Network structure of sodium aluminoborophosphate glasses from solid-state NMR spectroscopy and Pauling bond strengths

Krishnamurthy, Arun; Perillo, Jordan; Kroeker, Scott

doi:10.1016/j.jnoncrysol.2023.122328

Cited by 3 publications

(2 citation statements)

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“…Notably, this feature also explains the presence of directly interlinked BO 4 tetrahedra in BS glasses that only incorporate low-CFS cations, such as Na + and K + . Moreover, while it is well-known that the highly charged P 5+ cation readily forms P–O–Al [4] and P–O–B [4] linkages, , Kroeker and co-workers recently suggested from bond-valence considerations that B [4] –O–B [4] fragments bonded to PO 4 neighbors also become stabilized in Na–Al–B–P–O glasses …”

Section: Resultsmentioning

confidence: 99%

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BO₃/BO₄ Intermixing in Borosilicate Glass Networks Probed by Double-Quantum ¹¹B NMR: What Factors Govern BO₄–BO₄ Formation?

Lv,

Stevensson,

et al. 2023

J. Phys. Chem. C

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We examine the borate group intermixing in a series of 25 borosilicate (BS) glasses from the [0.5M (2) O−0.5Na 2 O]−B 2 O 3 −SiO 2 systems with M = {Li, K, Rb, Mg, Ca} along with ternary K 2 O−B 2 O 3 −SiO 2 and Na 2 O− B 2 O 3 −SiO 2 glasses by double-quantum−single-quantum (2Q−1Q) 11 B correlation nuclear magnetic resonance (NMR) experiments. The alterations of the fractional populations of B [3] −O−B [3] , B [3] −O−B [4] , and B [4] −O−B [4] linkages in the glass networks were monitored for variable n Si /n B molar ratios, nonbridging O contents of the glass, and the (average) cation field strength (CFS) of the M z+ /Na + network modifiers. A significant B [4] −O−B [4] bonding is observed in all glasses, thereby conclusively demonstrating that the normally assumed "BO 4 −BO 4 avoidance" is far from strict in BS glasses, regardless of the M z+ field strength. We show that the degree of B [4] −O−B [4] bonding depends foremost on its underlying BO 4 population and to a lesser degree on the NBO content of the glass; we also provide a straightforward prediction of the B [4] −O−B [4] population in an arbitrary BS glass from parameters readily obtained by routine 11 B NMR. The propensity for forming B [4] −O−B [4] linkages increases concurrently with either the CFS or the amount of glass network modifiers, roughly scaling as the square root of the "effective CFS" that encompasses both parameters. Although BO 3 −BO 3 and BO 3 −BO 4 pairs remain favored throughout all examined BS glass networks, the borate group intermixing randomizes significantly for increasing effective CFS, out of which the amount and charge of the glass-network modifier cations dominate over their size. Our results are discussed in relation to the two prevailing but formally mutually exclusive "random network" and "superstructural unit" models of borate and BS glasses.

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Section: Resultsmentioning

confidence: 99%

“…Moreover, while it is well-known that the highly charged P 5+ cation readily forms P−O−Al [4] and P−O−B [4] linkages, 12,88 Kroeker and co-workers recently suggested from bond-valence considerations that B [4] −O−B [4] fragments bonded to PO 4 neighbors also become stabilized in Na−Al− B−P−O glasses. 89 4.5.1. Critical Remarks.…”

Section: Thementioning

confidence: 99%

BO₃/BO₄ Intermixing in Borosilicate Glass Networks Probed by Double-Quantum ¹¹B NMR: What Factors Govern BO₄–BO₄ Formation?

Lv,

Stevensson,

et al. 2023

J. Phys. Chem. C

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Solid-state NMR spectroscopy

Aliev

2024

Nuclear Magnetic Resonance

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This solid-state NMR report summarises the subject and results of selected articles and original papers published in 2023. In addition to the published reviews, the two major sections in this report consider various methodological developments and a broad range of applications. The presented classification of papers into different sections and subsections is intended to ease the overview of the results, as well as to evaluate the directions in which solid-state NMR techniques and applications are likely to develop in the near future. The overall survey of published papers indicates that the number of electrolyte and battery materials studies by solid-state NMR has increased considerably in 2023 compared to previous years.

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Composition‐dependent structural role of lead in aluminoborate and galloborate glasses: A solid‐state NMR study

Krishnamurthy,

Wren,

Michaelis

et al. 2024

J Am Ceram Soc.

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Investigations on binary lead‐bearing glass systems have shown that Pb2+ functions as a charge compensator at low concentrations and can participate in network formation at higher loadings. We use multinuclear magnetic resonance spectroscopy to investigate the mechanism underlying this dual‐role nature of Pb2+ in ternary lead‐borate glasses containing aluminum or gallium. 207Pb nuclear magnetic resonance (NMR) spectra—in conjunction with charge‐balance calculations, bond‐valence principles, and precedents from crystalline lead‐borates—are interpreted in terms of high‐ and low‐coordinate Pb2+ species, representing charge‐compensating “network modifier” sites and covalently‐bound “network forming” sites, respectively. Both high‐field 27Al and 71Ga magic‐angle spinning NMR spectra indicate the presence of substantial fractions of four, five, and six‐fold coordinated Al/Ga, reinforcing the isostructural nature of these elements. However, systematic differences in the boron speciation in Al‐ and Ga‐bearing glasses reveal that their size difference has a measurable effect on the short‐range structure in these glasses.

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Network structure of sodium aluminoborophosphate glasses from solid-state NMR spectroscopy and Pauling bond strengths

Cited by 3 publications

References 88 publications

BO₃/BO₄ Intermixing in Borosilicate Glass Networks Probed by Double-Quantum ¹¹B NMR: What Factors Govern BO₄–BO₄ Formation?

BO₃/BO₄ Intermixing in Borosilicate Glass Networks Probed by Double-Quantum ¹¹B NMR: What Factors Govern BO₄–BO₄ Formation?

Solid-state NMR spectroscopy

Composition‐dependent structural role of lead in aluminoborate and galloborate glasses: A solid‐state NMR study

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Network structure of sodium aluminoborophosphate glasses from solid-state NMR spectroscopy and Pauling bond strengths

Cited by 3 publications

References 88 publications

BO3/BO4 Intermixing in Borosilicate Glass Networks Probed by Double-Quantum 11B NMR: What Factors Govern BO4–BO4 Formation?

BO3/BO4 Intermixing in Borosilicate Glass Networks Probed by Double-Quantum 11B NMR: What Factors Govern BO4–BO4 Formation?

Solid-state NMR spectroscopy

Composition‐dependent structural role of lead in aluminoborate and galloborate glasses: A solid‐state NMR study

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BO₃/BO₄ Intermixing in Borosilicate Glass Networks Probed by Double-Quantum ¹¹B NMR: What Factors Govern BO₄–BO₄ Formation?

BO₃/BO₄ Intermixing in Borosilicate Glass Networks Probed by Double-Quantum ¹¹B NMR: What Factors Govern BO₄–BO₄ Formation?