Lower Cretaceous (AJO and AJR) and Oligocene clays (AS) from northern Tunisia were analysed to evaluate their possible use in the production of earthenware tiles by dry processing and fast double-firing. The Cretaceous clays are carbonate-rich (AJO = 20%, AJR = 12%) while the Oligocene ones are carbonate-free. This led to noticeable differences in firing behaviour (shrinkage, sintering rate and loss on ignition) and consequently in functional properties (water absorption, mechanical strength, porosity). The AJO firing shrinkage is very small, which makes this clay suitable for rapid firing. The clays are illite-kaolinite-rich but the AS sample is mostly smectitic (44%) and so is used (10 wt.% maximum) only to adjust the consistency of the powder during pressing. The average agglomerate size ranges from 100 to 350 μm and the distribution is suitable for easy pressing of powders without any special need for further adjustments. Characterization of fired products confirms the high potential of these clays since all properties fall within the ceramic International Standards (ISO). For both technical and economic reasons dry processing is recommended for production of earthenware tiles, in particular for countries in sunnier climates, where solar energy can be exploited for clay drying.

The low-charge dioctahedral 2:1 phyllosilicates are an important group of clay minerals that have a low degree of cation substitution and very weak interlayer interatomic interactions which are difficult to reproduce with quantum mechanical calculations. In order to study the crystallographic properties of these compounds with density functional theory (DFT) quantum-mechanical methods, an optimization of norm-conserving pseudopotentials of Al, Si, O, H and Na atoms has been carried out, and an optimization of the cutoff radii of the basis sets has been accomplished. Crystallographic properties and vibrational stretching frequencies of the OH groups, ν(OH), have been calculated, being consistent with previous computational and experimental results. All frequencies can be related to the different molecular environment of the OH groups. The effect of octahedral Fe3+ substitution on the ν(OH) frequency is reproduced. Several configurations of cation substitutions and interlayer cation (IC) positions are studied in low-charge dioctahedral 2:1 phyllosilicates, such as Al4(Si7–xAlx)O20(OH)4Nax, with x = 0.25, 0.50 and 0.75, indicating that the IVAl3+ is highly dispersed and the IC tends to be in the substituted ditrigonal hole. For the Al4(Si7Al)O20(OH)4Na composition, the trans-vacant form is more stable than the cis-vacant one.

The thermal history of the Buntsandstein (Lower Triassic) sedimentary rocks that crop out in the Vosges Mountains, or are deeply buried in the Rhine Graben, was evaluated on the basis of a combined mineralogical, morphological, oxygen isotope and K-Ar-dating study of illite separates from five locations over a limited 120 km2 area. The results indicate a complex pre-rift evolution characterized by the following features: (1) in the northern Vosges, no record of diagenetic illite formation could be detected; (2) in the nearby Saverne rifting fracture-field, tectonic activity favoured the formation of faults in the crystalline basement ~210 Ma ago. This induced fluid migrations into the porous sandstone cover with illite precipitation occurring either repetitively over a period of ~25 Ma or as two separate events, the latter at ~185 Ma, affecting rocks to the east in the deeper part of the post-Eocene Upper Rhine Graben system; this latter stage of tectonic activity and fluid migration continued until 160 Ma, unless overprinted by another tectonic pulse at that time; (3) afterwards, the main tectonic activity moved to the Soultz-sous-Forêts area where two episodes could be identified at ~95 and 70 Ma by dating mineral crystallization; the latter illite age was also detected in more deeply buried Buntsandstein lithologies of the rift basin, west of Strasbourg, reflecting diverse crystallization under different physical and/or chemical conditions; (4) further illitization which at present is poorly constrained may have restarted ~55 My ago in the same deep part of the rift graben.

