To provide fundamental knowledge for studying the relative content of vacant sites and exploring the mechanism of interaction between Pb2+ and birnessite, Fourier transform infrared spectroscopy (FTIR) of birnessites with different Mn average oxidation states (AOS) before and after Pb2+ adsorption were investigated. The number of absorption bands of FTIR spectra was determined by using the second derivatives of the original spectra. The band at 899–920 cm–1 was assigned to the bending vibration of -OH located at vacancies. The bands at 1059–1070, 1115–1124 and 1165–1171 cm–1 could be attributed to the vibrations of Mn(III)-OH in MnO6 layers, and the intensities of these bands increased with decreasing Mn AOS. The bands at 990 and 1023–1027 cm–1 were ascribed to the vibrations of Mn(III)-OH in the interlayers. Mn(III) in MnO6 layers partially migrated to interlayers during Pb2+ adsorption, which led to an increased intensity of the band at 990 cm–1. The band at 564–567cm–1 was assigned to the vibration of Mn-O located at vacancies. This band could split by coupling of vibrations due to Pb2+ and/or Mn2+ adsorbed at vacant sites. The large distance between the band at 610–626 cm–1 and that at 638–659 cm–1 might reflect small Mn(III) ions located in Mn(III)-rich rows.

The adsorption of cerium(IV) by both natural and Na-exchanged kaolinite from aqueous solutions of ceric ammonium nitrate was studied in equilibrium systems. Cerium may be adsorbed either as a monomeric species or as a polymeric hydroxy cation. The species adsorbed depends on the concentration of cerium in the stock solution, the age of this solution prior to the preparation of the equilibrium system and on the equilibration period. Adsorbed cations undergo polymerization on the surface of the kaolinite; the resulting polymeric species forms strong bonds with the clay surface—it is not desorbed by sulphuric acid—and may be considered fixed. Adsorption of cerium reaches a maximum in solutions containing 0·15 M sulphuric acid.

A method has been developed to synthesize organo-hectorite clays directly from a Mg-silicate gel containing organic or organometallic molecules that are expected to be incorporated within the interlayer space. Complete crystallization occurs upon aqueous reflux for 48 h. The progress of clay layer formation was monitored by X-ray powder diffraction (XRD), differential thermal gravimetry (DTG), and infrared (IR) spectroscopy. Evidence of clay XRD peaks occurs after just 4 h of hydrothermal treatment, and Mg(OH)2 is no longer observable after 14 h. Observable changes in DTG and IR occur at about this time as well. Warren line-shape analysis of the 110 reflection indicates that when growth is complete the clay lamellae are on average ∼50% and 25% of the size of natural hectorites and montmorillonites, respectively. The N2 BET surface areas for all materials are also compared. Small angle neutron scattering shows that addition of tetraethyl ammonium (TEA) ions does not alter the structural integrity over that of the purely inorganic form of Li-hectorite, but that use of a cationic polymer does significantly alter the microstructure. The effect of temperature is critical, for at room temperature only the layered Mg hydroxide mineral brucite crystallizes unless very long time scales are used. The crystallizations carried out at room temperature show that clay will form after about 3 months, but that the presence of organics (at least TEA) acts to hinder this process greatly. The role of the organic molecules on silicate clay layer formation is compared with the role of organics in zeolite synthesis.

The phase changes that took place upon heating an Fe-rich illite (OECD #5) to 1300°C in an oxidizing atmosphere were studied by a variety of mineralogical techniques. Infrared spectra, showing the stepwise dehydroxylation of the illite, showed good agreement with variations in sample colour and Mössbauer spectra. Dehydroxylation did not lead to noticeable variations in X-ray powder diffraction patterns until the structural breakdown of illite and formation of new phases at about 900°C Mössbauer spectroscopy proved to be very sensitive to all changes induced by heating, showing the disappearance of Fe2+ at 250°C, the gradual dehydroxylation between about 350 and 900°C, and characteristic features of the products formed at higher temperatures, e.g. the formation of hematite as the illite structure breaks down and the subsequent disappearance of hematite due to the incorporation of Fe in glass above 1200°C. The formation of hematite in clusters large enough to order magnetically at room temperature was first observed in the sample heated to 900°C, whereas at 4.2 K, significant proportions of a magnetically ordered phase could already be identified in the sample heated to 650°C.

