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Comparison of Intercalation Methods for Differentiating Halloysite from Kaolinite

Published online by Cambridge University Press:  02 April 2024

B. K. G. Theng ,
G. J. Churchman ,
J. S. Whitton  and
G. G. C. Claridge
B. K. G. Theng
Affiliation:
Soil Bureau, Department of Scientific and Industrial Research, Private Bag, Lower Hutt, New Zealand
G. J. Churchman
Affiliation:
Soil Bureau, Department of Scientific and Industrial Research, Private Bag, Lower Hutt, New Zealand
J. S. Whitton
Affiliation:
Soil Bureau, Department of Scientific and Industrial Research, Private Bag, Lower Hutt, New Zealand
G. G. C. Claridge
Affiliation:
Soil Bureau, Department of Scientific and Industrial Research, Private Bag, Lower Hutt, New Zealand
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Abstract

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The intercalation of formamide, potassium acetate, and hydrazine by halloysite and/or ka-olinite-rich samples, with and without subsequent displacement of the interlayer species by water or glycerol/water, has been investigated. Halloysite, as such, or in mixtures with kaolinite is completely expanded by all the treatments used, thereby enabling halloysite concentrations to be determined from the basal X-ray powder diffraction (XRD) peak ratios of the appropriate complexes. The values so obtained are usually proportional to the abundance of tubes, laths, and spherules in the transmission electron micrographs of the samples. The analysis of kaolin samples (halloysite plus kaolinite) by intercalation methods is less straight forward because a proportion of the kaolinite component in the system may not expand, even after lengthy (≥ 18 days) contact of the sample with the intercalating agent. Only prolonged immersion in hydrazine produces complete or nearly complete expansion of this component. When allowance is made for the presence of non-clay mineral components, kaolin-mineral percentages estimated from XRD peak intensity ratios of the hydrazine complexes generally agree with values derived from differential thermal analysis to within ±10%. Kaolinite in mixtures with halloysite cannot be directly determined by intercalation procedures inasmuch as treatments which result in complex formation with kaolinite also expand halloysite. In such systems, kaolinite can be estimated by difference between the concentration of kaolin minerals and halloysite.

Резюме

Резюме

Исследовалось прослаивание формамида, ацетата калия и гидразина галлуазитом и/или обогащенными каолинитом образцами, с и без последующего замещения междуслойных веществ водой или смесью глицерола с водой. Использованые образцы представляли геологические, почвенные, керамические и промышленные материалы. Галлуазит, как таковой, или в смесях с каолинитом полностью расщирялся при всех примененных методах обработки, позволяя, таким образом, определить концентрации галлуазита на основе отношений пиков рентгеновской порошковой дифракции соответствующих комплексов. Полученные таким образом, величины обычно пропорциональны частоте появления трубок, пластинок и шариков в микрографах образцов, полученных при использовании трансмиссионного электронного микроскопа.

Анализ каолиновых минералов (галлуазита плюс каолинита) путем методов прослаивания является менее непосредственным, так как часть каолинитового компонента в системе может не расшириться даже после длительного (≥ 18 дней) контакта образца с включаемым реагентом. Только длительное погружение в гидразине приводило к полному или почти полному расширению этого компонента. После учета присутствия неглинистых минеральных компонентов процентные содержание каолиновых минералов, определенные на основе отношений интенсивности пиков гидразиновых комплексов, согласовывались с величинами, рассчитаными по дифференциальному термическому анализу, с точностью до ± 10% во всех почти случаях. Каолинит в смеси с галлуазитом не может быть непосредственно олределен при помощи методов прослаивания так как методы обработки, которые вызывают образование комплкеса с каолинитом также вызывают расширение галлуазита. В таких системах количество каолинита может быть определено как разница между концентрацией каолиновых минералов и галлуазита. [E.G.]

