A clinoptilolite was exposed to treatments with acid and base solutions that caused desilication, dealumination or a combination of both. The mineralogical and physicochemical properties of clinoptilolite were studied by X-ray diffraction, X-ray fluorescence, Brunauer–Emmett–Teller specific surface area, differential thermogravimetry, Fourier-transform infrared spectroscopy and scanning electron microscopy methods. The studies provided insight into the structural and textural properties of the treated zeolite. The applied post-synthesis modification techniques proved to be effective for the generation of secondary mesopores.

The Numidian Aquitano-Burdigalian nappe from the Jijel region (northeast Algeria) shows an important clay-rich basal series. In this study, seven representative clay samples were collected from the Djimla and El-Milia areas of this region in order to analyse their mineralogy using X-ray diffraction and Fourier-transform infrared spectroscopy, chemical composition by X-ray fluorescence, particle size, plasticity, morphology by scanning electron microscopy and their ceramic properties. Samples were prepared by pressing the clays and firing them at 800–1100°C, and bulk density, water absorption, linear firing shrinkage, weight loss and bending strength values were determined on the fired samples. The clays are mainly composed of kaolinite and illite, with a small amount of 10–14 Å interstratified clay minerals and chlorite, associated with quartz and feldspars. The main oxides in the samples were SiO2, Al2O3 and Fe2O3. The clays may be classified as moderately plastic according to their Atterberg limits. Ceramic tiles have been produced by dry pressing. At all tested firing temperatures, the clays present the required standard values for linear firing shrinkage, weight loss, bulk density, water absorption and bending strength, and they are defect-free. The main transformations were observed at 1000°C with the appearance of new crystalline phases. The measured technological properties of the investigated deposits confirm that the Numidian clays from the Djimla and El-Milia regions are suitable materials for the production of high-quality structural ceramics.

Illitic clay from the locality of Liepa, Latvia, was investigated using dynamic thermomechanical analysis during the heating and cooling stages of firing. Differential thermal analysis, thermogravimetry, thermodilatometry, X-ray diffraction and porosimetry were also performed to shed light on the processes influencing the elastic properties of clay. The increase in the Young's modulus (YM) at low temperatures was linked to the release of physically bound water. Above 850°C, the bulk density and YM both increased as a consequence of sintering. The YM was more sensitive to the progress of sintering compared to dimension changes. The YM values continued to increase during cooling until the glass-transition temperature was reached. At this temperature, the first microcracks caused by the differences in thermal expansion coefficients of the present phases were expected to appear. The YM showed a sharp V-shaped minimum at the β → α transition of quartz, which was a result of alternation of the mechanical radial stresses around the quartz grains. When the transition of quartz was completed, the YM continued to decrease because microcracks were still being created at the boundaries between the different phases. The decrease of the YM during cooling from the glass-transition temperature down to room temperature was ~50% for all of the firing temperatures and isothermal periods applied.

Two preferred textures were observed in the Alhama de Murcia Fault rocks: (a) foliated bands (>100 µm thick) rich in well-crystallized dioctahedral micas, quartz, hematite and dolomite; and (b) ultrafine-grained bands (<100 µm thick) made of patches composed of small mica crystals (<15 µm) and dispersed Fe-oxides. In both textures, kaolinite forms intergrowths or patches of randomly oriented crystals filling gaps or opening layers of presumably inherited detrital mica crystals, which is interpreted as an epitaxial growth from fluids. The Na/K ratio of mica crystals in the thin ultrafine-grained bands shows a wider range than the micas from the foliated bands including muscovitic, intermediate Na/K and paragonitic compositions. The absence of the 0.98 nm intermediate peak in the diffractograms indicates that the small micas are submicroscopically paragonite and phengite intergrowths. The d001 values of the K-dioctahedral micas in the <2 µm and whole fractions are clearly different from each other. The d001 values of micas of the <2 µm fraction are larger, indicating a higher K and lower Na content in the small micas. Their composition corresponds to lower temperatures, suggesting their growth during a genetic episode in the fault. The textural relationships indicate a late growth of kaolinite, probably due to the fluid–rock interaction along fault planes and fractures. The neoformed clay minerals might alter the stability of the fault plane. The absence of expandable clay minerals and the relatively high frictional strength of kaolinite under wet conditions might explain the observed velocity-neutral behaviour of this gouge and earthquake propagation towards the surface.

