Interlayer water and swelling properties of monoionic montmorillonites

Pennino, U. del; Mazzega, E.; Valeri, Sergio; Alietti, Alfredo; Brigatti, Maria Franca; Poppi, Luciano

doi:10.1016/0021-9797(81)90222-8

Cited by 43 publications

(23 citation statements)

References 8 publications

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“…On the other hand, others claim that water molecules are part of a structure that is probably determined by the silicate itself. 75 Furthermore, they conclude that one of the bonds of the water molecules in the interlayer space is almost orthogonal to the surface. Suquet et al 79 and Prost 80 proposed structures in which the water molecules have one bond parallel to the surface or one bond orthogonal to the surface, respectively.…”

Section: Models Of Interlayer Structuresmentioning

confidence: 99%

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Hysteresis in Clay Swelling Induced by Hydrogen Bonding: Accurate Prediction of Swelling States

et al. 2005

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We perform grand-canonical molecular simulations to study the molecular mechanism of clay swelling hysteresis as a function of the relative humidity. In particular, we focus on the transition from the one-to the two-layer hydrate and the influence of three types of counterions (Li + , Na + , and K + ). Our results cover the experimental relative humidity region where swelling and shrinking usually occur. We show that the thermodynamic origin of swelling hysteresis is a free-energy barrier separating the layered hydrates. This free-energy barrier is dominated by breaking and formation of hydrogen bonds between and within water layers. This network of water molecules is similar for all counterions, but the positions of these counterions depend upon their size. The relatively large K + counterions show more affinity for clay surface adsorption, which increases the free-energy barrier and inhibits swelling. On the other hand, the relatively small Li + counterions are quite well-accommodated in the water network, and thereby, they can form a new swelling state with a basal spacing of approximately 13.5 Å. This new swelling state is an alternative explanation for the widely accepted simultaneous occurrence of two or more swelling phases.

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Section: Models Of Interlayer Structuresmentioning

confidence: 99%

“…When X-ray diffraction measurements show intermediate values of the basal spacing, they must be attributed to interstratification of two or more swelling phases. 75 …”

Section: Molecular Mechanism Of Swelling Hysteresismentioning

confidence: 99%

Hysteresis in Clay Swelling Induced by Hydrogen Bonding: Accurate Prediction of Swelling States

et al. 2005

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“…The d(002) and d(003) spacings at different P/Ps values and temperatures were studied also as a function of the electric field (E) generated 3y the interlayer cation (Del Pennino et al, 1981). The dependence of spacings on the electric field, is shown in Figure 2b.…”

Section: X-ray Powder Diffraction (Xrd) Measurementsmentioning

confidence: 99%

“…Detailed studies of the interaction of H20, the compensating cation, and the silicate framework show that the stability of the complex at a given temperature and water vapor pressure depends on the magnitude and site of the layer charge and on the electrostatic energy of the water dipole in the cation field (Del Pennino et at., 1981). The XRD features ofa homoionic smectite with respect to the interlayer water can, therefore, be used to characterize the smectite itself.…”

Section: Introductionmentioning

confidence: 99%

Interlayer Water and Swelling Properties of Natural and Homoionic Corrensite

Brigatti¹,

Poppi

1985

Clays and clay miner.

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Abstract--A corrensite-like mineral, from near Borgotaro, Parma (Taro Valley, Italy), was studied by X-ray powder diffraction (XRD) and thermal analysis at different temperatures and water vapor pressures in the natural state and after exchange with ten different cations. In the natural state the mineral is characterized by a basal reflection at ~29 fi shifting to ~24 ~ on heating and to ~32 fit by glycerol treatment. The dehydration features of the homoionic minerals show that the stability of the complex of water, compensating cation, and silicate framework depends on the electrostatic energy of the water dipole in the cation field, similarly to smectite.XRD of the exchanged mineral shows a basal reflection of -58 fi particularly in the NH4-, Rb-, and Ba-exchanged states. This value suggests a structure characterized by a regular sequence of silicate layers with different layer charge, that generally results in a c periodicity of -29 fi, but which shifts to ~ 58 fi, and perhaps higher values, because of small differences in the compensating cation layers.

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“…The closest packing is generally reached at T > 400~ The d~oo2) spacings at different P/Po and T values were studied as a function of the electric field (E) generated by the interlayer cation on the water molecule in a smectite-like structure (Del Pennino et al, 1981). From (except Na), while it is constant above r > 1.3 ,/k (excluding Cs); (iii) at 400~ d(oo2) is ~9.6 h for all cations with r < 1-3 A and increases as the radius increases from r > 1.3 A.…”

Section: Xrd Measurementsmentioning

confidence: 99%

Natural and monoionic aliettite: hydration and dehydration states

Brigatti¹,

Poppi

1987

Clay miner.

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The dehydration of an interstratified talc-trioctahedral smectite mineral (aliettite) from Monte Chiaro, Taro Valley, Italy, saturated by Na, K, Rb, Cs, Mg, Ca, Sr, Ba and NH4 cations, was studied by X-ray powder diffraction and thermal analysis, under different conditions of temperature and relative humidity. Both in the natural and exchanged states the mineral exhibited several orders of basal reflections and, to varying relative humidity (P/Po) and temperature (T) conditions, behaved like a smectite except that: (i) the c-dimension was not very sensitive to relative humidity increase; (ii) the closest packing was for T > 400~ the collapsed state being reached gradually as Tincreased and an inverse trend was apparent between 20 ~ and 300~ (iii) the endothermic reactions at T = 400~ and T = 600~ appeared to be affected by the exchange treatment. The experimental data are consistent with a structural model in which it is possible to distinguish layers containing a patchwork of talc and smectite domains: the patchworks are superposed to make a regular alternation of the two domains.

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Interlayer water and swelling properties of monoionic montmorillonites

Cited by 43 publications

References 8 publications

Hysteresis in Clay Swelling Induced by Hydrogen Bonding: Accurate Prediction of Swelling States

Hysteresis in Clay Swelling Induced by Hydrogen Bonding: Accurate Prediction of Swelling States

Interlayer Water and Swelling Properties of Natural and Homoionic Corrensite

Natural and monoionic aliettite: hydration and dehydration states

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