Swelling deformation tests of Kunigel bentonite and its sand mixtures were performed in distilled water and NaCl solution. The salinity of NaCl solution has a significant impact on the swelling properties of bentonite, but not on its surface structure. The surface structure was characterized using the fractal dimension Ds. Based on the fractal dimension, a unique curve of the em–pe relationship (em is the void ratio of montmorillonite and pe is the effective stress) at full saturation was introduced to express the swelling deformation of bentonite–sand mixtures. In mixtures with a large bentonite content, the swelling deformation always followed the em–pe relationship. In mixtures with a small bentonite content, when the effective stress reached a threshold, the void ratio of montmorillonite em deviated from the unique em–pe curve due to the appearance of a sand skeleton. The threshold of vertical pressure for mixtures in different solutions and the maximum swelling strains were estimated using the em–pe relationship. The good agreement between estimates and experimental data suggest that the em–pe relationship might be an alternative method for predicting the swelling deformation of bentonite–sand mixtures in salt solution.

Systems consisting of layered structures and photoactive molecules have been studied extensively. The structures of resulting complexes may be controlled by UV–Vis radiation, which subsequently affects their materials properties. This study describes a synthesis route for obtaining a photoresponsive kaolinite intercalation compound. The material was prepared by co-intercalating azobenzene and benzylalkylammonium chlorides into a methoxy form of kaolinite. The resultant materials possessed large basal spacing values in the range of 45–55 Å. The UV–Vis and Fourier-transform infrared spectroscopy analyses confirmed the reversible photoisomerization of azobenzene upon exposure to UV and Vis radiation. This phenomenon was significantly influenced by the type and amount of co-intercalated molecules. Upon multiple trans–cis conversions, the azobenzene partially evaporated. For the first time, a kaolinite-based material was prepared that exhibited photochromic behaviour upon UV and Vis irradiation.

Portuguese gypsum deposits utilized by the cement industry were characterized mineralogically, chemically and technologically for possible application in dermocosmetics. The deposits studied (Loulé, Óbidos and Soure) correspond to small outcrops in diapiric anticline areas. In principle, they represent gypsites which are white, and generally of higher quality for traditional applications (e.g. white cement), or greyish, and generally not adequate for cements and mortars. The analytical methods used to characterize the materials were wet sieving and X-ray sedimentation, X-ray diffraction, X-ray fluorescence spectrometry and assessment of abrasiveness, plasticity, texturometrics (adhesivity and firmness), oil absorption and cooling rate. The Óbidos gypsum displayed greater mineralogical and chemical quality (almost pure calcium sulfate) and had a finer grain size (<63 μm), whereas Loulé and Soure gypsums contain mineralogical impurities (mainly quartz). The Óbidos gypsum shows good characteristics in general for application in dermocosmetics because of its absorption, plasticity, adhesivity, firmness and low abrasiveness.

The Neogene marls from the lower Kert area (northeast Morocco) were characterized to evaluate their suitability for the ceramics industry. Two cross-sections involving all of the Neogene facies were studied on both banks of the Kert River. Grey and green marls occurring between sandstone and tuffs were characterized by mineralogical (X-ray diffraction) and physicochemical (grain size, Atterberg limits, X-ray fluorescence and specific surface area) analyses. The Neogene clays studied are mainly calcareous silty marls containing 13–20 wt.% calcite. They consist of quartz, calcite, feldspars, dolomite, illite, kaolinite, chlorite and 10–14 Å illite-vermiculite mixed layers. Cristobalite was detected only in the uppermost level of the green marls, and it originates from a volcanic ash of Messinian age. Trace amounts of siderite and rhodochrosite indicate reducing or locally oxidizing conditions during sedimentation or shortly thereafter. The marls have medium to high plasticity, making them optimal for extrusion. Raw Neogene marls are suitable for manufacturing structural clay products. More specific uses, such as hollow products, roofing tiles and masonry bricks, were supported by the geochemical results and grain-size distribution.

