The strongly coloured Cu-triethylenetetramine complex (Cu-Trien) provides a fast and easy way to measure the cation exchange capacity of clay samples, but the reliability of this method has been questioned in recent publications. This work identifies several reasons for the poor reliability, thus improving both the precision and accuracy of the CEC method. Pure Trien is shown here to intercalate as does the Cu-Trien complex. Hence, the purity of Trien and also the Cu/Trien ratio require special attention. Using cold Cu-Trien solutions produces systematic deviations in CEC determinations caused by errors in the pipetted volumes. The present study demonstrates, for the first time, that the Cu-Trien complex protonates and changes its effective charge beyond 2+. Based on titration experiments at three different temperatures, a correction function is derived for calculating the total charge of the Cu-Trien complex as a function of pH. Accounting for these pH-corrected charges indicates that Cu-Trien may well be insensitive to edge charges on smectite. Finally, it is shown here that the ratio of sample mass to the initial amount of Cu-Trien is critical because excess adsorption of Cu-Trien in addition to CEC sensu strictu was observed.

The present study investigated the removal of methylene blue (MB) and orange II (OII) dyes from synthetic wastewater by means of adsorption and photocatalysis using natural kaolins. ForMB adsorption, the raw kaolinite-rich samples showed the greatest adsorption capacity, with rapid uptake (90% after 20 min). The experimental results were fitted better using the Langmuir isotherm model parameters compared to the Freundlich model, suggesting that the adsorption corresponds to monolayer coverage of MB molecules over the kaolinite surface. For OII, neither the Langmuir nor the Freundlich model gave reliable results, because the adsorption of anionic dye molecules by the clayey particles is not favoured.

Mixtures of kaolinite/Degussa TiO2 were also prepared, and their photocatalytic properties under UVlight exposure were investigated. Decolourization of MB solutions was observed, even in a mixture with low TiO2 content. This is related to the combined effect of adsorption and photocatalysis and, unlike the pure clay samples, the efficiency of such mixtures against OII was only slightly weaker (80–94%).

For TiO2-impregnated clays, with the kaolinite layers separated by sol-gel TiO2 particles, the MB removal was slow and effective only after >24 h due to the complexity of the bonding of MB molecules. On the other hand, the removal performance against OII solutions was very efficient (nearly 100%) within only 2 h. This excellent performance was attributed to morphological changes in clay particles.

An homogenous intercalated compound of dioctahedral 1:1 clay mineral with cesium chloride was prepared by immersing an homogeneous 8.4 Å hydrated nacrite in a CsCl-saturated solution. The nacrite/CsCl complex obtained was studied using X-ray diffraction and thermogravimetric analysis (TGA). The best agreement between the observed and the simulated ρ(z) (R = 7%) was obtained with one Cl− ion, one Cs+ ion and onewater molecule (per half-unit cell). The cation was located near the oxygen atom plane, while the anion was located near the hydroxyl groups of the adjacent layer. The number of the species intercalated in nacrite/CsCl was confirmed by TGA analysis. The best agreement between the calculated and the experimental hkl reflections, with h and/or k ≠ 0, corresponded to a stacking of 70% and 30% for T1 = −0.35a − 0.20b + 10.50n and T2 = +b/3 + 10.5n, respectively. These results indicate that the surface hydroxyls form hydrogen bonds with Cl− ions. The Cs+ ions are situated near the ditrigonal cavities of the tetrahedral sheet and they interact with the surface oxygen atoms whereas the H2O molecules interact with the intercalated species.

The use of Mg-montmorillonite in the production of organoclay without sodium activation was investigated. For this purpose, organophilization experiments were carried out by varying the concentration of two surfactants: hexadecyltrimethylammonium (HDTMA+) and dodecyltrimethylammonium (DTMA+) ions. These surfactantswere used at concentrations 0.7, 1.0 and 1.5 times that of the cation exchange capacity (62.6 meq/100 g) of the clay, with a reaction time of 8 h at temperatures of 25 and 80°C. X-ray diffraction (XRD) results confirmed the intercalation for both in natura and activated samples. The Fourier-transforminfrared (FTIR) spectroscopy and XRD results showed that the ratio of gauche/trans conformers decreased with increased basal spacing. The results of thermodifferential and thermogravimetric analysis (DTA/DTG) confirmed the thermal stability of the organoclay up to 200°C, permitting the use of suchmaterial in the synthesis of polymer/clay nanocomposites obtained by the melt blending. Thus, Mg-montmorillonite can be intercalated with alkylammonium ions without prior Na-activation to form organoclays. The possibility of using natural (non-activated) Mg-montmorillonite represents a significant difference in terms of processing cost in comparison with existing Ca-montmorillonite in Brazil or even with imported bentonites that require Na-activation during beneficiation.

