Organoclays are sorbent materials prepared from clays by exchanging inorganic with organic cations. Their properties depend on the loading and conformational structure of the organic cations, but little information is available about the surface structures of organoclays. In this work, X-ray photoelectron spectroscopy (XPS) and classical molecular dynamics (MD) simulations are combined to characterize the external interface of an organoclay prepared from hexadecylpyridinium (HDPy+) and bentonite. The XPS survey spectra show well the varying elemental composition of the surface with increasing amount of surfactant, showing a decreasing contribution of clay-derived elements with increasing organic coverage. The high-resolution C 1s XPS spectra depict sensitively the surface arrangement of the surfactant. In combination with MD simulations, the results implied a monolayer coating for low surfactant coverage and a disordered bilayer arrangement at high surfactant uptakes. Molecular dynamics simulations showed that for very high cation uptake a quasi-paraffin-like configuration is also possible. The combination of experimental and modelling methods yielded congruent information on the molecular-scale arrangement of organic cations at the organoclay surfaces and the controlling mechanisms.

Kaolin wastes from the Capim and Jari regions (Brazil) were used to produce sodalite under the same conditions used in the Bayer process, in order to control its formation when necessary. Of the two kaolin source materials, the kaolinite from the Jari region was more reactive in the synthesis of sodalite, which is attributed to the low degree of structural order of this clay mineral which increased its reactivity. At a temperature of 150°C and with a Na/Al ratio of 2, although the kaolinite did not react completely, sodalitewas the primary reaction product. An increase in the temperature to 200°C provoked the complete reaction of the kaolinite only for the products in which carbonate and sulfate were used. With a Na/Al ratio >2 and for both of the temperatures, the kaolinite reacted completely to form sodalite.

Non-isothermal dehydration kinetics of a heulandite-type zeolite-rich tuff from Turkey was investigated using thermogravimetric data recorded at three different heating rates (5, 10 and 20°C/min) under nitrogen flow. Isoconversional model-free methods gave a constant activation energy over the temperature range 30–200°C suggesting that the dehydration is a single-step process within this temperature range. The apparent activation energy was determined as: 34.54±1.18, 30.99±1.14 and 27.79±1.42 kJ/mol by the Flynn–Wall–Ozawa, the Kissinger–Akahira–Sunose and the Friedman methods, respectively. The activation energy values determined were less than the activation energy for vaporization of bulk water, indicating control of the dehydration rate by diffusion of water within this temperature range.

Anisotropy and compositional and structural heterogeneity in clays are causes of considerable deviations from homogeneous diffusion, in particular in terms of direction-dependent transport rates and preferred transport zones. Conventional diffusion experiments, in which the sample is treated as a homogeneous black box in a concentration gradient, are interminable and insensitive to spatial effects. In contrast, tomographic imaging methods are capable of both reducing the amount of observation time required and revealing space-dependent features of the diffusion process.

In the present study, positron-emission-tomography (PET) was applied as the most sensitive quantitative spatiotemporal tomographic modality for direct observation of positron-emitting radiotracers in opaque media at reasonable resolution (1 mm) on a laboratory scale (100 mm).

Geoscientific applications of PET, or GeoPET, have revealed anisotropic and heterogeneous effects in diffusion experiments that have been conducted on Opalinus clay samples of different sizes, as well as on other rock types. Applying the Comsol Optimization Module to 2D-image sections of the PET tomograms, effective parameter values were derived, thereby quantifying the anisotropic diffusion.

The removal of lead and zinc from a binary solution by fixed bed depths (40, 80 and 120 mm) of a natural zeolite was examined at a flow rate of 1 mL/min. The results obtained were fitted to the Bed Depth Service Time (BDST) model and the parameters of the model (q and k) were used to design a column system for flow rates of 2 and 3 mL/min at a bed depth of 80 mm. The experimental results were in excellent agreement with those predicted and experimental breakthrough curves for the binary systems were obtained. This approach facilitates the design of effective binary column processes without additional experimentation. Two major design parameters, the Empty Bed Contact Time (EBCT) and the zeolite usage rate, were calculated. The highest EBCT value of 13.56 min represents the optimal conditions for the binary (Pb+Zn) solution.

The removal of Cr(VI) from aqueous solutions under various conditions was investigated using a natural clinoptilolite and a synthetic zeolite derived from fly-ash (Na-P1), modified either with hexadecyltrimethylammonium bromide (HDTMA) or octadecyltrimethylammonium bromide (ODTMA). The study was focused mainly on the impact of the properties of the zeolite on the sorption capacity, the sorption mechanism, the influence of pH and the durability of the immobilization. The zeolites were modified with HDTMA and ODTMA surfactants up to 100% and 120% of their external cation exchange capacity. Batch and column studies were conducted to evaluate the influence of pH and the initial Cr(VI) concentration on their efficiencies for removing chromates. The organo-zeolites show a significant ability to remove Cr(VI) from aqueous solutions. The amount of Cr(VI) removed by organo-clinoptilolite and organo-zeolite Na-P1 is greater at low pH values, whereas the sorption efficiency decreased with increasing pH. Sorption of Cr(VI) was more efficient with the HDTMA-modified organo-clinoptilolite (150 mmol Cr(VI)/kg) than the ODTMA-modified clinoptilolite (132 mmol Cr(VI)/kg). The maximum sorption capacity was obtained with the 1.2 × ECEC ODTMA-modified clinoptilolite (237 mmol Cr(VI)/kg). The organozeolites Na-P1 adsorbed Cr(VI) from aqueous solutions more effectively and were much more durable than the organo-clinoptilolites.