The youngest detected illitization age is clearly older than the main Miocene rifting episode of the Rhine Graben, suggesting that no illite crystallization occurred in the Buntsandstein sandstones during this tectonic event. This is explained by the fact that these rocks, as well as most of the underlying crystalline basement, were already sealed by fluid migration and mineralization during late Mesozoic rifting, and were therefore almost impermeable to the circulation of Tertiary fluids. The overall evolution of the region between the Vosges Mountains and the central Rhine Graben appears to be more complex than that of equivalent rock lithologies elsewhere in Western Europe. Several episodes identified here have been detected in other regions, but no single location exists which was affected by all events.

Kaolin mined from the Ipixuna deposit of Pará Pigmentos S.A. in the Capim river area of northern Brazil has been studied at various stages of beneficiation to determine the behaviour of Fe- and Ti-bearing minerals which can reduce the brightness of the product. X-ray diffraction and Mössbauer spectroscopy showed the principal pigmenting minerals to be hematite and goethite, with chemical analyses showing a distinct decrease of both the total Fe and Ti contents in the course of processing. The Ti contents were primarily reduced due to the removal of anatase during particle size fractionation and dithionite reduction. While the Fe content of the final product is structurally bound in kaolinite, Raman spectroscopy indicates the remnant Ti to be bound both structurally in kaolinite and in remnant anatase.

The composition of Rhassoul clay is controversial regarding the nature of the pure-mineral clay fraction which is claimed to be stevensite rather than saponite. In this study, the raw and mineral fractions were characterized using various techniques including Fourier transform infrared spectroscopy and magic angle spinning nuclear magnetic resonance (MAS NMR). The isolated fine clay mineral fraction contained a larger amount of Al (>1 wt.%) than that reported for other stevensite occurrences. The 27Al MAS NMR technique confirmed that the mineral is stevensite in which the Al is equally split between the tetrahedral and octahedral coordination sites. The 29Si NMR spectrum showed a single unresolved resonance indicating little or no short-range ordering of silicon. The chemical composition of the stevensite from Jbel Rhassoul was determined to be ((Na0.25K0.20)(Mg5.04Al0.37Fe0.20☐0.21)5.61(Si7.76Al0.24)8O20(OH)4). This formula differs from previous compositions described from this locality and shows it to be an Al-bearing lacustrine clay mineral.

In this study, poly(methyl methacrylate-maleic anhydride) (P(MMA-MAh)) was synthesized in toluene from methyl methacrylate (MMA) and maleic anhydride (MAh) monomers via free radical polymerization, in the presence of 2,2′-Azo-bis-isobutyronitrile (AIBN), as initiator at 80ºC for 8 h. The molar ratio of monomers was found to be 1 MAh:8 MMA using hydrolysis and titration. The molecular weight of co-polymer was determined to be of the order of 104 (g/mol) by gel permeation chromatography. The co-polymer was characterized using Fourier transform infrared and nuclear magnetic resonance spectroscopy. Thermogravimetric analysis indicated the initial decomposition temperature was ~270ºC. Differential scanning calorimetry indicated that the glass transition temperature was near 126ºC.

Rectorite modified with benzyldimethyldodecylammonium chloride (OREC) was used as an additive to modify gel polymer electrolytes (GPEs) which consisted of P(MMA-MAh) used as a polymer matrix, propylene carbonate (PC) as a plasticizer and LiClO4 as the lithium ion source. X-ray diffraction analysis indicates that OREC can exfoliate well in GPEs when the amount of clay is suitable. The temperature dependence of the ionic conductivity of the resulting GPEs agreed well with the VTF (Vogel-Tamman-Fulcher) relation. OREC doses of 5 phr resulted in the greatest ionic conductivity. This OREC addition considerably improved the plasticized retention levels. As a consequence of OREC occupying the free volume space in the polymer matrix of GPEs, the bulk resistance of the GPEs was reduced and the glass transition temperature (Tg) increased.