Clay mineral ‘Crystallinity Index Standards’ (CIS) composed of Palaeozoic mudrocks from southwest England were investigated systematically in five sub-fractions per sample for the first time. X-ray diffraction was used to determine mineral assemblages, calibrated 001 illite full-width-at-half-maximum (FWHM) values and illite polytype compositions, in addition to K–Ar isotopic analyses of all fine fractions. The FWHM results of the <2 µm fraction are consistent with previous studies and reflect the range of diagenetic to epizonal grades covered by the sample set SW1 to SW7 (~0.61–0.26°2θ). Diagenetic and lower anchizone samples also show significant broadening of 001 illite reflections in the finer fractions and contain mixtures of authigenic 1M + 1Md illite and detrital 2M1 white mica polytypes suitable for illite age analysis. The estimated end-member ages of the Bude (SW1-1992) and younger Crackington (SW3-2000) mudstones yield detrital ages of Late Cambrian to Middle Ordovician (493–457 Ma) and a broad range of 1M + 1Md illite ages between Middle Permian and Early Jurassic (271–190 Ma). The detrital age of the stratigraphically older Crackington Formation mudrock (SW2-1992) is Late Devonian (384–364 Ma) with 1M + 1Md illite ages between Late Triassic and Early Jurassic (219–176 Ma). The origin of Mesozoic 1M + 1Md illite ages may represent neocrystallized illite associated with Mesozoic hydrothermal events or similar events that thermally reset older authigenic illite with partial loss of radiogenic argon and no renewed crystal growth. In contrast, upper anchizonal and epizonal Devonian slates (SW3-2012, SW4-1992, SW6-1992 and SW7-2012) contain only the 2M1 polytype, with K–Ar ages younger than the stratigraphic age. The three finest fractions of SW4-1992 yield consistent Late Carboniferous ages (331–304 ± 7 Ma) that are considered to date the neocrystallized 2M1 mica. Most fractions of epizonal slate (SW6-1992, SW7-2012) yield Early Permian ages (293.6–273 Ma) corresponding to published cooling ages of the Tintagel High-Strain Zone and the intrusion of the Bodmin granite (291.4 ± 0.8 Ma). These first K–Ar age constraints for the fine fractions of the CIS should provide useful reference values for testing analytical procedures of illite age analysis.

Expanded vermiculite with excellent thermal and chemical stability was investigated as a reliable sorbent for hazardous liquid spillages, including those leading to fire and explosion risks. Many expanded samples were prepared by rapid heating using both different temperatures and dissimilar vermiculite dimensions. Their capabilities for hazard clean-up were correlated with the structural characteristics of expanded vermiculite with slit-shaped porosity. When using optimized vermiculite, the moderate sorption capacities of 1.5–3.0 g g−1 were obtained for various hazardous chemicals, including hydrophilic/hydrophobic organic chemicals and strongly acidic/basic solutions. The sorption capacities depended more strongly on physical properties, such as the pore volume of the sorbent and the density of the absorbed liquid, rather than the vermiculite's chemical composition. The void space interconnected by interparticle/intraparticle pores worked as imbibing pathways due to their capillarity, resulting in the rapid, spontaneous sorption of hazardous chemicals. The hazardous chemicals may be removed from a testing vessel via sorption with an efficiency of >94 wt.% for 10 min. These results demonstrate that the expanded vermiculite may be a potential candidate as a reliable general-purpose sorbent for hazardous materials clean-up under harsh conditions.

A natural clinoptilolite nanostructure (CNS) along with ultrasonic irradiation was used to remove Cu2+ ions from polluted water. In the first part of this work, natural clinoptilolite was converted to CNS by ball milling. The natural clinoptilolite and prepared CNS samples were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction, N2 adsorption/desorption and pH at the point of zero charge analyses. The SEM images showed the development of CNS from natural clinoptilolite by ball milling. The N2 adsorption/desorption and FTIR spectroscopy confirmed the greater specific surface area, pore volume and number of surface groups of the CNS compared to the natural clinoptilolite. In addition, the crystalline phase of the CNS was the same as the natural clinoptilolite. In the second part of this work, the ultrasonic-assisted sorption of Cu2+ ions from polluted water by CNS was investigated. These experiments were optimized with response surface methodology based on central composite designs. The effects of initial pH of solution, CNS dosage, sonication time and temperature on Cu2+ ion-removal efficiency were investigated. By using a CNS dosage of 500 mg L−1, an initial pH of 6, a sonication time of 12 min and a sonication temperature of 45°C as optimal conditions, 97% of Cu2+ ions were removed from contaminated water. The initial pH was the most effective variable. Ultrasonic-assisted sorption of Cu2+ was more effective than sorption alone, onto the CNS.