Water-sorption isotherms and interlamellar spacings were measured for Ca montmorillonite (from Redhill. UK) over the relative pressure range 1 > P/P0 > 0. By taking account of the change in interlamellar volume with relative pressure, it is shown that internal and external surfaces can be calculated by a modified t-plot analysis. The results also show that sorption on the external surfaces of the montmorillonite is quantitatively similar to that on reference oxide surfaces. Desorption-sorption hysteresis occurred and was apparently caused by an ageing process in which the interlamellar volume increased at the expense of the external surfaces.

An investigation of the acid-leaching of a calcined kaolin was made to compare the reaction kinetics of hydrochloric, nitric, and sulphuric acids. The acid concentrations used were 5·9 and 8·6 normal. Reaction temperatures used were 95°, 80° and 60° C.

Particular attention was given to finding a reaction equation which would mathematically represent the kinetic data. A nucleation rate equation of the general form, was found to represent these data. Values of m varied from 1·10 to 1·55 depending on the experimental conditions.

Under the conditions employed the rate of alumina leaching is fastest with hydrochloric acid, slower with sulphuric acid, and slowest with nitric acid. The rate controlling steps are proposed from the experimental evidence.

Weathering profiles developed on the top surface of a bentonite (containing Al-Mg montmorillonite) and a K-bentonite (containing mixed-layer illite-smectite (I-S)) under Central European temperate conditions were studied by XRD, HRTEM, FTIR, K-Ar and chemical analyses. Weathering of montmorillonite results in the decrease of cation exchange capacity (CEC), total surface area and Mg content. The process is interpreted as montmorillonite dissolution and precipitation of amorphous SiO2. Weathering of I-S produces an increase in CEC and total surface area. The XRD data suggest dissolution of I-S and appearance of smectite as a separate phase at intermediate depths. The fixation of ammonium is documented in the topmost sample. In both profiles, abundant aeolian contaminants, including mica, were identified and their migration was traced using K-Ar dating.

The kaolin minerals in lateritic weathering profiles on dolerite and granite in Western Australia have been characterized by intercalation tests for halloysites, and also by their particle morphologies. Towards the surface of the profiles there is a decrease in both total kaolin mineral content, and in the expandibility of those minerals to intercalation. Tubular kaolinite that is non-expandible by any of the intercalation tests for halloysite was identified in the upper few metres of both profiles. Hydrated halloysite is most common at the base of both profiles. Formamide expands some anhydrous kaolin minerals while the sequence of hydrazine/water/glycerol (HWG) expands more of these minerals. Non-tubular (subhedral to sub-hexagonal platy) kaolinite is also present. Hydrated tubular halloysite apparently alters to tubular kaolinite via dehydrated halloysite that is expandible by formamide and a tubular ‘kaolin’ that is expandible by HWG but not by formamide.

An ab initio determination of the structure of sepiolite after acid treatment (HCl 0.5 N for 24 h) was carried out using X-ray powder diffraction data. After acid treatment, the sections normal to the a and c axes presented discontinuities, ∼2.25 Å wide, parallel to the (010) plane, with no electronic density maxima, thus suggesting that adjacent planes are joined by van der Waals-like residual links. Partial dissolution was detected on both octahedral and tetrahedral sheets, beginning by breaking the ribbons not along the edges, but in the centre, thus creating a 5.20 x 66.79 Å tunnel along the a axis. By interrupting the tetrahedral sheet, this mechanism changes the phyllosilicate-like nature of the sepiolite to an inosilicate-like structure.

