/5D0 → 7F1) was calculated to estimate the degree of asymmetry around the active ion, suggesting a location of Eu3+ in non-centrosymmetric sites. The higher Eu3+ luminescence emission observed in zinc borate glasses containing 1–5 mol% Nb2O5 compared to the Nb2O5-free zinc borate glass evidences that Nb2O5 is an appropriate component for modifying the host glass structure and improving the emission intensity.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Structure and Luminescent Properties of Niobium-Modified ZnO-B2O3:Eu3+ Glass

Iordanova,

Milanova,

Yordanova

et al. 2024

Materials

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“…These asymmetrical BO 3 units also give rise to complex 2nd‐order quadrupolar lineshapes, generally in the same MAS NMR shift area as the ring and nonring peaks described above, but with larger quadrupolar asymmetry parameters (η). If the population of asymmetric BO 3 units is sufficiently large, then fitting of the complex spectra can help distinguish between symmetric and asymmetric BO 3 units 46 . Tetrahedral boron peak positions reflect the nearest cation neighbors where higher and lower NMR shifts at ca.…”

Section: Resultsmentioning

confidence: 99%

“…If the population of asymmetric BO 3 units is sufficiently large, then fitting of the complex spectra can help distinguish between symmetric and asymmetric BO 3 units. 46 Tetrahedral boron peak positions reflect the nearest cation neighbors where higher and lower NMR shifts at ca. 0 and −2 ppm are characteristic of B 4 (1B,3Si) and B 4 (0B,4Si) connectivity, respectively.…”

Section: Nmr Spectroscopymentioning

confidence: 99%

Effect of femtosecond laser irradiation on structure‐terahertz property relationship in sodium borosilicate glasses

Tostanoski

Youngman

Sundaram

2023

Int J of Appl Glass Sci

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We report the effect of high‐repetition rate femtosecond (fs) laser irradiation on structure‐terahertz (THz) property relationship for sodium borosilicate glasses. We have used nuclear magnetic resonance (NMR), terahertz time‐domain spectroscopy (THz‐TDS), and Raman spectroscopy to examine pristine and laser irradiated regions of these glasses to determine and quantify boron speciation, THz refractive index, n(THz), and change (Δn) in n(THz), and spectral, that is, structural, changes due to laser exposure, respectively. Our results suggest that laser irradiation‐induced Δn(THz) values are dependent upon the glass composition, structural units, connectivity, and network, for example, the corresponding K‐ and R‐values of the borosilicate glass. Depolymerized glass networks show no changes in NMR B4 signal, slight changes in Raman spectral changes related to silicate structural units, for example, increase in Q3 tetrahedra with one nonbridging oxygen (nbO) atom, and higher measurable n(THz) and Δn(THz). More polymerized glasses, on the other hand, show changes in NMR B4 signal, varying degrees of Raman spectral changes in the borate subnetwork and structural units, and lower n(THz) and Δn(THz). The THz refractive index is most sensitive to modifier ions in the glasses, which are directly responsible for nbO formation, glass structure, and network polymerization.

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“…As fluence increases BO 3 decreases and leads to the formation of BO 4 giving rise to nonbridging oxygen (NBO) in the glass matrix. The changes in BO 4 and BO 3 relative population in ion irradiated LBO glasses are greater than in pristine LBO glass [51,52]. The decrease in the coordination of BO 3 to increase BO 4 and the formation of NBO in the residual glass matrix upon ceramization causes an expansion of the volume of the overall glass network [53].…”

Section: = +mentioning

confidence: 95%

Structural and optical properties of lithium borate glasses under extreme conditions of ion irradiation

et al. 2023

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Lithium borate (LBO) glasses of the composition 10LiO2.90B2O3 were prepared by melt quenching technique and characterized for morphological, structural, and optical properties before and after the exposure to the extreme conditions of 100 MeV Ni ion irradiation. Both the morphological images and structural properties confirm the transformation of LBO glasses from amorphous to polycrystalline nature. This Ni irradiation provides thermal energy that causes the ceramization of glass. The beam interacts with the material where the top layer of the glass remelts, and ultrafast re-solidification occurs after the termination of the ion beams. The Rietveld refinement using the X-ray diffraction data shows that the irradiated LBO possesses a monoclinic crystal structure of lithium pentaborate pentahydrate (B5H10LiO13). The FTIR spectra of Ni ion irradiated glasses show the creation of non-bridging oxygens (NBO) by the formation of BO4 units at the expense of BO3 units. The direct band gap and the Urbach energy of the glasses are affected by the nickel ion irradiation and are in the range 2.73 to 2.55 eV and 0.59 to 0.42 eV. The refractive index also reveals a minor change (1.66 to 1.63). The molar electronic polarizability, metallization criteria, and transmission coefficient were estimated. The coexistence of crystalline and amorphous phases leads to a multiscale phase structure that has multilevel relaxation processes. This is a suitable condition for the improvement of the rheological properties of glass and glass ceramics. Future work involves optimization of the coexistence of these two phases during irradiation.

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Zinc borate glasses: properties, structure and modelling of the composition-dependence of borate speciation

Abstract: The short-range order of binary zinc borate glasses, xZnO-(1-x)B2O3, has been quantitatively described as a function of ZnO content over the entire glass forming range for the first time, to...

Cited by 28 publications

References 94 publications

Structure and Luminescent Properties of Niobium-Modified ZnO-B2O3:Eu3+ Glass

Structure and Luminescent Properties of Niobium-Modified ZnO-B2O3:Eu3+ Glass

Effect of femtosecond laser irradiation on structure‐terahertz property relationship in sodium borosilicate glasses

Structural and optical properties of lithium borate glasses under extreme conditions of ion irradiation

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