Natural zeolite (clinoptilolite)-based geopolymers were synthesized using alkali aluminate solution, including aluminate anodizing waste solution. The effect of calcination of the clinoptilolite sample at 900°C was investigated. The samples were studied by powder X-ray diffraction, thermal analysis, scanning electron microscopy and N2-specific surface area. The alkali aluminate-activated clinoptilolite geopolymers are characterized by satisfactory compressive strength (up to 37 MPa), low density and acceptable shrinkage. The clinoptilolite geopolymer obtained contains an X-ray amorphous phase and newly formed phillipsite and zeolite NaP. The presence of zeolite phases in the geopolymer agglomerate could be beneficial in products with specific qualities and properties, such as ion exchange, passive cooling, antimicrobial activity, etc.

To reveal the factors that determine the different ranges of compositional variations in high- and low-temperature Al-rich K-dioctahedral micas, relationships between structural parameters and cation composition were analysed for: (1) a series of synthetic 2M1 muscovite–phengite–aluminoceladonite samples; and (2) Al-rich, K-dioctahedral 2M1 micas with previously published refined structural data. The dependences of the unit-cell parameters on cation composition and the variations in tetrahedral and octahedral lateral dimensions and sheet thicknesses, interlayer distances and tetrahedral rotation angles were analysed and compared with those found previously for the series 1M trans-vacant (tv) illite–1M aluminoceladonite. The similarities in the variations of unit-cell parameters with cation composition observed in 2M1 and 1M natural and synthetic K-dioctahedral micas imply that these variations are controlled by similar – albeit not identical – structural factors. A major structural factor is the readjustment of the differently sized tetrahedral and octahedral sheets, which is realized in a different manner in micas formed under different pressure and temperature conditions.

An iron catalyst supported on the modified Tamazert kaolin has been prepared and tested in catalytic wet peroxide oxidation using phenol and 4-chlorophenol (4-CP) as target compounds (100 mg/L initial concentration). Kaolin is not usually employed as a catalytic support due to its low developed porous structure, but its textural properties may be improved upon calcination and acid and basic treatment. The catalyst was characterized by N2 adsorption–desorption and chemical analysis by total-reflection X-ray fluorescence spectroscopy. The catalytic tests were carried out in a batch reactor with a stoichiometric amount of H2O2. The catalytic efficiency was studied within the temperature range of 25–55°C at an initial pH of 3.3 and 1 g/L catalyst. Complete phenol and 4-CP removal was achieved with no significant differences in phenol and 4-CP conversions within the temperature range tested. Meanwhile, total organic carbon (TOC) reduction was greatly favoured by increasing the temperature, which may be partially attributed to a probable contribution of a homogeneous reaction associated with iron leaching. However, this effect might be of limited significance because the highest concentrations of iron in the liquid phase were below 4.5 and 8.5 mg/L in the experiments with phenol and 4-CP, respectively. At 55°C, TOC was reduced by ~70% after 4 h reaction time, with the remaining by-products corresponding almost completely to low-molecular-weight carboxylic acids of very low ecotoxicity.

This research presents the mineralogical and chemical characterization and beneficiation study of two kaolin deposits from the Borborema Pegmatite Province, Brazil. Seven samples were collected and treated in two different beneficiation routes involving magnetic separation and chemical bleaching. The fractions obtained were studied by X-ray diffraction, X-ray fluorescence spectrometry, scanning electron microscopy, particle-size analyses, electron paramagnetic resonance and determination of optical properties. The samples are composed mainly of subhedral kaolinite in the form of booklets, as well as muscovite, quartz, microcline and illite impurities. The kaolinite structural formulae indicated significant replacement of Si4+ by Al3+ in tetrahedral sites and low replacement of Fe3+ by Al3+ in the octahedral sites. The first 30 min of chemical bleaching improved significantly the optical properties of kaolin, indicating that the process is more efficient than magnetic separation.