Powdered 2:1 Mg-clay samples were rehydrated up to the maximum hydration. Both scanning and transmission electron microscopy were used to characterize their structural organization i.e. particle arrangement, texture and crystal structure. Low-angle X-ray scattering experiments were carried out to quantify the microstructure of the system. The results showed that sample water contents reached at saturation are not directly related to changes in layer distance. The hydration mechanism is rather correlated to particle size and particle aggregate size. It is also shown that the a, b plane extension of the layers influences particle size and shape. Finally, it appears that for a better understanding of clay swelling mechanisms, at high water contents, it is necessary to take into account all organization levels and that the contribution of interlayer space to the total water content, for Mg-smectites, is small.

Diagenesis in the Podhale and Orava Paleogene flysch basins and in the underlying Mesozoic structural units was studied by XRD measurement of the percent smectite in the mixedlayer illite-smectite from shales and K-Ar dating of the illite-smectite from bentonites, supported by XRD quantitative mineral analysis, grain density, and porosity measurements of the bulk shales. The diagenetic mineral reactions identified in the flysch shales include illitization of smectite (>60 to <5%S), dissolution of K-feldspar and kaolinite, crystallization of quartz, albite and chlorite. An unusually large amount of basin history information was obtained by combining the illite-smectite data from wells and from the present erosional surface of the basin.

The rocks underwent burial diagenesis at a stable geothermal gradient similar to the present-day value of 21±2°C/km. The maximum burial temperatures were reached very quickly (high sedimentation rate) close to the basin inversion time, at ∼17 Ma in the western part and 18 Ma in the eastern part.

The basin floor, which included the present-day Tatra Mts., was inclined towards the East. The thickness of the sedimentary filling of the basin ranged from 3.5–4.5 km in the western Tatra (removed entirely), to 5–6 km in the western Podhale (<3–4 km removed), to 6.5–7.5 km in the eastern Podhale (>4–5 km removed), and even more in the eastern Tatra and Spisská Magura close to the Ružbachy Fault. These data imply a major subsidence followed by uplift of the Podhale plus Tatra block along the Ružbachy Fault and the deposition of a thick sequence of Lower Miocene sediments over the entire area (latter removed by erosion).

The Mesozoic rocks of all the structural units underlying the flysch basin underwent advanced diagenesis (maximum palaeotemperatures of 160–270°C) during an Upper Cretaceous tectonic burial event at ∼80–90 Ma. The tectonic overload was removed before the Eocene transgression (49–42 Ma).

Deeply buried (> 3·5 km) Rotliegend aeolian sandstones in the Southern North Sea Basin display a number of interesting diagenetic features including (i) zoned iron-rich carbonate cements, (ii) anhydrite, halite and baryte cements, (iii) at least two generations of authigenic illite, and (iv) significant secondary porosity created by cement and framework-grain dissolution. The creation and destruction of secondary porosity is the result of changes in porewater chemistry during burial and subsequent uplift. Three pore-fluid regimes can be identified: (1) alkaline, oxidizing conditions during shallow to intermediate burial; (2) acid, reducing conditions during intermediate to deep burial; (3) alkaline, reducing conditions during deep burial and uplift. The transition from stage 1 to stage 2 was probably caused by expulsion of waters from the underlying Carboniferous shales. The transition to stage 3 probably began when faulting associated with uplift allowed invasion by alkaline fluids derived from Zechstein sediments.

Authigenic clay minerals in the German Rotliegend formed mainly at burial depths >1.5 km. Illite is the dominant cement, although kaolinite, dickite and early radial chlorite are abundant locally. Illites contain more AI and late chlorites more AI and Fe in sequences showing extensive grain dissolution. This relationship between clay chemistry and grain dissolution suggests that clay cementation is linked to grain dissolution. Sequences at relatively shallow burial depths (<3-5 km) contain less clay cement. In the more deeply buried sections, increased illite and kandite cementation, together with extensive grain dissolution, is evident where the Rotliegend is juxtaposed against Carboniferous Coal Measures. Faults also acted as important conduits for acidic fluids. Illite and kandite growth occurred at similar depths and from waters of similar isotopic composition (618O = 1-6‰ SMOW) throughout most of the Southern Permian Basin. However, the timing of illite growth varied between areas and corresponded to periods to tectonic activity.