The Lembo clay deposit occurs on orthogneiss, but it also comprises clays with litho-relicts of volcanic rocks. In this study, ten samples from two sites were investigated. The mineralogical compositions consisted of kaolinite + halloysite + illite + quartz + hematite + anatase ± rutile ± orthoclase ± sanidine ± magnetite ± maghemite ± goethite ± Ba-Al-Fe-phosphates ± carbonates ± sulphates. Kaolinite-halloysite and quartz are the prevailing minerals. Some volcanicderived clays contain Fe-rich kaolinite-halloysite (9.6–14.1 wt.% Fe2O3). The chemical compositions, colours and specific surface area (SSA) measurements reveal two groups of clays: one with a positive whiteness index (IB), small SSA and small Fe content, and the other showing a large SSA, negative IB and relatively large Fe contents. The compositions of the first group are close to those of clays from the Mayouom deposit (Cameroon), and from some European commercial kaolins used in ceramics. Relatively Fe-rich clay materials may conform to most formulations of earthen bricks. As a whole, the Lembo clay deposit comprises various compositions of kaolinitic clays, which may yield the opportunity for extensive application in ceramics.

The transformation of schwertmannite to goethite was studied by ageing one synthetic and five natural schwertmannites in water at room temperature. Additionally, one synthetic and two natural schwertmannites were kept at variable pH (2, 4, 6 and 8). After one year, only the synthetic sample and one natural schwertmannite had transformed to goethite. However, the oxalate solubility of Fe and trace elements in all the samples decreased, whereas the total Fe/S ratios and specific surface areas of all samples increased. Arsenic and organic matter appeared to suppress the schwertmannite-to-goethite phase transformation. At pH 2, synthetic schwertmannite fully-transformed to goethite, but at pH 4–6 only minor transformation occurred. Depending on pH, many trace elements were released into solution during ageing of the natural schwertmannites. In general, Co, Mn, Zn and Si were released to solution, whereas As was enriched in the remaining iron oxide fraction. Al was dissolved at pH <4.

The sedimentation characteristics of two commercial bentonites, Tixoton (organically treated) and Montigel-F (untreated), were investigated using a 3% w/v clay suspension at different concentrations (1, 3.5 and 10%) of NaCl and pH values (2, 7 and 12). Settling rates, floc diameters and sediment volumes were derived from changes in light transmittance using a Turbiscan Ma 2000 instrument.

Both bentonite suspensions were unstable (flocculated) in NaCl solutions. The settling rate increased with increasing concentration of NaCl and was directly related to floc diameter. The sediment volume reduced with increasing NaCl concentrations, a result of greater double layer compression caused by increased ionic strength. At comparable salt concentrations, the organically-treated bentonite (Tixoton) settled at a much slower rate and had a greater sedimentation volume. The suspensions of both organically-treated and untreated bentonites were stable (dispersed) above pH 7 and unstable in acidic conditions. The settling rate for Tixoton under acid conditions was much smaller than that for the Montigel-F. Differences in sedimentation characteristics between the two bentonite samples are probably due to the presence of an anionic polymer (carboxymethyl cellulose: CMC) in Tixoton.

The viscosity of the bentonite suspensions was also studied. The viscosity of the clay suspension is closely related to clay dispersivity in solution. The CMC was highly effective in increasing the viscosity of the bentonite suspensions, but only under neutral and alkaline conditions.

The kaolinite from Albian sedimentary deposits (Escucha and Utrillas Formations) of the Iberian Range (Spain) have been investigated. This research has shown the presence of different types of kaolinites (detrital and diagenetic) along with micaceous phases in these deposits. Detrital kaolinites show anhedral morphology, low crystallinity and a degree of ordering as well as the presence of interstratified smectite layers. They constitute the matrix of the claystones and siltstones and were probably formed as a consequence of intense weathering processes in the source area during the warm period of the early Cretaceous. Diagenetic kaolinites have been recognized in the sandstones and siltstones, with kaolinite growing between ‘expanded’ mica flakes and vermiform and euhedral kaolinite forming the matrix. They have euhedral morphologies, high crystallinity and a high degree of ordering. They grew in situ as a response to incipient diagenesis by K-feldspar dissolution and/or organic acid-rich fluids derived from the maturation of organic matter in shales.