Calcigel bentonite-polyacrylamide (PAA) composites were investigated for their formation characteristics and their macroscopic hydro-mechanical and microscopic structural properties. The composites prepared were different in terms of the polymer charge, i.e. cationic (PAA+), anionic (PAA−), non-ionic (PAA°) and in terms of the polymer-to-clay ratio. The latter varied according to the individual maximum sorption capacity established from adsorption isotherms. Oedometer and waterretention testswere conducted on composites prepared under initial slurry conditions. The microstructure of the composites was investigated using environmental scanning electron microscopy (ESEM). At low stress, distinctly increased void ratios were found for all types of the composites, whereas under highstress conditions only the PAA+-composite prepared at 100% of the maximum sorption capacity showed an increase in void ratio. Analyses by ESEM on this composite indicated structural changes related to the preferential face-to-face aggregation, which help to explain the macroscopic behaviour and also account for the increased hydraulic permeabilities observed.

The two high-pressure water-retaining dams at the Ibbenbüren coalmine in Münsterland (Germany) have to perform reliably under the induced tension caused by further exploitation of the current mining area. The load-bearing and the sealing functions of the new barriers were separated and new sealing materials were developed. An innovative multilayer sealing system of bentonite and sandwiched equipotential layers (SANDWICH) supporting homogeneous swelling and sealing, independent of formation water (Nüesch et al., 2002), was applied in this project. A testing program of strain-controlled swelling pressure tests on compacted bentonite specimens and on a bentonite/sand mixture was conducted to ensure an adequate potential for swelling-pressure development.

The measurements under constant volume for dry densities between 1.45 g/cm3 and 1.67 g/cm3 showed an evolving swelling pressure between 1.04 and 1.8 MPa for 100% bentonite samples. Straincontrolled oedometer tests for zero strain and step-wise applied strain up to 2% revealed that a sufficient magnitude of swelling pressure existed at maximum applied strain.

The sorption properties of iron-modified zeolite (IMZ) and the kinetics of zinc and cadmium uptake by the IMZ were investigated by the batch method. Two kinetic stages were observed, fast uptake up to 240 min, followed by slow uptake up to equilibrium. Kinetic results were fitted to the reaction and diffusion kinetic models, which indicated that intra-particle diffusion was the rate-limiting step. The Vermeulen’s approximation model was used to predict the quantity of Zn and Cd ions removed per gram of IMZ. The results of the successive sorption and desorption of Zn and Cd ions, with different electrolyte solutions, showed the best desorption efficiency with sodium salt solutions. Four successive repetitions of the sorption/desorption cycles showed a small difference between the amount of sorbed and desorbed Zn and Cd ions from the second to the fourth cycle. This indicates excellent sorption/regeneration properties of the IMZ.

This contribution is the second part of an in-depth study on the hydration and strength evolution of blended cement pastes at a water to binder (W/B) ratio of 0.3, cured by two different methods. The blended cement pastes showed significant hydration up to 7 days, when almost all of the hydration products had already formed; thereafter, carbonation played an important role up to, and possibly beyond, 91 days. Likewise, the hydration of alite (tricalcium silicate, Ca3SiO5, C3S) proceeded up to 14 days and then started to slow down. However, the hydration of belite (dicalcium silicate, Ca2SiO4, C2S) was affected most strongly, as it nearly ceased, under the air-curing conditions. During hydration, some of the blended cement pastes had a larger calcium hydroxide (CH) content than the unblended (plain) ones. The accelerating effects of the addition of supplementary cementitious materials (SCMs), the air-curing conditions and the low W/B ratio may explain these unusual results. Under these experimental conditions, the water incorporated into hydrates was about 50% of the total amount of water used during full hydration of the cement pastes. The pozzolanic reaction predominated during the early ages, but disappeared as time passed. In contrast, the carbonation reaction increased by consuming ∼45% of the total amount of CH produced after aging for 91 days. Only one blended cement paste reached the compressive strength of the plain cements. The blended cement pastes containing 5% of the zeolitic tuffs, Zeo1 or Zeo2, or 10% of the calcareous siltstone, Limo, developed the greatest compressive strength under the experimental conditions used in this study.

The present study determined the mineralogy and thermal properties of kaolin from Acoculco (Puebla), at the eastern Trans-Mexican Volcanic Belt and compared it with the nearby deposits of Agua Blanca (Hidalgo) and Huayacocotla (Veracruz). The mineralogy of the kaolins was determined by X-ray diffraction, infrared spectroscopy and scanning electron microscopy. Thermal behaviour was studied by differential thermal analysis, dilatometry and hot-stage microscopy. The Acoculco deposit is composed mainly of kaolinite and SiO2 minerals. In the case of Agua Blanca and Huayacocotla, alunite is abundant in places and minor anatase is also present locally. The Acoculco kaolins are Fe-poor and relatively rich in some potentially toxic elements (Zr, Sb, Pb). They undergo a relatively small amount of shrinkage (∼3–4 vol.%), during firing at 20–1300°C and cooling down to 20°C, except when >10 wt.% alunite is present. These kaolins are a suitable raw material for the ceramics industry. Other applications (pharmaceuticals, cosmetics) would require an enrichment process to eliminate impurities such as Fe oxides.