Carbonate-bearing ceramic bodies are frequently used in the manufacture of bricks, roofing tiles, wall and floor tiles, pottery and tableware. During the firing of these bodies, clinopyroxene is usually formed in very small crystals, 1-5 µm in diameter or less. In the literature this phase is generally referred to as diopside, but no quantitative data are available. In order to chemically characterize these ‘ceramic’ pyroxenes, nine industrial products were analysed by XRF and XRD (bulk sample) and SEM-EDS (fracture surface). Quantitative ZAF analyses of pyroxene crystals showed a certain chemical variability: SiO2 35-50%, Al2O3 9-20%, Fe2O3 1-15%, MgO 3-14%, and CaO 16-25%. Sodium, K and Ti are always <1%, while ferrous iron is always <0.2% in the bulk sample. Overall, ‘ceramic’ clinopyroxenes present wide chemical analogies with ‘fassaite’, e.g. the abundance of aluminium and ferric iron, and the excess ofwollastonite molecules with respect to the diopside-hedenbergite series.

This study focuses on the mineralogical and geotechnical characterization of northern Moroccan clays from the Tangier and Tetouan areas and compares them with the main clay deposits used in the Moroccan ceramic industry (from Meknes, Fes, Salé and Safi regions). Sampled clays were analysed by X-ray diffraction on bulk and clay (<2 μm) fractions to identify the mineralogical assemblages of the clay outcrops. Further analyses were conducted to determine the particle size distribution (laser diffraction particle analyser), the total organic matter content (Loss- On-Ignition measurements) and the Atterberg limits of the raw clays. The study aims at investigating the spatial variability of the clay samples and at evaluating their potential application as raw materials in the ceramic industry.

Tetouan and Tangier clays are characterized by diversified mineralogical assemblages (in particular a variable proportion of clay, quartz and calcite) compared with the Meknes, Fes, Salé and Safi clays (high clay content, quartz and calcite). The clay fraction of the Tetouan and Tangier samples is dominated by illite and kaolinite with variable amounts of chlorite, smectite and/or vermiculite. Illite is the dominant phase in the Meknes, Fes, Safi and Salé clays, but is associated with kaolinite. No direct relationship between the mineral assemblage composition and the lithology of the series was found.

The clays materials studied consist generally of fine particles with medium to high plasticity and low organic matter content. Due to their mineralogy, grain-size distribution and plasticity the clays appear to be suitable as raw material for the growing Morocco ceramic industry.

Widespread chemical weathering of Tertiary alkaline volcanic rocks in the vicinity of Trabzon (NE Turkey) has led to the formation of well developed reddish-brown saprolite. These saprolites are dominated by kaolin minerals (predominantly kaolinite), with minor quantities of halloysite, pyrophyllite, chlorite, smectite, hematite and illite. Other common minerals are opal-CT, quartz and occasional feldspar, clinopyroxene, hematite and Fe-Mn-Ti oxides. The significant degree of fracturing and fragmentation of primary igneous minerals within the pyroclastic units, and subsequent penetration by reactive fluids, resulted in partial chloritization of clinopyroxene, albitization of plagioclase and precipitation of Fe-Mn-Ti-oxides within fractures and dissolution voids. Kaolin minerals occur as spongy fibrous meshes surrounding partly dissolved volcanic glass and devitrified sub-rounded grains that may be relict allophane. Field observations and mineralogical-chemical characteristics indicate that the alteration of the Tertiary volcanic units of the Black Sea region was controlled by chemical weathering during circulation of oxic meteoric or mixed meteoric and marine waters. Intense fracturing and fragmentation of the pyroclastic rocks resulted in the formation of clay minerals in the upper saprolite level under acidic and largely oxidizing conditions. Incongruent dissolution was associated with the leaching and downward transport of Si, Na, K and Ca and the concentration of Al. In such an environment, early precipitation of halloysite from allophane was probable, and it gradually transformed into kaolinite during aging and progressive weathering.

