Sodium montmorillonite and pyridine form a regular complex of spacing 23·3 kX in the presence of traces of moisture. The minimum interlamellar composition necessary for the formation of the complex is approximately Na+ (C5H5N)4 (H2O)2. The intensities of the 00l reflections are considered incompatible with the complex having a five layer structure and an alternative arrangement is proposed.

The crystalline swelling of sodium and potassium montmorillonites immersed respectively in solutions of sodium and potassium chloride of different concentration exhibits hysteresis in the swelling-contraction cycles. The position and extent of the hysteresis can be varied by altering the method of preparation of the clays; in all cases the hysteresis loops for potassium montmorillonite were more extensive than those for sodium montmorillonite.

The results have been explained in terms of a structural rigidity of montmorillonite crystals, where the crystals consist of five to ten aluminosilicate sheets (lamellae). The extent of hysteresis depends on this rigidity, which varies in a co-operative manner with the spacing between the lamellae in the crystal.

Electrical interactions between pairs of lamellae are also considered in analysing the swelling behaviour.

The changes in X-ray diffraction patterns of layer silicates which result from dry heat-treatments below 550°C have been studied and the results are tabulated in order of increasing temperature at which these changes are observed; the structural implications are briefly considered. In order to evaluate the effects of composition, particle size and disorder, synthetic clay minerals have been used in addition to natural clays. This summary of X-ray data may be of value in the identification of clay minerals in mixtures.

Iron cations in the octahedral sheet are a disadvantage to the industrial application of palygorskite clays. In this study, a palygorskite sample from eastern China (Mayaoshan deposit, Jiangsu Province) is shown to have an Fe content that is much greater than usual. The structural formula of the Fe-rich palygorskite sample was established as (Si7.48Al0.52) (Al1.24Fe0.94Mg1.77Ti0.03⁏1.02)O20(OH)2(OH2)4. The palygorskite is seen to be dioctahedral according to the structural formula, consistent with Fourier transform infrared data. Occurrences of AlFe3+ɏOH and Fe3+Fe3+ɏOH vibrations in the OH-stretching and -bending regions show that Fe atoms occupy inner sites of octahedral sheets. A Mössbauer spectrum confirmed that Fe ions occupy inner octahedral sites as trivalent Fe cations (Fe3+).

Specimens of palygorskite from Warren Quarry, Enderby, Leicestershire, have been studied in the laboratories. The mineral is found in dioritic rocks in association with angular dolomitic rock fragments as the filling material of a joint, the walls of which are sometimes lined with calcite and dolomite. Palygorskite occurs as 3-10 mm long bundles of fibres, 0·03-0·1 μm wide. X-ray diffraction data indicate that the mineral may occur in the monoclinic form. The structural formula for the half-unit cell is Si8(Al1.89Fe0.053+Ti0.01Mg1.99)O20(OH)2(OH2)4 3·61 H2O.Ca0.07. Data obtained from differential thermal and infrared analyses are comparable with those for palygorskite in the literature, but the six-sided transversal cross-section of the fibres as revealed by electron microscopy is unexpected. The mineral was formed after the deposition of the overlying basal Triassic rocks when ground waters penetrated cracks in the dioritic rocks, causing Si and Mg to be released there and above the unconformity.

A semi-quantitative mineralogical analysis of colliery spoil by XRD has been developed and used to compare spoils from eight collieries, in connection with work on the production of synthetic dense aggregates from spoil. Phase analysis of clay, which constitutes over half of all these spoils, is carried out by comparing X-ray peak areas of oriented specimens after heating and treatment with ethylene glycol. Total clay is obtained by difference, after determination of quartz and other minerals by an internal standard technique, allowing calculation of the proportion of each clay mineral. The results are tested against chemical analysis and a semiquantitative X-ray analysis of the chlorite present indicated that it is a highly ferruginous variety. Differences are detected in the mineralogy of all eight spoils but, except for the predominance of kaolinite in the spoils from Scotland, these differences are small.

Microprobe and atomic absorption analyses of large vermiculite crystals present in the upper horizon of a weathering profile on gabbro show that they differ appreciably in chemical composition. This together with the lack of any phyllosilicate precursor of comparable grain size, strongly suggests that the vermiculites were formed by precipitation of dissolved silicate matter, higher in the profile the vermiculite becomes unstable and is replaced by an Fe-rich smectite.

