Montmorillonite space

Two classes of clays are known [3] (i) cationic clays (or clay minerals) that have negatively charged alumino-silicate layers balanced by small cations in the interlayer space (e.g. K-10 montmorillonite) and (ii) anionic clays which have positively charged brucite-type metal hydroxide layers balanced by anions and water molecules located interstitially (e.g. hydrotalcite, Mg6Al2(0H)igC034H20. 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

FIG. 4 Experimental (vertical bars) and simulated (symbols) values of the d-spacings for aUcy-lammonium-exchanged clay at three different cation exchange capacities (CECs) (a) SWy2 mont-morillonite, CEC = 0.8 meq/g (b) AMS montmorillonite (Nanocor), CEC = 1.0 meq/g (c) fluoro-hectorite (Dow-Corning), CEC = 1.5 meq/g. (Erom Ref. 30.)... 

Osmotic swelling is a second type of swelling. Where the concentration of cations between unit layers in a clay mineral is higher than the cation concentration in the surrounding water, water is osmotically drawn between the unit layers and the c-spacing is increased. Osmotic swelling results in larger overall volume increases than surface hydration. However, only certain clays, like sodium montmorillonite, swell in this manner. 

XRD was used to investigate the spacings of silicate layers of montmorillonite (from 1.9 to 4nm) in PP/montmorillonite (MMT) nanocomposites prepared by in situ graft-intercalation in the presence of acrylamide [331]. Similarly, XRD and TEM were used to study the dispersibility of PP/MMT nanocomposites prepared by melt intercalation using organo-montmorillonite and conventional twin screw extrusion [332]. Various delaminated and intercalated polymer (PA6, PA 12, PS,... 

PP-g-MA) silicate nanocomposites and intercalated thermoset silicate nanocomposites for flame-retardant applications were characterised by XRD and TEM [333], XRD, TEM and FTIR were also used in the study of ID CdS nanoparticle-poly(vinyl acetate) nanorod composites prepared by hydrothermal polymerisation and simultaneous sulfidation [334], The CdS nanoparticles were well dispersed in the polymer nanorods. The intercalation of polyaniline (PANI)-DDBSA (dodecylbenzene-sulfonate) into the galleries of organo-montmorillonite (MMT) was confirmed by XRD, and significantly large 4-spacing expansions (13.3-29.6A) were observed for the nanocomposites [335],... 

The intercalated catalysts can often be regarded as biomimetic oxidation catalysts. The intercalation of cationic metal complexes in the interlamellar space of clays often leads to increased catalytic activity and selectivity, due to the limited orientations by which the molecules are forced to accommodate themselves between sheets. The clays have electrostatic fields in their interlayer therefore, the intercalated metal complexes are more positively charged. Such complexes may show different behavior. For example, cationic Rh complexes catalyze the regioselective hydrogenation of carbonyl groups, whereas neutral complexes are not active.149 Cis-Alkenes are hydrogenated preferentially on bipyridyl-Pd(II) acetate intercalated in montmorillonite.150 The same catalyst was also used for the reduction of nitrobenzene.151... 

The catalytic application of clays is related closely to their swelling properties. Appropriate swelling enables the reactant to enter the interlamellar region. The ion exchange is usually performed in aquatic media because the swelling of clays in organic solvents, and thus the expansion of the interlayer space, is limited and it makes it difficult for a bulky metal complex to penetrate between the layers. Nonaqueous intercalation of montmorillonite with a water-sensitive multinuclear manganese complex was achieved, however, with the use of nitromethane as solvent.139 The complex cation is intercalated parallel to the sheets. 

When organic cations (e.g., cationic tensides) are employed, clay organo-complexes are formed, which can be used in organic solvents. A Pd-hexadecy-lammonium montmorillonite catalyst was prepared by the reduction of Pd(OAc)2 by ethanol in the interlamellar space. At small ethanol concentrations in toluene, selective interlamellar sorption of ethanol was established consequently, the reduction also occurred only in the interlamellar space.160 The catalyst was used for the hydrogenation of alkenes.161... 

The original epoxidation with titanium-tartrate is homogeneous, but it can be carried out heterogeneously without diminishing enantioselectivity by using titanium-pillared montmorillonite catalyst (Ti-PILC) prepared from titanium isopropoxide, (+)-DAT, and Na+-montmorillonite.38 Due to the limited spacing of Ti-PILC, the epoxidation becomes slower as the allylic alcohol gets bulkier. 