Textural, mineralogical and chemical parameters of clays belonging to the Upper Cretaceous ‘Argilas de Aveiro’ formation were determined and correlated, using geostatistical analysis, with some relevant geotechnical parameters. The data obtained made it possible to subdivide the region under study into distinctive sectors on the basis of geotechnical behaviour. Clay fraction content and composition control geotechnical parameters such as the expandability and the Atterberg plastic and liquid limits. A positive correlation was found between both expandability and the Atterberg plasticity index values and the total phyllosilicates, smectite, MgO and Al2O3. However, Atterberg plasticity index values were relatively independent of the diverse clay mineral assemblages.

Samples of natural clinoptilolite modified by treatment with NH4Cl or HCl solutions, followed by thermal treatments, have been characterized, and their catalytic activity evaluated, in o-xylene isomerization and ethanol dehydration reactions. The substitution of the compensating cations by NH4+ does not produce structural changes in the original material, but it opens the channels and increases its acidity and thermal stability. The treatment with HCl increases both the acidity and the effective diameter of the channels and pores but it produces an important loss of zeolite phase. Calcination of the acidic forms above 973 K leads to the breakdown of the zeolite structure. Catalytic activity of the samples is related to the surface acidity. For the original and NH4Cl-treated samples, however, the conversion of o-xylene is limited by the access of the reactant inside the channels of the zeolite. A comparative study with modified sepiolite in dehydration of ethanol has also been performed.

The addition of clay minerals in drilling fluids modifies the dispersion's viscosity. In this article, scientific advances related to the use of clays and clay minerals (bentonite, palygorskite, sepiolite and mixtures of clay minerals) in drilling fluids are summarized and discussed based on their specific structure, rheological properties, applications, prevailing challenges and future directions. The rheological properties of drilling fluids are affected by the temperature, type of electrolytes, pH and concentration of clay minerals. Bentonites are smectite-rich clays often used in drilling fluids, and their composition varies from deposit to deposit. Such variations significantly affect the behaviour of bentonite-based drilling fluids. Palygorskite is suitable for use in oil-based drilling fluids, but the gelation and gel structures of palygorskite-added drilling fluids have not received much attention. Sepiolite is often used in water-based drilling fluids as a rheological additive. Dispersions containing mixtures of clays including bentonite, kaolin, palygorskite and sepiolite are used in drilling fluids requiring specific features such as high-density drilling fluids or those used in impermeable slurry walls. In these cases, the surface chemistry–microstructure–property relationships of mixed-clay dispersions need to be understood fully. The prevailing challenges and future directions in drilling fluids research include safety, ‘green’ processes and high-temperature and high-pressure-resistant clay minerals.

Oedometer swelling and compaction tests up to a maximum pressure of 32 bars were made on the Wyoming montmorillonite SWy-1 with a range of mixed (Na,K) exchange ion compositions. The permeabilities and water diffusivities of the compacted clays were calculated using soil physics theory. Significant inhibition of swelling from that of the Na-montmorillonite is developed for K fractions in the range 0·30 < K+ < 0·56. However, the water diffusivity increases by a factor of approximately six as the K exchange fraction increases from 0 to 0·7. Permeabilities to water flow show a power-law dependence on the void ratio e.

XRD measurements at controlled humidity yield equilibrium interlayer spacings which in general increase with both increasing relative humidity and increasing Na exchange fraction. The extent of swelling is strongly inhibited in clays having Na exchange fractions of 0·44 or less, in good agreement with the oedometer studies.