Temporary excavations during the construction of the Glendoe Hydro Scheme above Loch Ness in the Highlands of Scotland exposed a clay-rich fault gouge in Dalradian Supergroup psammite. The gouge coincides with the mapped trace of the subvertical Sronlairig Fault, a feature related in part to the Great Glen and Ericht–Laidon faults, which had been interpreted to result from brittle deformation during the Caledonian orogeny (c. 420–390 Ma). Exposure of this mica-rich gouge represented an exceptional opportunity to constrain the timing of the gouge-producing movement on the Sronlairig Fault using isotopic analysis to date the growth of authigenic (essentially synkinematic) clay mineralization. A series of fine-size separates was isolated prior to K–Ar analysis. Novel, capillary-encapsulated X-ray diffraction analysis was employed to ensure nearly perfect, random orientation and to facilitate the identification and quantification of mica polytypes. Coarser size fractions are composed of greater proportions of the 2M1 illite polytype. Finer size fractions show increasing proportions of the 1M illite polytype, with no evidence of 2M1 illite in the finest fractions. A series of Illite Age Analysis plots produced excellent R2 values with calculated mean ages of 296 ± 7 Ma (Late Carboniferous–Early Permian) for the oldest (2M1) illite and 145 ± 7 Ma (Late Jurassic–Early Cretaceous) for the youngest (1M) illite. The Late Carboniferous–Early Permian (Faulting event 1) age may represent resetting of earlier-formed micas or authigenesis during dextral displacement of the Great Glen Fault Zone (GGFZ). Contemporaneous WNW(NW)–ESE(SE) extension was important for basin development and hydrocarbon migration in the Pentland Firth and Moray Firth regions. The Late Jurassic–Early Cretaceous (Faulting event 2) age corresponds with Moray Firth Basin development and indicates that the GGFZ and related structures may have acted to partition the active extension in the Moray Firth region from relative inactivity in the Pentland Firth area at this time. These new age dates demonstrate the long-lived geological activity on the GGFZ, particularly so in post-Caledonian times where other isotopic evidence for younger tectonic overprints is lacking.

Natural zeolites in the Aksitero sedimentary formation of the western Luzon area of the Philippines were evaluated. The natural washed zeolite (NW-Z) was preconditioned with acid to purify it and increase its surface area. Acid treatment with 3 M HCl for 12 h yielded optimum acid treatment of the NW-Z, causing increases in the Si/Al ratio, the specific surface area by 32.5% and the porosity of the acid-treated zeolite (HC-Z). The HC-Z was washed with 4 M NaCl for 3, 6, 12, 18, 24, 48 and 72 h to improve its cation-exchange capacity for copper. The sodium-treated zeolite (Na-Z) was immersed in 100 ppm CuSO4 solution to test the copper-uptake capacity. Pretreatment of HC-Z with 4 M NaCl for 24 h is optimal for sodium treatment of the preconditioned HC-Z. The preconditioning techniques did not significantly alter the structure and morphology of the zeolite samples. It is suggested that the preconditioned Philippine natural zeolite samples are readily available for further functionalization that will enhance their antibacterial, catalytic and adsorption properties, with various useful applications in the field of catalysis, biomedicine, environmental mitigation and wastewater treatment.

A Pickering emulsion was prepared via synergistic stabilization of a lipase and palygorskite particles. The optimum conditions for the stabilization of the Pickering emulsion, such as the concentrations of the palygorskite particles and lipase, were explored. The morphology of emulsion droplets was examined using digital optical microscopy and polarizing optical microscopy. The palygorskite–lipase co-stabilized Pickering emulsions were investigated by determination of the adsorption rate, pH and zeta potential of the aqueous dispersion, as well as by determining the contact angle values of the lipase solution on a palygorskite disc that was immersed in toluene. The catalytic performance of the immobilized lipase in the Pickering emulsion was studied via the investigation of its thermal stability, storage stability and reusability. The immobilized lipase showed greater stability than the free lipase. The lipase immobilized by Pickering emulsion retained a high level of activity even after seven periods of recycling.

The planned final disposal repositories of spent nuclear fuel in several countries, including Finland, pose significant scientific challenges due to their extremely long lifespan. One of the key materials proposed for use in Posiva Oy's repository in Finland is MX-80 bentonite in a compacted, water-saturated state. Border cases of calcium and sodium forms of purified bentonite were included in this study. The MX-80 in the repository is expected to undergo cation exchange due to the composition of the groundwater. The clays were studied at different dry densities between 0.7 and 1.6 g cm–3. The microstructure of the water-saturated, compacted clays was investigated using small-angle X-ray scattering, nuclear magnetic resonance and transmission electron microscopy. Additionally, atomic force microscopy was used to characterize the shape and size of the fine-fraction clay platelets. As expected, the average shape of the fine fractions was smaller than the bulk material, but a more elongated shape was present in the purified material. Mainly due to sample density, the pore structure was noticeably different for the Na form of purified bentonite at 0.7 g cm–3 density, but at higher degrees of compaction, no significant differences were noted between the samples. The laboratory results obtained in this study could be useful for safety and performance analysis of this high-level waste repository where sodium bentonite is used and is expected to change its charge-compensating cation composition during the repository's lifetime. Microstructural data may be used in modelling of diffusion and sorption by surface complexation modelling, for example, or as a basis for mechanical and water transport models.