The isomerization of limonene over natural the zeolite, clinoptilolite, was studied. The main products of limonene isomerization were terpinolene, α-terpinene, γ-terpinene and p-cymene. These products have numerous applications in the cosmetic, food and pharmaceutical industries. The main parameters affecting limonene isomerization were reaction time, temperature and catalyst content. These parameters varied within the following ranges: reaction time 15–1440 min; temperature 155–175°C; and catalyst content 5–15 wt.%. Terpinolene was obtained after reaction for 60 min at 175°C using 10 wt.% catalyst. p-Cymene was produced using similar conditions as for terpinolene except for a longer reaction time of 1440 min. The use of optimum experimental conditions allowed the greatest amounts of the desired products to be obtained in the shortest time.

This work examines a tuff from the Tinebdar deposit located in Sidi Aich (east Algeria) for possible use as an alternative material for the adsorption of Asucryl red (a textile dye). Natural tuff represents an economic and environmentally friendly alternative compared to synthetic zeolites. The starting materials were characterized by means of powder X-ray diffraction, Brunauer–Emmett–Teller-specific surface area and pore diameter analysis. Batch experiments were performed and various parameters that have an effect on the adsorption process (i.e. pH, clay amount, contact time and initial concentration) were investigated. The <125 μm grain-size fraction of the tuff contains 45 wt.% mordenite. The adsorption equilibrium was established in 10 min and the adsorption kinetics were better described by the second-order kinetic model. The adsorption isotherm of the results obtained fits better to the Langmuir and Timkin models. The adsorption capacity qt varies from 60 to 70 mg g–1 with temperature increasing from 293 to 333 K. The thermodynamic nature of the adsorption process was determined by calculating ΔH°, ΔS° and ΔG° values. The positive value for ΔH° confirms that the adsorption is endothermic.

Nitrogen influx was identified in the Harghita Bãi area, where the mechanism of NH4+-fixation in illitic clays is relevant for the N-input budget estimation. The nanotextural features of K-illite (K-I), NH4,K-I and NH4-illite-smectite (NH4-I-S) mixed layers observed in argillic-altered andesitic rocks from the hydrothermal area of Harghita Bãi (East Carpathians) were studied by X-ray diffraction, infrared spectroscopy and transmission and analytical electron microscopy (TEM-AEM). The texture of undisturbed argillic-altered andesite rocks exhibits chaotic intergrowths of randomly oriented and curved illitic packets with abundant pore spaces and high porosity between packets. The TEM images of K-I and NH4,K-I intergrowths show subparallel packets with clear contacts, exhibiting a diffuse contrast across layers. The thicknesses of K-I and NH4,K-I packets range from 150 to 500 Å, and 1Md and 1M polytypes were identified by selected area electron diffraction patterns. Crystal chemistry of K-I, NH4,K-I and NH4-I-S was carried out by AEM. A third interlayer cation Na+ beside K+ was detected in several NH4,K-I packets. The NH4,Na,K-I packets interleaved with NH4,K-I or NH4-I-S (12% smectite layers) packets were also identified by TEM. The thicknesses of NH4,Na,K-I packets range from 300 to 1200 Å, with abundant lenses and lenticular layer separation along the boundaries between them. The 1Md polytype dominates the NH4,Na,K-I packets. Straight and parallel packets, continuous 00l layers and collapsed swelling layers at the boundary of individual NH4-I (5% smectite layers) packets with thicknesses ranging from 20 to 95 Å were observed. The nanotextural observations indicate direct crystallization of NH4-I crystals within a NH4-I-S series from a pore fluid, where NH4-I packets occupy void spaces previously occupied by fluids.