Respirable forms of crystalline silica including the mineral cristobalite are known carcinogens and the subject of increasing regulation and codes of good practice. Some bentonites may contain cristobalite, but more commonly they contain opal-CT, or opal-C, which can be confused with cristobalite. In the light of increasing regulation there is a clear need for simple and reliable methods that can distinguish cristobalite from the opals in bentonites and other clay materials. Here we propose the use of a simple NaOH method that is easily applied to bulk samples of bentonites. The method consists of boiling the clay in 0.5 M NaOH for 10 min and measuring the weight of undissolved solid. The method is shown to be accurate for both the identification and quantification of opal in bentonites since these phases are soluble when thus treated. It is also a straightforward method to distinguish the opals from cristobalite as the latter is essentially insoluble. Adoption by industry of a simple operationally-defined method such as this would be preferable to ad hoc reliance on direct instrumental methods alone such as X-ray powder diffraction, as the latter almost always require a large element of judgement and experience on the part of the analyst, although direct methods do need to be used in a supporting role.

The Fe3+ uptake from aqueous and methanol solutions of FeCl3·6H2O in two vermiculites from Santa Olalla and Ojén (Spain) and in a montmorillonite from Wyoming has been investigated by Mössbauer spectroscopy at room temperature and 4.2 K. The samples were further characterized by X-ray diffraction. The low temperature Mössbauer spectra reveal the deposition of akaganeite and perhaps some ferrihydrite on the external surface of the clay minerals. The room temperature spectra exhibit two Fe3+ quadrupole doublets in addition to the Fe2+ components of the structural iron in the sheet silicates. On treatment in ⩾0.04 M Fe3+ solutions the Fe3+ quadrupole splittings of 0.90 mm/s and 0.55 mm/s can be assigned to the mineral akaganeite; at smaller Fe3+ concentrations one of these doublets has a quadrupole splitting similar to that of the Fe3+ in the original vermiculites, the other one a quadrupole splitting of 0.6–0.7 mm/s, which can be considered as a hint for an uptake of Fe dimers in the interlayer space irrespective of the solvent used for iron deposition. Preliminary results show that the adsorption of pyrrole in all of our Fe3+-containing samples, regardless of the preparation in aqueous or methanol solution, results in the formation of polypyrrole and a concomitant reduction of some of the Fe3+. An uptake of pyrrole into the interlayer space has been observed only in the Fe3+-containing Wyoming montmorillonite and in the Ojén vermiculite treated with the methanol solution of iron chloride.

Two natural clays (kaolinite and montmorillonite) were deposited onto a platinum electrode surface using two deposition techniques and under different experimental variables. For both clays, the percentages of surface coverage (%θ) were optimized in the 75–96% range. A greater surface coverage was observed at higher temperatures for both clays, which confirms the endothermic nature of the deposition process. The maximum surface coverage (96%) was achieved for kaolinite. The surface coverage of kaolinite on a platinum electrode was constant for deposition times between 6 and 20 h. A surface coverage of 91% with montmorillonite particles was achieved. There was a very small increase in surface coverage by increasing the concentration of clay in the modified solution. The maximum surface coverage was observed under acidic conditions and smaller coverage values were reported for neutral and basic solutions. For both clays, a complete surface coverage for the electrode surface was achieved using the spin-coating technique. The experimental variables that affect the deposition of the clay, such as the stoichiometric ratio of clay/PVC and centrifugation speed and time, were studied and optimized to obtain full surface coverage. The spin-coating method achieved the required durability and stability for the modified-electrode. The characterization showed that the metallic surface chemistry of the platinum electrode was totally suppressed. Both modified electrodes were found to be useful for determination of Ag(I) ion with a detection limit as small as 1.00×10–10 M. The analytical precision was also satisfactory (RSD <5.0%).