Fig. 1.8 (A) Design of a chitosan-montmorillonite sensor. Arrangement of chitosan chains in the clay interlayer space as a monolayer (B) or a bilayer (C) resulting in opposite behavior when measuring NaCI solutions of increasing concentration by...

Fig. 2. Diagram showing the intercalation of compact quaternary ammonium cations, such as trimethylphenylammonium (TMPA) into different smectites, giving rise to type I organoclays with a basal spacing of about 1.5 nm. SWa is a high-charge nontronite (iron-rich smectite) and SAz is a high-charge montmorillonite, while SAC is a low-charge montmorillonite. After Jaynes and Boyd (1991b).

Ti(H), for intercalated Ph is more than four orders of magnitude shorter than that for the pure compound. Equally striking is the close similarity of the Ti(H) value between TDTMA and Ph in the TDTMA-montmorillonite-Ph interlayer complex. All these observations strongly indicate that the TDTMA chains become relatively disordered and closely mixed with Ph in the interlayer space of montmorillonite. 

Na-montmorillonite (89) (Clay Spur) and Na-vermiculite (90) (Palabora) and the C-spacings... 

Cation Anion Montmorillonite AH (kJ Eq ) C-spacing Vermiculite AH (kJ Eq 0 C- spacing... 

This fact may explain the superiority of montmorillonite over vermiculite as an adsorbent for organocations (3, 4). Complicating this description, however, is the fact that a sample of any particular layer silicate can have layer charge properties which vary widely from one platelet to another (j>). By measuring the c-axis spacings, cation exchange capacity, water retention, and other properties of layer silicates, one obtains the "average" behavior of the mineral surfaces. 

The CEC of clay minerals is partly the result of adsorption in the interlayer space between repeating layer units. This effect is greatest in the three-layer clays. In the case of montmorillonite, the interlayer space can expand to accommodate a variety of cations and water. This causes montmorillonite to have a very high CEC and to swell when wetted. This process is reversible the removal of the water molecules causes these clays to contract. In illite, some exchangeable potassium is present in the interlayer space. Because the interlayer potassium ions are rather tightly held, the CEC of this illite is similar to that of kaolinite, which has no interlayer space. Chlorite s CEC is similar to that of kaolinite and illite because the brucite layer restricts adsorption between the three-layer sandwiches. 

The same evolution of the basal spacing (d 001) for the pillared montmorillonite in which the Li has been introduced after the Zr is illustrated in fig. 5. It has to be mentioed that, after saturation of the solids by ethylene glycol, the interlayer distance of the samples calcined at 400°C is always slightly higher than before saturation. 

A small increase of the (d 001) basal spacing is observed for the Li containing Zr pillared clays. However, the thermal stability of these solids drastically decrease. At high temperature, the collapse of the strucutre is also supported by the decrease of the surface area which is, at 700°C, almost identical to those measured for the montmorillonite. Different hypothesis may be proposed to explain the increase of the interlayer distance at low temperature (i) a better polymerization of the intercalated complex (ii) a modification of the distribution of the pillars (iii) a lower interaction between the pillar and the silica layer. The first hypothesis may easily be eliminated since the small variation of the height of the pillars (less than 1 A) cannot be explained by structural changes of the... 

Ion exchange reactions between cations present in groundwater and in the interlayer space of the montmorillonite structure. These are mainly the replacement of 2Na+ by Ca2+ and Mg2+ present in ground-waters. This triggers the dissolution of carbonates according to equilibria like the one exemplified by equation (1). The ion-exchange reactions can be described by ... 

The peculiar layer structure of these clays gives them cation exchange and intercalation properties that can be very useful. Molecules, such as water, and polar organic molecules, such as glycol, can easily intercalate between the layers and cause the clay to swell. Water enters the interlayer region as integral numbers of complete layers. Calcium montmorillonite usually has two layers of water molecules but the sodium form can have one, two, or three water layers this causes the interlayer spacing to increase stepwise from about 960 pm in the dehydrated clay to 1250, 1550, and 1900 pm as each successive layer of water forms. 

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