Electrical Properties and the Structure of Glasses in the Li2SO4–LiPO3System

Соколов, И. А.; Valova, N. A.; Tarlakov, Yu. P.; Пронкин, А. А.

doi:10.1023/b:gpac.0000007930.11101.ee

Cited by 13 publications

(10 citation statements)

References 5 publications

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“…It is interesting to think about what these pairs of peaks mean structurally; we have found no evidence in the literature of SO 4 2– interacting with the phosphate backbone in sodium-containing sulfophosphate glasses, and only in H-, Li-, or Ag-containing sulfophosphate glasses has indirect evidence of this being observed through electrical conductivity, Raman, or 31 P NMR spectroscopy. ,− Although our NaPS-Ag spectra (Figure b) look very similar to Scotti et al .’s x Ag 2 SO 4 /(1 – x )AgPO 3 31 P NMR spectra, the authors only discuss “middle” phosphates (MP) and “end” phosphates (EP), Q 2 and Q, without the possibility of the existence of orthophosphate, Q 0 . Instead, they assign the intensity in the Q 0 region (10–0 ppm) to Q 1 units with various S–O–P bonding.…”

Section: Resultssupporting

confidence: 50%

Structural Origin of the Optical Properties of Ag-Doped Fluorophosphate and Sulfophosphate Glasses

et al. 2021

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Given the ubiquity of glass formulations that are functionalized with silver compounds, the electronic interaction between isolated silver cations and the glass network deserves more attention. Here, we report the structural origin of the optical properties that result from silver doping in fluorophosphate (PF) and sulfophosphate (PS) glasses. To achieve this, solid-state nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) are combined with optical spectroscopic analysis and physical property measurements. Comparing the 31 P NMR, 27 Al 1d NMR, and 27 Al multi-quantum magic-angle spinning NMR of doped glasses and glasses with large amounts of Ag + added, we deduce silver's bonding preference in these mixed-anion aluminophosphate glasses. We show that such understanding provides an explanation for the large Stokes shift observed for Ag + in PF and PS glasses, which is related to absorption by the ionic Ag + ••• − O−P species and transfer of the excitation energy within more covalently bonded Ag 2 O-like clusters. This is corroborated by DFT calculations, which show that the Ag + ••• − O−P and Ag + ••• − O−S bonds in corresponding crystals are mostly ionic. The introduction of more silver ions into the crystal structure results in more covalent bonding between Ag + and the phosphate matrix.

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Section: Resultssupporting

confidence: 50%

Structural Origin of the Optical Properties of Ag-Doped Fluorophosphate and Sulfophosphate Glasses

et al. 2021

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“…Analysis of the activation energies show that for these glasses, E n ≪ E m < E σ as can be seen in Figure 9, and thus the ionic conductivity is determined mainly by the ionic mobility. More specifically, the mobility of the sodium cation, as previous studies have shown that for sulfate-and chloride-containing alkali metaphosphate glasses the contributions of the anions is negligible (Sokolov et al, 2003;Bhide and Hariharan, 2007;Rao et al, 2009;Hraiech and Ferid, 2013). Despite that, charge carrier formation does play a non-negligible role in this glass system, as illustrated by the Walden plot of the conductivity data in Figure 10, where it is clear that the NaPO 3 -NaCl-Na 2 SO 4 glasses show a broad distribution, covering over two orders of magnitude along the log (σ dc .T) axis for each measured frequency, suggesting that the addition of sodium chloride and sodium sulfate enhances the number of effective charge carriers.…”

Section: Impedance Spectroscopymentioning

confidence: 96%

Correlation Between Ionic Mobility and Plastic Flow Events in NaPO3-NaCl-Na2SO4 Glasses

et al. 2019

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We report on the evolution of the mechanical and electrical properties of sodium metaphosphate glasses with addition of sodium sulfate or sodium chloride. The addition of these two sodium salts converts the medium-range order of our glasses from 2D phosphate chains to a mixed 1D + 2D network similar to ionic glasses, while the short-range order of the phosphate units remains unaffected. Replacing the phosphate units by chloride ion monotonically decreases the glass transition temperature, but enhances the Young's modulus and moderately increases the ionic conductivity. On the other hand, the sulfate group decreases the glass transition temperature as well, though the Young's modulus remains constant, while the ionic conductivity strongly increases. The changes in conductivity are related to the enhancement of the ionic mobility in these glasses, which in turn affect the size and distribution of the plastic events taking place during indentation-driven deformation.

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“…Both fluorine and SO 4 2bond more ionically, and as such enhance ionic conductivity by loosening the initial structure and reducing the binding energy between the charge carriers and glass matrix. 43 Thus, from the high σ, we may expect the MAE to be large for dynamic properties in both series, however, especially so in sulfate-containing systems. Similarly, since hardness involves plasticity, it is expected to also have large deviations from linearity.…”

Section: Introductionmentioning

confidence: 98%

“…Between the two glass families, that is, with and without SO 4 2 , we compare the magnitude of the MAE and position of the maximum alkali molar fraction (defined as [M]/[M + M′]). Both fluorine and SO 4 2– bond more ionically, and as such enhance ionic conductivity by loosening the initial structure and reducing the binding energy between the charge carriers and glass matrix 43 . Thus, from the high σ , we may expect the MAE to be large for dynamic properties in both series, however, especially so in sulfate‐containing systems.…”

Section: Introductionmentioning

confidence: 99%

Influence of glass network ionicity on the mixed‐alkali effect

Calahoo

Xia

Zhou

2020

Int J of Appl Glass Sci

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Most studies of the mixed-alkali effect (MAE) have focused on relating the differences between the cations to the strength of the MAE; here we examine the effect of the glass former by comparing the MAE in aluminofluorophosphate (FP) and aluminosulfofluorophosphate (FPS) glasses. The sulfate anion in the FPS series does not bond directly to the aluminophosphate network, decreasing connectivity and increasing the ionicity of the FPS glasses. The increased degrees of freedom imparted by the sulfate are evident in the single-alkali FPS glasses, which have lower E a , hardness, shear moduli, and Young's moduli, and higher T g than the corresponding single-alkali FP glasses (without sulfate). Conversely, for the mixed-alkali FPS compositions, the sulfate's mobility is reduced by the mixed cations, resulting in a magnified MAE for the FPS series. For dynamic properties, this phenomenon is explained by reduced plasticity and slippage along ion channels, while understanding T g and elastic properties requires examination of the shape of the sulfate's potential energy well and the resulting regions of compressive and tensile stress. We posit that glass compositions with higher plasticity, that is, less covalent bonding, will exhibit a larger MAE, but, simultaneously, sufficient conventional glass network must be present to constrain the mobile ions.

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Electrical Properties and the Structure of Glasses in the Li₂SO₄–LiPO₃System

Cited by 13 publications

References 5 publications

Structural Origin of the Optical Properties of Ag-Doped Fluorophosphate and Sulfophosphate Glasses

Structural Origin of the Optical Properties of Ag-Doped Fluorophosphate and Sulfophosphate Glasses

Correlation Between Ionic Mobility and Plastic Flow Events in NaPO3-NaCl-Na2SO4 Glasses

Influence of glass network ionicity on the mixed‐alkali effect

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