The reactions of ten C6-alkenes over a Cu2+-montmorillonite catalyst have been examined between room temperature and 100°C. The reaction products depend upon inter alia the branching in the alkene, the position of the double bond, and the temperature. Hex-2-ene, cis and trans-4-methyl-pent-2-ene and 4-methyl-pent-1-ene do not react at all, whereas 2-methyl-pent-1-ene and 2-methyl-pent-2-ene and 3,3-dimethyl-but-1-ene form alcohols below ∼40°C and dimers at higher temperatures. Hex-1-ene forms the di-2,2′-hexyl ether.

The potential of platy nanofillers like clays in polymer nanocomposites is mostly determined by their aspect ratio. The degree of improvement that may be achieved in respect to reinforcement, gas-barrier properties and flame retardancy critically depends on the aspect ratio. Thus, increasing the aspect ratio is highly desirable in order to explore the full potential of the clay filler. Mechanical shear stress as generated in the grinding chamber of a stirred media mill (ball mill) induced an efficient exfoliation of highly hydrated and therefore ‘shear-labile’ synthetic Mg-fluorohectorite in aqueous dispersion. The attainable degree of exfoliation can be tuned and controlled through the shear forces applied by changing process parameters such as solid content and grinding media diameter. Characterization and evaluation of the exfoliation efficiency during milling was achieved by combining and cross-validating data obtained by powder X-ray diffraction (XRD), static light scattering (SLS), specific surface area measurements applying the Brunauer-Emmett-Teller (BET) equation, and scanning electron microscopy (SEM). This led to the identification of optimal processing parameters, allowing for control of the degree of exfoliation and, consequently, the aspect ratio of the nanoplatelets. Not surprisingly, besides exfoliation, increasing the magnitude of the shear stress also resulted in some reduction in platelet size.

The clay platelets obtained showed a high average aspect ratio (>600), several times greater than that of original synthetic fluorohectorite. The increase of aspect ratio was reflected in a significant enhancement of both specific surface area and cation exchange capacity (CEC) of the external basal surfaces. This method has substantial advantages compared to microfluidizer processing with respect to feasibility, batch size and particle diameter size preservation. The exfoliated nanoplatelets obtained by milling have great potential to improve mechanical properties of polymer layered silicate nanocomposites (PLSN).

A kaolin clay was activated with 1.0 M H2SO4 solution at minimum liquid to solid ratio (L/S) using microwave heating. The optimum experimental conditions for activation were L/S ratio 3.0 mL 1 M H2SO4 per gram kaolin, microwave input power 500–600 W, and heating time 5–10 min. Activation at L/S < 3.0 mL/g using 1.0 M H2SO4 was not efficient, indicating the influence of solvent for absorbing microwaves more intensively and thus improving activation. Significant physicochemical changes were observed by the proposed procedure with smaller volumes of activator compared to the conventional heating method. Microwave input power and heating time have a strong influence on the quality of the final material; activation at high input power (>700 W) and longer heating times (>10 min.) are not recommended since they cause dissolution of kaolinite structure. Microwave-heated kaolin manifested better adsorption for tartrazine dye due to improvements in textural and chemical properties of kaolinite. Moreover, irradiation of used kaolinite has significantly improved dye desorption, increasing the importance of microwaves in regeneration/recycling studies. Detailed dielectric measurements of kaolin-acid mixtures recorded at frequencies much lower than 2.45 GHz revealed that absorption of radiation is highly dependent on the activator solution in the mixture. For 3.0 mL/g mixtures, high dielectric constant ε’ 5223, dielectric loss factor ε” 5083, tangent loss tan d 1.30, penetration depth dp 0.57 cm at (103 Hz), and AC-conductivity σ 0.032 Om–1 were determined at 105 Hz. Filling the pores of kaolin by acid solution increased the microwave absorption and hence de-alumination of kaolinite.

