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Results in Physics 12 (2019) 113–117
Contents lists available at ScienceDirect
Results in Physics journal homepage: www.elsevier.com/locate/rinp
Driving force for the swelling of montmorillonite as aﬀected by surface charge and exchangeable cations: A molecular dynamic study ⁎
Jianfei Penga, Hao Yia, , Shaoxian Songa,b, Weiquan Zhana, Yunliang Zhaoa,b, a b
T
⁎
School of Resources and Environmental Engineering, Wuhan University of Technology, 122 Luoshi Road, Wuhan, Hubei 430070, China Hubei Key Laboratory of Mineral Resources Processing and Environment, Wuhan University of Technology, 122 Luoshi Road, Wuhan, Hubei 430070, China
A R T I C LE I N FO
A B S T R A C T
Keywords: Swelling Montmorillonite Surface charge Exchangeable cations Molecular dynamic simulations
Swelling of montmorillonite (MMT) is a nonnegligible factor in many industrial processes owing to its great ability to absorb water in interlayer space. It is not easy to determine whether the exchangeable cations or the MMT layers interacts much stronger with water molecules to provide the dominant driving force for the swelling of MMT. In this work, driving force for the swelling of montmorillonite as aﬀected by surface charge and exchangeable cations has been investigated through molecular dynamics simulations (MDs). The adsorption energy between water molecules and MMT layers and between interlayer cations and water molecules was calculated to qualitatively characterize the driving force for the swelling of MMT, and higher negative adsorption energy means greater driving force. It is found that the adsorption energy between interlayer cations and water molecules are far higher than that between MMT layers and water molecules. Thus, it is the exchangeable cations that provide the dominant driving force for MMT to swell. Besides, it is observed that interlayer cations with stronger hydration ability (Mg > Ca > Na > K) have more negative adsorption energy to water molecules, which indicates that the stronger the hydration ability of exchangeable cations the greater contribution they make to the total driving force for the swelling of MMT.
Introduction Montmorillonite is a typical clay mineral with one alumina octahedral sheet sandwiched by two silica tetrahedron sheets [1]. Isomorphous substitutions in the crystal structure of the smectite clay are pervasive in a natural state, such as substitution of Al3 + in octahedral sites by Mg2 + and Si4 + by Al3 + in tetrahedral sites, and thus result in negatively charged layers [2]. Exchangeable cations, such as Na+, K+, Ca2+, or Mg2+, are introduced in the MMT interlayer space to compensate the negative charge [3]. When exposed to the water, MMT can absorb enough water to enlarge its volume greatly owing to the presence of interlayer cations and negatively charged layers [4,5]. Swelling of MMT is a ubiquitous phenomenon and plays an important role in various industrial processes or fundamental research activities. In the pharmaceutical ﬁeld, the swelling and adsorption properties of MMT promote drug delivery systems to improve the pharmaceutical disadvantages of drugs, such as low solubility and poor pharmacokinetic properties [6]. In plate-boundary faults, swelling of smectite produces high pressure and exerts a key inﬂuence on the development of decollement fold [7].Besides, the swelling of MMT can be applied to the
exfoliation of MMT and then used as two dimensional materials, and show excellent properties [8–10].On the other hand, in the oilﬁeld, swelling of MMT leads wellbore instability problems and causes an adverse inﬂuence on drilling operations when using water-based drilling ﬂuids [11]. Understanding the MMT swelling is thus of great importance for a better application of montmorillonite in many ﬁe