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.
Co- and Ni-montmorillonites adsorb in aqueous suspensions up to 13 mmol alizarinate per 100 g clay, onto the broken-bonds
whereas Cu-clay adsorbs up to 25 mmol dye per 100 g clay into the interlayer space. Unloaded Co-, Ni- and Cu-clays and samples
loaded with increasing amounts of alizarinate, were gradually heated in air to 360C and analyzed by X-ray diffraction. All
diffractograms were curve-fitted. Fitted diffractograms of non-heated samples, showed two peak components labeled C and D,
nm, characterizing tactoids with mono- and non-complete bilayers of water, respectively. After heating at 120C component
D decreased or disappeared and two new components A and B appeared at0.99 and1.08
nm, representing collapsed tactoids and tactoids with interlamellar oxy-cations, respectively. At 250C, C and D decreased
or disappeared but A and B appeared in all fitted diffractograms. Co- and Ni-clay after heating at 360C did not show C and
D. Components A and B proved that these clays collapsed indicating that initially there was no alizarinate in the interlayers.
At 360C, C and D persisted in the fitted-diffractograms of Cu-clay, representing tactoids with interlamellar charcoal formed
from the partial oxidation of adsorbed dye initially located in the interlayers.
Montmorillonite and Laponite loaded with
different amounts of tributylammonium cations (TBAH+),
up to 40 and 30 mmol, respectively, per 100 g clay, were studied by thermo-XRD-analysis.
TBAH-smectites heated at 300 and 420°C exhibited basal spacings of 1.30
and 1.24 nm, attributed to smectite tactoids with low- and high-temperature-stable
monolayer charcoals, respectively in the interlayers. DTA-EGA and TG of the
TBAH-smectites showed four stages of mass loss labeled A, B, C and D. Stage
A below 250°C, accompanied by an endothermic DTA peak, resulted from the
dehydration of the clay. Mass loss stages B, C and D, at 250–380, 380–605°C
and above 605°C, respectively, accompanied by exothermic DTA peaks, were
due to three oxidation steps of the organic matter. In mass loss stage B (first
oxidation step) mainly organic hydrogen was oxidized to H2O whereas carbon
and nitrogen formed low- and high-temperature-stable charcoals. In stages
C and D (second and third oxidation steps) low- and high-temperature- stable
charcoals were oxidized, respectively. Dehydroxylation of the smectites occurred
together with the second and third oxidation steps. Thermal mass loss at each
step was calculated from the TG curves showing that in montmorillonite the
percentage of high-temperature-stable charcoal from total charcoal decreased
with higher TBAH+ loadings of the clay whereas
in Laponite this percentage increased with higher loadings of the clay.
The mechanochemical solid-state adsorption of the cationic dye crystal violet (CV) by montmorillonite was investigated by XRD and simultaneous DTA-TG. Solid CV was ground with the clay for 5 min and four different varieties of CV mechanochemically treated clay were investigated. X-ray and DTA data were compared with those of CV-montmorillonite obtained from an aqueous suspension. X-ray and DTA studies of a ground mixture and a ground mixture heated at 110°C suggest that the mechanochemical adsorption of organic cations takes place on the external surfaces of the clay. The study of a ground mixture washed with water, and washed with water and acetone reveal that water is essential for the penetration of CV into the interlayer space.
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
Montmorillonite (M) saturated with H+,Li+,Na+,K+,Rb+,Cs+,NH4+,Mg2+,Ca2+,Sr2+,Ba2+,Mn2+,Co2+,Cu2+,Al3+ and Fe3+ were dry-ground with urea (U) in mass ratios U/M between 0.1 and 2.0 in an agate mortar and diffracted by X-ray. Extensive swellings occurred with H-, Li-, Na-, di-and trivalent
cation-clays, suggesting the formation of urea-montmorillonite intercalation complexes. Mechanochemically treated samples
were heated at different temperatures up to 375°C. The rise in temperature was accompanied by a decrease in the basal spacing.
There was a correlation between the results of the thermo-XRD-analysis and the fine structures of the urea-montmorillonite
complexes described in the literature. Five stages in the basal spacing vs. temperature curves were identified. In the first stage (at 150°C) the decrease was due to dehydration. In the second stage
(175°C) this dehydration was accompanied by some thermal intercalation of excess urea. The other stages (at 225, 325 and 375°C)
were associated with the degradation of urea and the condensation of the degraded species to polymeric products. At 375°C
Li-, Na-, K-NH4-, Mh-, Co- and Cu-montmorillonite collapsed, indicating that urea was evolved. The other urea-clay complexes did not collapse
due to intercalated polymers formed by the degradation products of urea.
Authors:Z. Malek, V. Balek, D. Garfinkel-Shweky, and S. Yariv
The dehydration and dehydroxylation of the smectites, beidellite and montmorillonite (dioctahedral) and saponite and laponite (trioctahedral), were investigated by ETA, DTA, TG and X-ray diffractions. There are differences between the behaviors of di- and trioctahedral clays which are due to the differences in the ability of the exchangeable cations to migrate into hexagonal holes of the SiO4 network and due to the fact that the dehydroxylation and recrystallization of dehydroxylated trioctahedral smectites occur simultaneously, whereas there is a temperature gap of about 300°C between the dehydroxylation and the recrystallization of dioctahedral smectites.