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Formation, Compositions, and Properties of Hydroxy-Al- and Hydroxy-Mg-Montmorillonite

Published online by Cambridge University Press:  01 July 2024

G. W. Brindley  and
Chih-Chun Kao
G. W. Brindley
Affiliation:
Mineral Sciences Building, The Pennsylvania State University, University Park, Pennsylvania 16802
Chih-Chun Kao
Affiliation:
Mineral Sciences Building, The Pennsylvania State University, University Park, Pennsylvania 16802
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Abstract

Hydroxy-Al- and hydroxy-Mg-montmorillonite were prepared by treating dispersed Na-montmorillonite with aluminum and magnesium nitrate solutions and titrating with NaOH solutions so that the OH/Al ratio varied from zero to 3.0 and the OH/Mg ratio from zero to 2.0. External precipitation of Al and Mg hydroxides was observed when the OH/M ratios (M = metal) approached 3 and 2, respectively. From chemical analyses of the initial Na-montmorillonite and the hydroxy-metal montmorillonites, structural formulae were derived by assuming that the silicate layer compositions remained unchanged. Prior to the addition of NaOH, the average interlayer material approximated in composition to [Al(OH)2]+ and [Mg(OH)]+. With additions of NaOH the interlayer compositions moved progressively towards Al(OH)3 and Mg(OH)2. When the hydroxy interlayers approached completion, external precipitation was observed. X-ray powder diffraction data showed that the hydroxy-Mg products have less tendency to swell in ethylene glycol and water, and greater thermal stability than the hydroxy-Al products. Initially, when the average interlayer compositions were near Al(OH)2 and Mg(OH), swelling followed more nearly the normal behavior.

Резюме

Резюме

Гидрокси-А1 и гидпокси-М§-монтмориллониты были подготовлены путём воздействия растворов алюминиевых и магниевых нитратов на дисперсный Иа-монтмориллонит с последующим титрованием растворами КаОН, так что соотношение ОН/А1 изменялось от нуля до 3,0, а соотношение ОН/Мg от нуля до 2,0. Внешнее осаждение гидроокисей А1 и Мg наблюдалось, когда соотношение ОН/М (М = металл) достигало 2 и 3 соответственно. На основе химического анализа, исходя из предположения, что силикатный состав слоев не изменялся, были получены структурные формулы исходных Ка-монтмориллонитов и гидрокси-металл монтмориллонитов. Перед добавкой NaOH межслойный материал напоминал по состоянию [А1(ОН)2]+ и [Мg(ОН)]+. После добавки NаОН межслойный состав постепенно сдвинулся в сторону А1(ОН)3 и Мg(ОН)2. Внешние осаждения выступали, когда гидрокси-слои достигали завершения. Данные по рентгеновской порошковой дифракции показали, что гидрокси-Мв продукты имеют меньшую тенденцию к набуханию в этиленовом гликоле и воде, и большую термическую стабильность, чем гидрокси-А1 продукты. В случае, когда средние межслойные составы были близки к Аl(ОН)2 и Мg(ОН), набухание проходило по более нормальному пути. [Е.С.]

Resümee

Resümee

Hydroxy-Al- und Hydroxy-Mg-Montmorillonite wurden hergestellt, indem man dispergierten Na-Montmorillonit mit Aluminium- und Magnesiumnitratlösungen behandelte und mit NaOH-Lösungen titrierte, so daß das OH/Al-Verhältnis von 0 bis 3,0, und das OH/Mg-Verhältnis von 0 bis 2,0 variierte. Al- und Mg-Hydroxyde fielen aus, wenn das OH/M-Verhältnis (M = Metall) 3 bzw. 2 erreichte. Aus chemischen Analysen des ursprünglichen Na-Montmorillonites und der Hydroxy-Metall-Montmorillonite wurden unter der Annahme Strukturformeln abgeleitet, daß die Zussammensetzung der Silikatlagen unverändert bleibt. Vor der Zugabe von NaOH hatte die durchschnittliche Zwischenschichtsubstanz etwa die Zusammensetzung [Al(OH)2]+ bzw. [Mg(OH)]+. Durch die Zugabe von NaOH verschob sich die Zusammensetzung der Zwischenschict immer mehr in Richtung Al(OH)3 bzw. Mg(OH)2. Wenn die Hydroxy-Zwischenlagen vollständig waren, war eine Ausfällung zu beobachten. Röntgendiffraktometerdaten zeigten, daß die Hydroxy-Mg-Produkte eine geringe Tendenz zum Quellen in Ethylenglycol und Wasser, sowie eine größere thermische Stabilität haben als die Hydroxy-Al-Produkte. Anfänglich, wenn die durchschnittliche Zusammensetzung der Zwischenschicht etwa AI(OH)2 bzw. Mg(OH) ist, zeigt sich nahezu das übliche Quellverhalten. [U.W.]

Résumé

Résumé

Les montmorillonites hydroxy-Al et hydroxy-Mg ont été préparées en traitant de la montmoril-lonite-Na dispersée avec des solutions de nitrate d'aluminium et de magnesium et en titrant avec des solutions de NaOH, de telle façon que la proportion OH/Al variait de zéro à 3,0 et la proportion OH/Mg de zéro à 2,0. Une précipitation externe d'hydroxides d'Al et de Mg a été observée lorsque les proportions OH/M (M = metal) approchaient 3 et 2, respectivement. A partir d'analyses chimiques des montmorillon-ites-Na initiales et des motmorillonites hydroxy-metal, des formules structurales ont été dérivées en assumant que les compositions de la couche silicate demeuraient inchangées. Avant l'addition de NaOH, la composition moyenne du matériel intercouche était approximativement [Al(OH)2]+ et [Mg(OH)]+. Avec l'addition de NaOH, les compositions intercouche se sont déplacées progressivement vers Al(OH)3 et Mg(OH)2. Lorsque les intercouches hydroxy étaient presque complètes, la precipitation externe a été observée. Les données de diffraction poudrée aux rayons-X ont montré que les produits hydroxy-Mg avaient moins tendance á gonfler dans le glycol éthylène et dans l'eau, et avaient une plus grande stabilité thermale que les produits hydroxy-Al. Initialement, lorsque les compositions moyennes d'intercouches étaient près d'Al(OH)2, et Mg(OH), la conduite du gonflement était plus près de la normale. [D.J.]

Keywords

HydrolysisHydroxy interlayerMontmorilloniteSwellingThermal stability
Type
Research Article
Information
Clays and Clay Minerals , Volume 28 , Issue 6 , December 1980 , pp. 435 - 443
Copyright
Copyright © Clay Minerals Society 1980

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