Transmission powder patterns of random and of highly oriented samples of natural micas have been recorded and compared with those calculated from structural data with the aid of the DIFK computer program modified to correct for preferred orientation. Intensities calculated from structural data for random and for highly oriented samples (symmetrical and oblique settings) are presented for 1M, 2M1, 2M2, 3T polytypes of muscovite, 1M, 2M1, 3T polytypes of paragonite and 1M (C2/m and C2 space groups), 2M1, 2M2, 3T polytypes of lepidolite.

In situ migration experiments using different radiotracers have been performed in the HADES Underground Research Facility (URF), built at a depth of 225 m in the Boom Clay formation below the SCK–CEN nuclear site at Mol (Belgium). Small-scale experiments, mimicking laboratory experiments, were carried out with strongly retarded tracers (strontium, caesium, europium, americium and technetium). Contrary to europium, americium and technetium which are subjected to colloid mediated transport, the transport of strontium and caesium can be described by the classic diffusion retardation formalism. For these last two tracers, the transport parameters derived from the in situ experiments can be compared with the laboratory-derived values. For both tracers, the apparent diffusion coefficients measured in the in situ experiments agree well with the laboratory-derived values.

In the large-scale experiments (of the order of metres) performed in the URF, non-retarded or slightly retarded tracers (HTO, iodide and H14CO3–) were used. The migration behaviour of these tracers was predicted based on models applied in performance assessment calculations (classic diffusion retardation) using migration parameter values measured in laboratory experiments. These blind predictions of large-scale experiments agree well in general with the experimental measurements. Fitting the experimental in situ data leads to apparent diffusion coefficients close to those determined by the laboratory experiments. The iodide and H14CO3– data were fitted with a simple analytical expression, and the HTO data were additionally fitted numerically with COMSOL multiphysics, leading to about the same optimal values.

The Cu,Cr-, Zn,Cr- and Cu,Al-layered double hydroxides have been synthesized by the coprecipitation method and characterized by elemental analysis, PXRD, SEM/EDS and BET. The mixed oxide materials obtained upon calcination at 873 K show very high catalytic activity for the combustion of toluene and ethanol. The best sample is derived from the Cu,Cr-LDH precursor with a Cu:Cr ratio of 2, composed of copper oxide and copper chromite. This catalyst gave 50% conversion of toluene and ethanol at temperatures of 45 and 15 K lower, respectively, than the reference commercial catalyst. Catalytic tests with a mechanical mixture of CuO and CuCr2O4 demonstrate that the use of an LDH precursor is essential for optimum results. The importance of the simultaneous presence of both Cu and Cr, the influence of the Cu:Cr ratio on the catalytic activity and the role of the interface boundaries in the CuO-CuCr2O4 mixed oxide system are discussed.

This study aims to find alternatives to some overexploited deposits in the north of Tunisia. The clays of the Sidi Khalif formation, of Uppermost Jurassic to Lower Cretaceous age, seem suitable to support this strategy, due to their abundance. In terms of mineralogy, they can be divided into two distinct groups, related to their palaeogeographic and eustatic contexts. The clays of the Sidi Khalif formation from Jebel Houareb (JH) and Jebel Meloussi (JM) are richer in clay minerals, while those of Jebel Rhouis (JR) and Jebel Boudinar (JB) zones are dolomite-rich. The compositional differences between the two groups influenced their technological behaviour in production of ceramic tiles. Upon firing, forsterite and gehlenite crystallized in the carbonate-rich JR and JB clays, whereas mullite formed in the JH and JM clays. Concerning their ceramic properties, the tiles made from JR or JB clays showed low bending strength and high water absorption. For JH and JM, the tiles had slightly greater mechanical resistance, but exhibited considerable linear shrinkage. These defects were partially corrected by introducing new formulations based on the same clays and by altering the firing cycles (HM1, HM2, RB1 and RB2). With these modifications, “Porcelanico” and “Monoporosa” technologically conforming tiles were obtained from HM2 and RB2 formulations, respectively.