This research aims to characterize the mineralogical and crystal-chemical purity of two samples of natural talc (BTT6, BTT7) from the occurrence ‘Ecole1’ in the deposit of Minzanzala, southwest Gabon. X-ray diffraction and modal-composition calculations demonstrated the presence of quartz and Al–Fe-bearing phases (kaolinite and/or chlorite and/or Al–Fe oxyhydroxides) as accessory minerals in both ores. In contrast, the chemical and spectroscopic characterization of the talc component revealed remarkable chemical purity expressed by very low Fe contents. According to these results, the talc of Minzanzala might be used as a filler in a wide range of industrial applications, such as in cosmetics, paints, polymers or ceramics.

Iran has significant deposits of high-purity natural zeolites. Many Iranian scholars conduct scientific research on porous materials, from natural and synthetic zeolites to metal organic framework materials. Iranian zeolite deposits and associated research are reviewed here. Various industrial applications of natural zeolites, from agriculture to animal husbandry to the construction industry and beyond are discussed here.

Early Copper Age pottery sherds discovered in a cave within the crystalline dolomites of the Southern Carpathians (Romania) were investigated by polarized light optical microscopy (OM), X-ray powder diffraction (XRPD) and electron microprobe analysis (EMPA) to obtain information on the pottery production in the Copper Age in the territory of present-day Romania. Microscopically, the clayey matrix of the ceramic body is highly birefringent or consists of low-birefringent and isotropic parts mixed together, containing fragments of quartz, muscovite, alkali feldspar, plagioclase, biotite, chlorite, heavy minerals and metamorphic and magmatic rocks, as well as an opaque material. The EMPA data revealed an Fe-rich illite-like matrix and helped to identify the mineral nature of the inclusions. Local pottery production in bonfires or surface clamps is envisaged. Miocene illitic clays may have been used as raw materials, mixed with a small amount of sandy temper. The thermal changes revealed by OM, the modification of the XRPD peaks and the EMPA data suggest firing temperatures of between 800 and 850°C.

The solvent-casting method was used to synthesize a silver–zeolite–chitosan (AgZ-Ch) composite from Philippine natural zeolites. X-ray diffraction, ultraviolet–visible (UV-Vis) spectroscopy, optical emission spectroscopy (OES), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG) were used to investigate the different properties of the composite before and after plasma treatment. The major phase of the zeolite is Na-clinoptilolite with trace amounts of mordenite, feldspar and quartz. UV-Vis and OES analyses confirmed the presence of Ag and zeolite on the chitosan matrix. The decrease in the transmittance signal at 290 nm and the emission spectra of the discharge showed the presence of Ag I, Al I and Si I signals at 705–852 nm. The TGA and DTG curves revealed the thermal stability of the natural zeolites after ion exchange and after incorporation in the chitosan matrix, where the onset of degradation was observed to occur above ~37°C, the human body temperature. Bacterial count showed minimal growth of colonies on all samples, both pristine and plasma-treated, suggesting that the surface of the composites does not influence bacterial habitation. The fabricated composites meet the minimum requirements for biomedical application such as thermal stability with respect to the average human body temperature and absence of bacteria.

A zeolite-montmorillonite (zeolite-Mt) nano-adsorbent was prepared by calcination at 600°C. The synthesized nano-adsorbent was tested for removal of a toxic and cationic dye (crystal violet) from water, and it was characterized by various techniques. The effects of variables such as pH, temperature, adsorbent dosage and initial dye concentration on the removal efficiency of the dye were investigated by response surface methodology (RSM). Experimental conditions were optimized by RSM to achieve the maximum dye removal efficiency. Optimum conditions for maximum removal of dye were obtained at pH 9, temperature of 25°C, adsorbent dosage of 2 g L−1 and initial dye concentration of 40 mg L−1. Under these conditions, the maximum removal efficiency obtained was 99.9%. Various isotherms were applied to study adsorption equilibrium, and of these, the Freundlich isotherm provided the best fit. In addition, the fractal-like integrated kinetic Langmuir model was the most appropriate among several kinetic models. The thermodynamic parameters were also determined. The zeolite-Mt prepared under optimum conditions displayed a greater adsorption capacity than activated carbon (manufactured by Merck) and than various other adsorbents.

