Quasi-elastic neutron scattering studies on clay interlayer-space highlighting the effect of the cation in confined water dynamics

被引:83
作者
Bordallo, Heloisa N. [1 ]
Aldridge, Laurence P.
Churchman, G. Jock [2 ]
Gates, Will P. [3 ,4 ]
Telling, Mark T. F. [5 ]
Kiefer, Klaus [1 ]
Fouquet, Peter [6 ]
Seydel, Tilo [6 ]
Kimber, Simon A. J. [1 ]
机构
[1] Helmholtz Zentrum Berlin Mat & Energie, D-14109 Berlin, Germany
[2] Univ Adelaide, Sch Earth & Environm Sci, Glen Osmond, SA 5064, Australia
[3] SmecTech Res Consulting, Bentleigh E, Vic 3165, Australia
[4] Monash Univ, Dept Civil Engn, Clayton, Vic 3800, Australia
[5] Rutherford Appleton Lab, ISIS Facil, Chilton OX11 0QX, Oxon, England
[6] Inst Max Von Laue Paul Langevin, F-38042 Grenoble 9, France
关键词
D O I
10.1021/jp803274j
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
It has long been realized that cations play a critical role in the readsorption of water into the interlayer region in clay minerals. To explore possible differences in the water dynamics related to the presence of cations in clays, and to examine the dynamics of its surface water, which plays a prominent role in diffusion of water in clay barriers a comparative study was carried out to highlight differences between water dynamics in montmorillonite and halloysite. Whereas montmorillonite has interlayer cations that interact with interlayer water, and which can rehydrate after dehydration at temperature, halloysite has no interlayer cations. Water is found in both interlayers and on the surface of these clay particles. In this study we show that by combining incoherent inelastic neutron scattering (quasi-elastic and elastic fixed window) and neutron spin echo, it was possible to discriminate the dynamics Of Surface water (by collapsing the interlayer region by heating and rehydrating the surface layer) from interlayer water. The analysis of the elastic fixed window scans in the temperature range 5-300 K revealed an extension of water dynamics in montmorillonite to lower temperatures than in halloysite. These differences suggested mechanisms that cations (Na+ in this case) in the interlayer regions facilitate water mobility allowing interlayer water to be readmitted to montmorillonite. Finally it was shown that the occurrence of magnetic fluctuations, caused by the presence of paramagnetic Fell ions in the crystalline clay lattice, gave rise to a quasi-elastic contribution that disrupted the evaluation of water diffusion computed from such measurements. Therefore previous estimates of water diffusion coefficients might have been overestimated in recent literature.
引用
收藏
页码:13982 / 13991
页数:10
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