Silylated kaolinites were synthesized at 80°C without the use of inert gas protection. The method presented started with mechanical grinding of kaolinite, followed by grafting with 3- aminopropyltriethoxysilane (APTES). The mechanical grinding treatment destroyed the ordered sheets of kaolinite, formed fine fragments and generated broken bonds (undercoordinated metal ions). These broken bonds served as new sites for the condensation with APTES. Fourier transform infrared spectroscopy (FTIR) confirmed the existence of −CH2 from APTES. 29Si cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy (29Si CP/MAS NMR) showed that the principal bonding mechanism between APTES and kaolinite fitted a tridentate silylation model (T3) with a chemical shift at −66.7 ppm. The silane loadings of the silylated samples were estimated from the mass loss obtained by TG-DTG curves. The results showed that the 6-hour ground kaolinite could be grafted with the most APTES (7.0%) using cyclohexane as solvent. The loaded amount of APTES in the silylated samples obtained in different solvents decreased in the order as: nonpolar solvent > polar solvent with low dielectric constant (toluene) > polar solvent with high dielectric constant (ethanol).

The proposed impact event at the end of the Cretaceous resulted in mass extinctions and subsequently significant variations in the geochemical and mineralogical composition of the sediments marking the K/T boundary. The impact-generated material derived from target rocks produced the ejecta layer deposits around Chicxulub crater, which were subsequently diagenetically altered to mainly smectite in marine sections and to kaolinite in continental sections. The fireball layer represents the cosmic dust dispersed and deposited globally and contains smectite derived from the alteration of microkrystites and the finest fraction. The lowermost Danian clay layer, recognized in marine sections, resulted from the sudden decrease in ocean productivity and represents a reduced sedimentation deposit. Its clay mineral associations depend on local environmental conditions and diagenetic processes. Overall, the diagenetic alteration of the boundary materials resulted in a significant modification of original signatures. The composition of the clay mineral phases can, however, still be evidence of the nature of the precursor materials providing evidence for an extraterrestrial impact event.

Ten raw materials, typical of those used by the majority of British manufacturers of structural clayware, are shown to cover a wide range of mineralogical composition. Kaolin, mica minerals and quartz are always present, though their relative percentages vary widely. Other minerals which may be present in more than trace amounts, are montmorillonite, dolomite, calcite, sepiolite and chlorite. The correlation between the mineralogy of a raw material and its physical characteristics is reasonably good; the presence of montmorillonite, in particular, can have a marked effect. The importance, however, of the degree of compaction of the raw material (largely a function of geological age) is emphasized. Variations in clay mineralogy appear to affect firing behaviour less than variations in the content of alkaline earths, where present.

Precise identification of clay minerals found in granular rocks has always posed a great problem to the clay petrographer. Even if it is possible to locate the position of authigenic clay mineral formation in a thin section, subsequent identification of this same material by X-ray diffractometry is usually very difficult. Attempts have been made using selected-area radiation of thin sections (Pawluck & Dumanski, 1973; Wicks & Zussman, 1975; Wilson & Clark, 1978) but the area analysed remains relatively large, i.e. of the order of several mm2. The other solution is micro-picking of material from a thin section and subsequent identification by Debye-Scherrer camera methods (Wallace, 1955; Rickwood, 1977). This method, however, does not allow preferred orientation, and thus precise identification, of many clay species. The ideal method is to combine micro-picking from thin sections from areas of several hundreds of square microns with an oriented sample preparation, which can then be treated in the traditional way (glycolation, heating, etc.) for characterization by X-ray diffractometry.

Smectites of sedimentary series from a playa lake system from Calatayud Basin have been studied by XRD and TEM chemical microanalyses. Clay particle microanalyses show complete continuity between dioctahedral aluminous and trioctahedral magnesian smectites. Aluminous smectites have been classified as montmorillonites and ferribeidellites, both with compositional variability. They represent detrital phases resulting from weathering in the source area. Compositionally-intermediate smectites (beidellite-saponite and montmorillonite-stevensite) seem to correspond to weighted mean compositions of di- and trioctahedral phases stacked together in the same particle. They represent intermediate transitional stages from detrital to authigenic smectites in more distal basin facies. Trioctahedral smectites, although called saponites and stevensites, are actually random mixed-layer kerolite-Mg-smectite with a high percentage of expandable layers. They represent authigenic clays formed from solutions with high pH and Mg content as a result of evaporative concentration. The variability in composition of smectites, both within the same sample and amongst different samples, is a possible consequence of the heterogeneity in the local chemical environment, and so, equilibrium may be only reached locally in a large variety of microsystems.