Local cation environments in mixed alkali silicate glasses studied by multinuclear single and double resonance magic-angle spinning NMR

Gee, Becky; Janssen, Michael; Eckert, Hellmut

doi:10.1016/s0022-3093(97)00037-9

Cited by 70 publications

(153 citation statements)

References 34 publications

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“…However, these fi ndings contradict the evidence for like-cation association discussed above. Similar results to those of Gee et al (1997) have been made for sodium-cesium (Dupree et al 1986) and sodium-rubidium (Hater et al 1989) silicate glasses. Florian et al (1996) used NMR to probe the structure of sodium and potassium mixed-alkali glasses of varying composition.…”

Section: Mixed Alkali Silicate Glassessupporting

confidence: 84%

“…As an alternative, Gee et al (1997) studied mixed Li-Na silicate glasses. They found the NMR chemical shifts to move in the same direction as an increase in the compositional parameter Na/(Na + Li), thus providing evidence in support of the two-site hypothesis; the Na Na site probability will increase with increasing Na/(Na + Li), and the Li Na site probability also will increase with increasing Na/(Na + Li).…”

Section: Mixed Alkali Silicate Glassesmentioning

confidence: 99%

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The Structure of Silicate Melts: A Glass Perspective

Henderson

2005

The Canadian Mineralogist

126

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Glasses are widely used as analogues for the study of silicate melts. Although they are solid materials, their structure is inherently complex and diffi cult to study. However, progress has been made in elucidating this structure, its relationship to composition, and how it behaves at high temperatures and pressures. Recent research has brought to light some new fi ndings with important implications for natural melts. These include the observation that the structure is dependent upon the type and size of alkali or alkaline-earth cations incorporated into the glass network, with Li behaving very differently than other alkali cations. In addition, the presence of more than one type of alkali cation can cause non-linear physical behavior. Elements such as Al, Ti and Fe, which play important roles in petrological phenomena, can exhibit coordination environments (e.g., 5-fold) or polyhedral arrangements (e.g., triclusters) that are not common in crystalline phases. Furthermore, polyamorphic phase-transitions may occur at high temperature and pressures; the application of new theoretical models like mean fi eld-constraint hypothesis suggests that several glass phenomena, and probably melt phenomena as well, may be related to stress-rigid to fl oppy transitions. The state of understanding of glass structure, although still rudimentary relative to crystalline materials, has grown exponentially over the last few decades, often with geological researchers at the forefront.Keywords: melts, structure, glasses, petrology, spectroscopy, behavior, model. SOMMAIREOn se sert couramment des verres pour étudier les bains fondus silicatés. Quoiqu'ils sont des matériaux solides, leur structure est naturellement complexe et diffi cile à étudier. Toutefois, des progrès ont été faits dans l'étude de cette structure, sa relation à la composition, et son comportement à températures et pressions élevées. Les projets de recherche récents font ressortir les implications importantes aux bains fondus naturels. A titre d'exemple, la structure dépendrait de la sorte et la taille d'ion alcalin ou alcalino-terreux qui se trouve incorporé dans le réseau du verre. Le Li se comporte de façon très différente des autres alcalins. De plus, la présence de plus d'une sorte d'alcalin peut causer des comportements physiques non-linéaires. Les élements tels Al, Ti et Fe, dont l'importance pétrologique est évidente, peuvent adopter une coordinence inhabituelle, cinq par exemple, et un arrangement polyédrique, des groupements par trois, par exemple, qui ne sont pas communs dans les phases cristallines. De plus, des transitions de phases polyamorphiques pourraient avoir lieu à températures et à pressions élevées. L'application de nouveaux modèles théoriques, par exemple le modèle de contrainte moyenne du champ, fait penser que plusieurs phénomènes impliquant les verres, et tout probablement les bains fondus, pourraient résulter de transitions de matériau rigide face aux contraintes à maté-riau déformable. Quoique les connaissances de la structure du ve...

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Section: Mixed Alkali Silicate Glassessupporting

confidence: 84%

Section: Mixed Alkali Silicate Glassesmentioning

confidence: 99%

The Structure of Silicate Melts: A Glass Perspective

Henderson

2005

The Canadian Mineralogist

126

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“…lithium). Inspection of a large body of chemical shift trends in various mixed-alkali glasses suggests that these structural readjustments are rather universal [59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74]: substitution of an alkali ion A by larger homologue B always leads to a slight compression of the A site and an expansion of the B site, compared to the situation in the corresponding single-alkali glass. Based on this evidence for site modification, we have suggested an additional ("secondary") mismatch effect as a fundamental principle underlying the MAE, which seems particularly relevant in the dilute foreign ion limit (see Fig.…”

Section: Site Modifications and Secondary Mismatch Effectsmentioning

confidence: 99%

Short and Medium Range Order in Ion-Conducting Glasses Studied by Modern Solid State NMR Techniques

Eckert¹

2010

Zeitschrift Für Physikalische Chemie

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Glass Structure / Solid State NMR Spectroscopy / Structure-Property RelationsGlassy ionic conductors have attained considerable importance in the solid state battery technology field. To understand the influence of composition on ionic mobility and transport, information about the local and dynamic environments of the mobile ions in glasses is required. Solid state NMR spectroscopy is one of the most powerful tools for addressing these questions. Our research effort in this area comprises (1) the development of efficient techniques and strategies for the study of disordered materials, (2) the detailed application of optimized measurement and data analysis protocols to different glass systems under systematic compositional variation, and (3) the comprehensive interpretation of the results obtained in the overall literature context. This article attempts to convey a concise overview of our contribution to this field over the period from 2004 to 2010, to describe the most significant insights obtained and to place them into the overall field of Solid State Ionics.

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“…[6,16] These techniques are also extremely useful in the study of glasses, e.g., TRAPDOR of aluminosilicate glasses [17,18] and REDOR of silicate and aluminoborate glasses. [19,20] This research news article has highlighted the development of double resonance NMR echo techniques in solids, in particular the 29 …”

Section: Other Applications and Scopementioning

confidence: 99%

“…However, materials that lack longrange order such as glasses or even crystalline materials that exhibit disorder often rely on a variety of methods that are sensitive to short-range interactions for definition of structure. Nuclear magnetic resonance (NMR) spectroscopy has contributed to the understanding of local interactions in solids since its earliest days, mainly by the use of abundant nuclei such as 1 H and 19 F. The ever-advancing state-of-the-art of NMR spectroscopy now makes it possible to tackle a wide range of complex problems using a variety of nuclear spins as probes. With the general availability of multi-channel instruments and high magnetic fields, much of the periodic table becomes accessible to anyone with access to a modern commercial high-field spectrometer.…”

Section: Introductionmentioning

confidence: 99%

Double Resonance NMR Echo Spectroscopy of Aluminosilicates

Ratcliffe

Ripmeester

2000

Adv. Mater.

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NMR spectroscopy is a powerful method for the characterization of materials. Here the development of double resonance NMR experiments is summarized and their application to materials science highlighted using the synthesis of silicon nanoclusters within aluminosilicate molecular sieves (see Figure) as an example. Not only can the structure of the product be elucidated but also that of the reaction intermediates.

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Local cation environments in mixed alkali silicate glasses studied by multinuclear single and double resonance magic-angle spinning NMR

Cited by 70 publications

References 34 publications

The Structure of Silicate Melts: A Glass Perspective

The Structure of Silicate Melts: A Glass Perspective

Short and Medium Range Order in Ion-Conducting Glasses Studied by Modern Solid State NMR Techniques

Double Resonance NMR Echo Spectroscopy of Aluminosilicates

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