Resümee

Resümee

Es wurde der Einbau von Formamid, Kaliumacetat, und Hydrazin in Halloysit- und/oder Kaolinit-reiche Proben mit oder ohne Austausch der Zwischenschichtart durch Wasser oder Glyzerin/ Wasser untersucht. Halloysit an sich oder in Mischungen mit Kaolinit wird durch alle verwendeten Methoden vollständig expandiert. Dadurch ist es möglich, den Gehalt an Halloysit aus den Verhältnissen der basalen Röntgenpulverdiffraktometer (XRD)-Peaks der geeigneten Komplexe zu bestimmen. Die derart bestimmten Werte sind im allgemeinen proportional der Menge an Röhren, Leisten und Spiralen in den transmissionselektronenmikroskopischen Aufnahmen der Proben. Die Untersuchung von Kaolinproben (Halloysit und Kaolinit) durch die Wechsellagerungsmethode ist weniger exakt, da ein Teil der Kaolinitkomponente im System u.U. nicht expandiert, selbst nach einer langen Reaktionszeit (≥ 18 Tage) der Probe mit dem Wechsellagerungsagens. Nur eine lange Einwirkung von Hydrazin führt zum vollständigen oder nahezu vollständigen Expandieren dieser Komponente. Wenn man die Anwesenheit von Nicht-Tonmineralkomponenten berücksichtigt, dann stimmen im allgemeinen die aus den XRD-Peakin-tensitätsverhältnissen der Hydrazinkomplexe geschätzten Kaolinmineralanteile mit den Werten aus der Differentialthermoanalyse mit einer Genauigkeit von ± 10% überein. Kaolinit in Mischungen mit Halloysit kann durch Wechsellagerungsmethoden nicht direkt bestimmt werden, da die Methoden, die zu einer Komplexbildung mit Kaolinit führen, auch Halloysit expandieren. In diesem System kann der Kaolini-tanteil aus der Differenz zwischen der Konzentration der Kaolinminerale und der von Halloysit abgeschätzt werden. [U.W.]

Résumé

Résumé

On a investigué l'intercalation de formamide, d'acétate de potassium et d'hydrazine par des échantillons riches en halloysite et/ou en kaolinite, avec et sans le déplacement subséquent de l'espace interfeuillet par l'eau ou le glycol/eau. Les échantillons utilisés représentent des matériaux géologiques, de sol, et céramiques industriels. L'halloysite en tant que telle, ou en mélange avec la kaolinite est complètement dilatée par tous les traitements employés, permettant de cette manière que les concentrations d'halloysite soient déterminées par les proportions des pics XRD de diffraction aux rayons-X de base des complexes appropriés. Les valeurs obtenues ainsi sont généralement proportionnelles à l'abondance de tubes, de lattes, et de sphérules dans les micrographes d’électrons à transmission des échantillons. L'analyse d’échantillons de kaolin (halloysite plus kaolinite) per des méthodes d'intercalation est moins directe parce qu'une proportion du composé kaolinite dans le système pourrait ne pas se dilater, même après que l’échantillon ait été en contact avec l'agent intercalant pendant longtemps (≥ 18 jours). Seule l'immersion prolongée dans l'hydrazine produit l'expansion complète ou presque complète de ce composé. Lorsqu'on tient compte de la présence des composés de minéraux non-argileux, les pourcentages de minéral kaolin estimés à partir de proportions d'intensité de pics XRD des complexes d'hydrazine s'accordent généralement bien avec les valeurs derivées de l'analyse thermale differentielle à ±10% près dans la plupart des cas. La kaolinite, dans des mélanges avec l'halloysite, ne peut pas être directement determinée par des procédés d'intercalation dans la mesure où les traitements qui resultent en la formation de complexe avec la kaolinite dilatent aussi l'halloysite. Dans de tels systèmes, la kaolinite peut être estimée par la différence entre la concentration de minéraux kaolins et halloysites. [D.J.]

Keywords

FormamideHalloysiteHydrazineIntercalationKaolinitePotassium acetateTest
Type
Research Article
Information
Clays and Clay Minerals , Volume 32 , Issue 4 , August 1984 , pp. 249 - 258
Copyright
Copyright © 1984, The Clay Minerals Society

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