The present work describes the removal of Direct Red 81, Methyl Orange, Methylene Blue and Crystal Violet from aqueous solution using halloysite nanotubes. The clay mineral was physicochemically characterized using various methods. The influences of pH, interaction time, initial dye concentration, adsorbent amount and temperature on adsorption were monitored and interpreted. Although previous work has shown that acidic pH conditions favour the adsorption of pollutants from aqueous systems by clay materials, in this study maximum removal was possible over a wide range of pH conditions (pH ≥2–12). Adsorption was very rapid, and equilibrium was attained within 30 min. For all four dyes studied, chemical reaction seemed significant in the rate-controlling step, and the pseudo-second-order chemical reaction kinetics provided the best correlation of the experimental data. Thermodynamically, the process was spontaneous, with Gibbs energy decreasing with increasing temperature. Halloysite would be suitable for removing dyes from aqueous solution. This was further tested by using the halloysite nanotubes for the removal of complex dyes from printing and ink industry effluents.

In a high-level radioactive waste repository, bentonite may react with the alkaline solution produced by cement degradation. In this study, bentonite was mixed with alkaline solution in a closed system and reacted for 3–24 months. Furthermore, swelling tests were conducted on the alkaline-dissolved bentonite immersed in distilled water. The swelling deformation decreased significantly with increases in the concentration of NaOH solution and reaction time, and this was mainly due to montmorillonite dissolution. The fractal e–p relationship (e is the void ratio and p is the vertical pressure) with two calculation coefficients (the swelling coefficient and the fractal dimension) was employed to determine the swelling of alkaline-dissolved bentonite. The fractal dimension increased slightly with increasing reaction time or concentration of NaOH solution, as the dissolution traces caused by the alkaline solution favoured an increase in the irregularity and fractality of the bentonite surface. The swelling coefficient decreased linearly with decreasing montmorillonite content. In addition, the swelling coefficient and the fractal dimension were related exponentially to the reaction time in alkaline solution. A relationship between the swelling of alkaline-dissolved samples and the reaction time was proposed, which might be used to assess the swelling properties of bentonite barriers that would be affected by long-term dissolution of the alkaline solution in a closed repository.

Bentonite clay is often included as a buffer, backfill and/or sealing material in designs for deep geological repositories for radioactive wastes. It is expected that bentonite materials may undergo some mineralogical alteration as they interact with in situ groundwaters over long timescales on the order of thousands to millions of years. Long-term modelling of these materials is therefore important in order to demonstrate confidence that the engineered designs will continue to perform as required over their intended lifetimes (required assessment timescales can be up to 1 million years). The key geochemical processes that must be considered in such modelling are mineral dissolution and precipitation and cation exchange. These processes are expected to occur simultaneously and so modelling of their coupled effects and their rates (kinetics) is necessary. Illustrative reactive-transport models of the geochemical alteration of montmorillonite (the primary mineral in bentonite exhibiting cation exchange) are presented which demonstrate that one possible approach to fully coupling cation exchange and clay mineral dissolution kinetics, referred to here as the ‘all-component coupling’ approach, may lead to unrealistic behaviour due to feedback that may occur in the formulation. This feedback can be avoided if a ‘common-component’ conceptual model for the dissolution of exchanger end members is adopted, where only the saturation of the exchanger ‘structural unit’ is considered when evaluating the potential for dissolution of the mineral. Such considerations have been proposed historically in stability analyses for montmorillonite, but have not been explored widely in the modelling literature.

There is growing interest in the use of natural materials as alternatives to medicinal products composed of chemicals. For this reason, it is important to study materials which fill this need (e.g. the formulation of peloids). Historically, the Azores archipelago has long been visited for its mud baths, mainly on São Miguel Island, where volcanic muds demonstrate beneficial properties. The volcanic muds are scarce, however. Thus, residual clay materials of Santa Maria Island were studied to assess their suitability for the formulation of peloids. The results of tests from 20 samples, collected from all over the island, presented evidence that they are very favourable for peloid formulations, due to their mineralogical, chemical and technological properties. The materials showed good potential for blending with the São Miguel volcanic muds. The deposits studied show extensive outcrops.