Few reports exist on the use of Diffuse Reflectance Infrared Fourier Transform Spectrometry coupled with Mass Spectrometry (DRIFTS-MS) in situ to monitor the dehydroxylation of kaolinitic clays. The use of DRIFTS-MS in situ allows study of the effect of heat treatment on the dehydroxylation, identifying intensities and temperatures at which the hydroxyl groups are released, forming metakaolinite and meta-alunite. The effluent gases from the infrared cell were analysed by mass spectrometry. The decrease in intensity of the bands at 3694, 3669, 3650 and 3621 cm−1 associated with the −OH stretching vibration modes of AlVI−OH−AlVI of kaolinite began at 450°C. Two additional bands at 3513 and 3485 cm−1 are associated with the vibration of AlVI−OH of alunite that also began to disappear during thermal treatment. Monitoring of the fractions m/e 17 and 18 using a mass spectrometer revealed that the intensity of these fractions increased starting at 450°C. Therefore, it is possible to study the dehydroxylation process of clays during thermal treatment.Chemical and mineralogical characterization of a kaolinitic clay (KN) fromMexico showed that the clay consists of 64.8% kaolinite, 11.0% alunite and 24.4% quartz based on PXRD, EDS, TG/DTA, TEM and FTIR results, and suggested that the material might have potential for use in the manufacture of ceramics, refractory bricks or geopolymers.

The milling process in the solid-state 2:1 clay minerals, montmorillonite and talc, which have different cation exchange capacities, is reported here. Several instrumental techniques were used to monitor systematically the products formed. The dehydroxylation/amorphization of the montmorillonite and talc structures occurs within 3 and 6 h of milling, respectively. Electron paramagnetic resonance spectra indicated that structural Mn2+ was oxidized more quickly in the montmorillonite structure than in talc, while the paramagnetic defects increased during milling. Nuclear magnetic resonance was also used to monitor the environmental changes for Si and Al during milling.

Diffuse reflectance (DR) spectra in the visible (VIS) and near-infrared (NIR) region of methylene blue (MB) adsorbed on clay samples of different mineral composition and varying MB/clay ratios were analyzed. This type of investigation is not affected by unadsorbed MB molecules and can be used in clay-mineral determination. When the MB dye/clay loading was increased, enhancement of bands in the DR-VIS and DR-NIR was observed. The distribution of various MB aggregates was interpreted according to mineral composition and MB loading. The NIR spectrum of H2O overtone provides insights about the intercalated MB aggregation, consistent with VIS spectra. Critical MB concentration for formation of dimeric structure was between 0.7 and 1.75 mmol/100 g followed with suppression of monomers. Different orientations of vectors of polarized light allowed calculations of the possible orientation and tilting angle of MB molecules on the surface of the clay particles in accordance with XRD data.

Commercial bentonite from the Kopernica deposit, Slovakia, is currently mined by the CERTECH Company, Poland, to produce materials intended for animal-care applications and other industrial purposes. The present study aimed to assess the mineralogical, petrographic and physicochemical characteristics of three bentonite varieties from Kopernica used by the company. The X-ray diffraction, optical microscopy, field emission scanning electron microscopy (FESEM), nuclear magnetic resonance, thermal analysis, infrared spectroscopy and chemical analyses showed that the main component of the rocks is montmorillonite with the average structural formula Ca0.31K0.08Na0.04(Al3.23Mg0.54Fe0.23)[(Si7.80Al0.20)O20](OH)4. In addition, opal-C/CT, biotite, potassium feldspar and plagioclase, quartz, clinoptilolite and kaolinite are present. Key information about the textural relationships between the mineral components identified was obtained from detailed thin-section petrography and FESEM studies. The rocks studied have fragmented, eutaxitic texture. They are composed of pumice fragments collapsed into lenticular masses (fiamme) which were strongly deformed and altered, though the shard structures were retained. The compressed glass shards were moulded around pyroclastic grains such as crystal fragments of quartz, biotite and zoned plagioclases, and clasts of volcanic rocks. Observations by FESEM showed that the axes of shards and the walls of the flattened vacuoles are outlined by the inward-growing microlites of silica (axiolitic texture), whilst the interiors of shards are altered to clay. Grain-size distribution, textural properties and microscope observations of grain-size fractions reveal that the Kopernica bentonite contains montmorillonite-opal aggregates difficult to disperse in water.