In situ X-ray diffraction study of the swelling of montmorillonite as affected by exchangeable cations and temperature

Shoji Morodome, Katsuyuki Kawamura

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The swelling property of smectite is dominated by the hydration of exchangeable cations in the interlayer spacing ('interlayer hydration'). By investigating systematically the swelling behavior of various exchangeable cations with different valences and ionic radii, the interlayer hydration of smectite was explored. The swelling behavior of Li +-, K +-, Rb +-, Cs +-, Mg 2+-, Sr 2+-, Ba 2+-, and La 3+- montmorillonites in undersaturated conditions was measured precisely over the range 50-150°C by in situ X-ray diffraction (XRD) analyses. The systematic swelling behavior of ten homocationic montmorillonites, the aforementioned eight homoionic montmorillonites, plus Na + and Ca 2+ froma previous study, and the cation hydration energies were analysed by studying the changes occurring in the basal spacing and the 001 peak width. With decreasing cation hydration energy, swelling curves (i.e. plots of basal spacing vs. relative humidity (RH)) change from continuous (Mg 2+, La 3+, and Ca 2+) to stepwise (Sr 2+, Li +, Ba 2+, and Na +) to one-layer only (K +, Rb +, and Cs +). For the first two groups, the RH at the midpoint between the one- and two-layer hydration states increased as the cation hydration energy decreased. Under low RH, with increasing temperature, the basal spacings of Mg-, La-, Ca-, Sr-, Li-, and Ba-montmorillonites decreased continuously to the zero-layer hydration state, whereas Na-, K-, Rb-, and Cs-montmorillonites swelled from the zero-layer hydration state even at the lowest temperature (50°C). A decrease in the basal spacing at the same RH but at different temperatures suggests the existence of metastable states or that the layer-stacking structure changes with temperature. The systematics of the swelling behavior of various homocationic montmorillonites as functions of RH and temperature (

Original languageEnglish
Pages (from-to)165-175
Number of pages11
JournalClays and Clay Minerals
Volume59
Issue number2
DOIs
Publication statusPublished - Apr 2011

Fingerprint

Bentonite
exchangeable cations
montmorillonite
hydration
X-ray diffraction
Hydration
swelling
Swelling
Cations
relative humidity
cation
spatial distribution
X ray diffraction
cations
Atmospheric humidity
spacing
smectite
temperature
energy
Temperature

Keywords

  • Basal spacing
  • Hydration
  • Interlayer exchangeable cation
  • Montmorillonite
  • Relative humidity
  • Smectite
  • Swelling
  • Vapor pressure
  • X-ray diffraction

ASJC Scopus subject areas

  • Soil Science
  • Earth and Planetary Sciences (miscellaneous)
  • Geochemistry and Petrology
  • Water Science and Technology

Cite this

In situ X-ray diffraction study of the swelling of montmorillonite as affected by exchangeable cations and temperature. / Morodome, Shoji; Kawamura, Katsuyuki.

In: Clays and Clay Minerals, Vol. 59, No. 2, 04.2011, p. 165-175.

Research output: Contribution to journalArticle

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