Modelling of experimental X-ray diffraction (XRD) patterns is used to determine the phase composition of partially dehydroxylated kaolinite samples. To identify unambiguously the presence of two or three phases in the heated kaolinite samples, the full range of their XRD patterns has to be analysed. Two different kaolinites, from Imerys (UK) and from Georgia (USA; KGa-21), were studied. The heating temperatures were selected to cover the entire range of dehydroxylation for both kaolinites (400–550°C for Imerys and 400–495°C for KGa-21). Two different dehydroxylation pathways were observed. At each stage of partial dehydroxylation, the kaolinite from Imerys consisted of the original, non-dehydroxylated kaolinite and of a fully dehydroxylated phase, metakaolinite. During partial dehydroxylation of kaolinite KGa-21, each product formed at a given heating temperature consisted of three phases: the original kaolinite; a dehydroxylated phase, metakaolinite; and a phase with diffraction features corresponding to a defective kaolinite-like structure. To determine the content of metakaolinite in a partially dehydroxylated specimen, its experimental XRD pattern was reproduced by the optimal summation of the diffraction patterns of the initial kaolinite and metakaolinite. A procedure that reveals the basic diffraction features of the third phase is suggested. The XRD patterns and thus the structures of the metakaolinites formed after dehydroxylation of the Imerys and KGa-21 samples differ substantially. The conventional determination of the initial kaolinite and metakaolinite contents in partially dehydroxylated kaolinite based on the analysis of basal reflections and weight losses may lead to overlooking the formation of the intermediate phases.

This study examines the leaching of aluminium from calcined kaolin (metakaolin) with citric, oxalic and lactic acid and binary combinations of these organic acids. The investigated parameters were the pulp density, acid concentration, pH, agitation speed, temperature and contact time. The kinetics of aluminium dissolution from metakaolin in binary organic acid mixtures were determined and scanning electron microscopy examination and energy-dispersive spectrometry mapping of Si and Al of untreated kaolin and residual solids were also carried out. Aluminium dissolution increased with temperature, time, acid concentration, pulp density and acidity. At maximum dissolution, citric–oxalic (1:4 w/w) and lactic–oxalic (1:4 w/w) mixtures dissolved 77% and 78% aluminium, respectively, from metakaolin in 11 h. The activation energy ranged from 57.8 to 74.6 kJ/mol. The most effective parameter in the dissolution of aluminium was the temperature, indicating that the reaction was not diffusion-controlled. It was concluded on the basis of the activation energy values and the sensitivity of the reaction to temperature that the dissolution was under chemical-reaction control.

Three samples of bulk smectite clay from the Pilori and Velanida bentonite deposits of the Ventzia basin, western Macedonia, Greece, were characterized in detail. Chemical analyses and X-ray diffraction (XRD; Rietveld method) showed that the samples are rich in Fe and Mg (8–13 mass% and 6–10 mass% as oxides, respectively) and contain ~60–65 mass% smectite. The high Fe and Mg content as well as the high Cr (0.3–0.5 mass%) and Ni content (0.1–0.3 mass%) are consistent with the formation of these clays from ultramafic precursor sediments of the Vourinos ophiolite complex. Both XRD and infrared spectroscopy indicate the presence of other clay minerals besides smectite, such as minor amounts of kaolinite, trioctahedral-rich palygorskite, serpentine and talc (depending on the sample). The position of the d060 reflection (1.51–1.52 Å) is compatible with either high Fe content or partial trioctahedral character, or probably both. The predominance of ferruginous smectite or nontronite was confirmed by infrared spectroscopy, but the minor presence of a trioctahedral magnesian smectite in some of the samples cannot be excluded. Layer charge densities, determined by the νO-D (oxygen-deuterium IR-stretching) method calibrated against the structural formula method, are in the 0.48–0.52 eq/FU range. Various methods point to the existence of a significant amount of tetrahedral charge, which is typical of ferruginous smectites. The major exchangeable cation is Mg2+ (73–90%), which represents a special property of these materials compared with other bentonites.