Transition metal montmorillonites were saturated with benzidine (BEN) and heated gradually to 200°C, in a vacuum cell supported
by KBr windows. IR spectra were recorded before and after the thermal treatment and at various temperatures during this treatment.
X-ray diffractions were recorded before and after the thermal treatment. Hg clay shows properties similar to those of Mg and
Ca clays. In the interlayer BEN is bound to Hg through a water molecule bridge, either by proton accepting (typeA) or by proton donation (typeB). Some BEN is also protonated (typeD). Initially typeA predominates, but after the thermal treatment, when the film is rehydrated, the amounts of typesB andD increase. With Mn-, Co-, Ni-, Zn- and Cd-montmorillonite a direct coordination of the benzidine by the dehydrated metallic
cation is obtained (typeC), in addition to small amounts of typesA,B andD. During the thermal treatment water is evolved and associationsA andB are completely transformed toC. At elevated temperatures the following associations were identified in trace amounts, ammonium-amine, BEN bound to non-structured
water, hydrophobic adsorbed BEN and BEN bound to the oxygen plane (typesE, F, H andJ, respectively). During the thermal treatment of Co and Cd clays some of the benzidine was oxidized, probably to semiquinone
and quinoidal cation.
The swelling properties of Al-pillared clays, obtained from five different smectites, were studied using X-ray diffraction.
These clays, the dioctahedral beidellite and montmorillonite and the trioctahedral saponite, hectorite and laponite differ
in source of isomorphic substitution and represent a series of decreasing basicity along the siloxane plane. An Al oxyhydroxy
cation was inserted between the layers to form the respective pillared clays and these clays were heated incrementally to
600°C. The XRD peaks at each stage of heating were recorded as well as the same samples subsequently wetted. Basal spacings
of each clay at each stage of dehydration ↭d rehydration indicated that the swelling of tetrahedrally substituted saponite
and beidellite was indeed restricted, compared with the other three clays. This was attributed to greater basicity of the
oxygen plane of beidellite and saponite due to tetrahedral substitution of Si by Al, resulting in an increase in the strength
of hydrogen bonds between either water or the interlayer polyhydroxy cation and the clay.
The data from the XRD analyses helped in addition, to clarify the thermal transformations of the Keggin ion itself. According
to the changes in thed-spacings of the pillared clays it was concluded that the Keggin ion lost its structural water at ∼200°C and dehydroxylated
in a range beginning at 350°C. Between 500 to 600°C this polymer cation, which is thought to form the Al2O3 oxide, did not rehydrate.
Li-, Na-, K-, Rb- and Cs-montmorillonites were saturated with benzidine, these organo-clay complexes heated under vacuum to
200°C and IR spectra recorded at various temperatures. Benzidine is mostly bound to interlayer cations through water molecules,
except in Cs-clay where bonding to hydrophobic water and to water molecules which are hydrogen bonded to the oxygen plane
predominates. During the thermal treatment water is lost and alkali, cations coordinate directly with benzidine. In Cs-, and
to some extent also in Rb- and K-montmorillonite, benzidine is oxidized to semiquinone and quinoidal cation during the thermal
Authors:S. Yariv, I. Lapides, K.H. Michaelian, and N. Lahav
Solid state intercalation of alkali halides into kaolinite takes place by heating pressed disks of dimethylsulfoxide (DMSO)-kaolinite
complex ground in different alkali halides. This reaction involves diffusion of the DMSO outside the interlayer space and
the alkali halide into the interlayer space. IR and Raman spectroscopy reveal two types of intercalation complexes: (i) almost
non-hydrous, obtained during thermal treatment of the DMSO complex; and (ii) hydrated, obtained by regrinding the disk in
air. The strength of the hydrogen bonds between intercalated water or halide anions and the inner surface hydroxyls decreases
in the order Cl−>Br−>I−. Chlorides penetrate the ditrigonal holes and form hydrogen bonds with the inner OH groups.
Authors:I. Lapides, N. Lahav, K. H. Michaelian, and S. Yariv
Intercalation complexes of kaolinite with a series of alkali halides (NaCl (trace amounts), KCl, RbCl, CsCl, NaBr, KBr, CsBr, Kl, Rbl and Csl) were obtained by a thermal solid state reaction between the kaolinite-dimethylsulfoxide intercalation complex and the appropriate alkali halide. The ground mixtures (1∶1 weight ratio) were pressed into disks that were gradually heated up to 250 °C for different times. X-ray diffractograms of the disks were recorded after each thermal treatment. At the end of the thermal treatment the disks were ground and basal spacings of the powders obtained. As a result of thermal treatment, alkali halide ions diffuse into the interlayers, replacing the intercalated dimethylsulfoxide molecules. Such a replacement may take place only if the thermal diffusion of the penetrating species is faster than the evolution of the intercalated organic molecule. With increasing temperature the intercalated salt diffused outside the interlayer space or underwent a thermal hydrolysis which resulted in the evolution of hydrogen halides from the interlayer space. Consequently, the amounts of intercalation complexes decreased at elevated temperatures.
Authors:N. Lahav, D. Ovadyahu, A. Gutkin, E. Mastov, T. Menjeritzki, A. Adin, L. Rubinstein, D. Tropp, and S. Yariv
A device was constructed in which a clay suspension is hermetically heated at 220°C for a few minutes. This thermal treatment
is accompanied by a pressure increase in the cell. Once the valve is opened, there is a fast release of the pressure inside
the cell and a sudden evolution of the interparticle water. This shock leads to a quasi explosion of the clay particle. This
technique was named thermal vapour pressure shock explosion (TSE). The effect of TSE treatment on the properties of palygorskite
suspensions was investigated. Palygorskite suspensions in water are rather unstable and particles smaller than 3 μm in size
are not found before a TSE treatment. Stabilization of the suspension can be obtained by TSE treatments and/or by using a
dispersing agent such as pyrophosphate, or both. As a result of TSE treatments smaller particles are obtained, the dispersiveness
of the particles is improved and electrophoretic mobility is increased. Electron microscopy scans showed that the aggregates
of needles which form the palygorskite fibres, disintegrate to separated thin needles as a result of the TSE treatment.