The stability of organoclays prepared from smectites and organic cations depends on the type of used cation, among other factors. This study provides a prediction of the structure, stability and dynamic properties of organoclays based on montmorillonite (Mt) intercalated with two types of organic cations – tetrabutylammonium (TBA) and tetrabutylphosphonium (TBP) – using first-principle density functional theory. The results obtained from simulations were also used in the interpretation of the experimental infrared spectrum of the TBP-Mt organoclay. Analysis of interatomic distances showed that weak C–O···H hydrogen bonds were important in the stabilization of both TBA- and TBP-Mt models, with slightly stronger hydrogen bonds for the TBP cation. Calculated intercalation and adsorption reaction energies (ΔEint//ΔEads*/ΔEads**) confirmed that TBP-Mt structures (–72.4//–32.8/–53.8 kJ/mol) were considerably more stable than TBA-Mt structures (–56.7//–22.6/–37.4 kJ/mol). The stronger interactions of the alkyl chains of the TBP cation with Mt basal surfaces in comparison to those of the TBA cation were also correlated with the positions of the calculated bands of the C–H stretching vibrations.

The application of clay minerals in therapeutics is becoming important due to their structural and surface physicochemical properties. 5-aminosalicylic acid (5-ASA) is a very common pharmaceutical drug and is used worldwide. The interactions between the 5-ASA molecule and both the aluminol and siloxane surfaces of kaolinite are studied by means of atomistic calculations using force fields based on empirical interatomic potentials and quantum mechanics calculations based on density functional theory. A conformational analysis of 5-ASA has been performed and the anion of 5-ASA was also studied. The calculated adsorption energy values indicate that 5-ASA is likely to be adsorbed on the kaolinite surfaces with greater affinity to the aluminol surface. Hence, kaolinite may be considered as a promising pharmaceutical carrier of 5-ASA.

The zeta potential and yield-stress behaviour of gels prepared from as-received SHCa-1 hectorite (Ht) containing 50 wt.% impurities, mainly of calcite, dolomite and quartz, were characterized. The zeta potential is negative in the pH range 4–12. At pH <5, reaction of CaCO3 producing CO2 and Ca2+ increased the solution conductivity significantly and reduced the zeta potential. The buffering effect due to this chemical reaction was also observed in the yield stress–pH characterization below pH 8. Low yield stress was observed below pH 6 and above pH 12. The yield stress peaked at pH ~8, where Ht displayed a zeta potential of –20 mV. The relationship between maximum yield stress and Ht content (wt.%) was linear and was not affected by impurities. The ageing behaviour was characterized by an initial phase of rapid yield-stress increase and then by a phase of gradual increase. The Leong model performed better than the two-parameter glassy polymer ageing model in describing this ageing behaviour. However, the empirical power law model was more accurate. The timescale of the ageing process is long, lasting several days. An open cellular microstructure was observed to form in the gels. Impurities appeared not to interact with or bind to the Ht platelets.

Molecular dynamics simulations of different defective kaolinites under tension were performed to reveal the effects of defect location, type, density and temperature on their mechanical properties. Four types of defective kaolinite with Si vacancies were constructed. Based on the atomic-scale deformation and failure processes of defective kaolinite and its stress–strain curves, the Young's moduli and tensile strengths in three crystal directions were obtained and compared with the existing theoretical values from the literature. The defect location at each layer does not affect the mechanical properties of kaolinite and the cracks initiated at the defective sites. The atom density of each model was calculated in order to investigate the defect-type effect on the mechanical properties of kaolinite. The simulation results also showed that kaolinite exhibits brittle failure behaviour and the mechanical properties degrade significantly with increasing defect density and temperature. The influence of temperature on the mechanical properties of defective kaolinite is discussed in detail.

This study focuses on the mineralogical characterization of four raw clay samples from Dobrodo deposit, Serbia. Several analytical methods were applied to determine the chemical and mineralogical composition, morphology and physical properties (colour, plasticity, specific surface area, particle size and cation-exchange capacity) of the clay samples. Kaolinite, smectite and illite are the predominant phases in all of the samples studied that contain between 60.2 and 87.1 wt.% of clay. Quartz, feldspars, paragonite and Ti- and Fe-bearing phases were also identified. The relatively high SiO2/Al2O3 mass ratio indicates abundant quartz. The cation-exchange capacity of the samples varied between low and moderately charged clay minerals (12–52 mmol 100 g–1) with specific surface area values ranging from 94 to 410 m2 g–1. The plasticity index values (11–23%) suggest low to moderate plasticity. Preliminary results show that most of the raw clay from Dobrodo deposit might be suitable for use in ceramic applications.