This study uses transmission electron microscopy (TEM) and analytical electron microscopy (AEM) supported by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to investigate the mineralogical and textural changes produced in carbonated clays by firing. Sample bars were prepared using raw clays composed of quartz, illite and carbonates with minor amounts of smectite, chlorite, feldspars and Fe oxides. The raw samples were then fired at temperatures of between 800 and 1050°C. The XRD data show that increases in firing temperature result in dehydroxylation of clay minerals, carbonate decomposition and the formation of Ca-bearing silicates (e.g. gehlenite, wollastonite, pyroxenes and anorthite). The sizes of the Ca-silicate crystals make the use of the SEM inappropriate since they lie below the resolution threshold. However, TEM/AEM do provide the required textural and compositional characterization, revealing that there is a broad range of pyroxene compositions, some of which resemble fassaite, and that Ca/Mg ratios increase with temperature. The TEM also shows significant dehydroxylation and vitrification of the clay-rich matrix at T of ~800°C. Observed mineralogical and textural changes probably occurred in a system with a local disequilibrium much like small-scale, high-temperature metamorphic reactions (i.e. pyrometamorphism). The importance of these results is that they enable the selection of more appropriate raw clay composition and firing dynamics (temperature, firing duration and cooling rate) for both the brickmaking industry and brick conservation in the field of cultural heritage.

The fractal dimension values of several kaolins with different structural order and properties have been calculated from N2-adsorption isotherm data according to the Neimark method. All kaolins show a fractal regime in the same nitrogen relative pressure range, with fractal dimension values ranging between 2.38 and 2.57.

The correlation between fractal dimension and other kaolin characteristics (structural order of kaolinite, BET surface area, brightness and particle-size distribution) was determined. The correlation matrix shows that the fractal dimension (Ds) is highly correlated with the degree of structural order-disorder and is also moderately correlated with the particle-size distribution and brightness. No correlation was observed between BET and Ds, probably because the first is a measurement of the accessible surface while Ds represents the scaling properties of the area.

As Ds is a parameter easily calculated and related to the degree of surface heterogeneity, and well correlated with other kaolinite parameters, it can be used to estimate a set of kaolin technical properties for suitability of the kaolin in the paper industry.

The thermal decomposition of hydrotalcite (HT), with chemical composition Mg1-xAlx(OH)2(CO3)x/2.(1-3x/2)H2O, (0.20 < x ≤ 0.33), is a complex sequence of dehydration, dehydroxylation and decarbonization and leads to the formation of a series of metaphases: HT-D (dehydrated HT), HT-B (partially dehydroxylated HT) and MO (mixed oxides with periclase-like structure). The evolution of water and CO2 in natural and synthetic hydrotalcites (a Mg/Al ratio between 2:1and 3.7:1), heated to 800°C, was investigated by differential thermal analysis, thermogravimetry and evolved gas analysis. At least six endothermic and two exothermic effects were established by computer-aided resolving of the curves. The formation of each HT metaphase was related to the release of a discrete number of water molecules depending on the Al content in the samples and each appeared as a corresponding endothermic peak in the DTA curves. The exothermic processes associated with the crystallization of HT-B and MO metaphases were specified by decomposition of DTA curves. The evolution of CO2 during the thermal decomposition of the carbonate groups was found to be different for the samples studied. The preservation of CO3 even at high temperatures was established for synthetic samples with a high Al content. The release of volatile H2O and CO2 (which comprise ~40% of the sample mass) provokes fine cracking both along and across the layers.

Pyrophyllite from a Triassic sedimentary formation from the Coastal Range of Chile has been investigated by transmission/analytical electron microscopy (TEM/AEM). The mineral assemblage includes pyrophyllite, muscovite, paragonite, a kaolin mineral, boehmite, rutile and hematite. The textures indicate that the protolith was a volcanoclastic rock. Petrographic evidence, chemistry, and the mineral assemblage suggest the intense leaching of the parent rock by a weathering process, before the metamorphic episode, to create the protolith for the pyrophyllite. Pyrophyllite always grows from the kaolin mineral, and both phases show close orientation relationships. The presence of parallel intergrowths of pyrophyllite and muscovite indicate that muscovite also grew from the kaolin mineral. Nevertheless, the composition of muscovite suggests that this phase must also form from another precursor, probably Al smectite. The AEM data and textural relationships between pyrophyllite and muscovite reveal the presence of two generations of muscovite and suggest that Na-rich muscovite recrystallized into a Na-free muscovite and paragonite.

Fe-rich smectites from lateritic weathering profiles have previously been studied by XRD, ICP-AES, SEM-EDX and TEM-EDX analyses (Gaudin et al., 2004). These smectites exhibit intermediate chemistries between five end-members: Al-Fe beidellites, Al-Fe montmorillonites and Mg+Ni-saponite. The spectroscopic study by FTIR and XAS of these smectites reveals that: (1) tetrahedral Fe3+ is near or below the detection limit (0.05 cation for 4Si); (2) the large chemical variability is due to substitution of the three major cations (Fe, Al, Mg) within adjacent octahedra; (3) Ni is not concentrated in another clay phase such as Ni-kerolite and is located in the octahedral sheets of smectite; (4) octahedral cations are not randomly distributed but ordered in separated Fe, Al, Mg, Ni clusters; (5) the Mg-Ni saponite end-member actually appears as small trioctahedral clusters of Mg and Ni distributed within the dioctahedral smectite.

Factors influencing the degree of intercalation (‘reactivity’) of kaolinite group minerals have been investigated using six kaolin minerals, with variable crystallinity and particle size. Tests were performed to measure the degree of intercalation with potassium acetate, formamide, dimethylsulphoxide and hydrazine.

These experiments indicate that intercalation degree depends on a number of factors, including particle size, degree of ordering, type of guest molecules, method of intercalation, and presence and types of impurities. Anew method for determination of the degree of intercalation is proposed, which is not dependent on the intensity of complex reflections. The results indicate that formamide is the most sensitive reagent to distinguish differently ordered kaolin minerals whereas hydrazine appears as the most appropriate reagent to differentiate kaolin minerals from other 7 Å phases.

The Fe oxide mineralogy behind the reddish colour (up to Munsell 10R) of a soil and four Quaternary surface deposits from central Jutland (Denmark) was investigated by XRD, TEM, Mo¨ssbauer spectroscopy and bulk saturation magnetization. The red soil (Naesset) consists of a 1 m deep patch, ∼10 m2 in area. It is one of at least 5 –10 isolated spots of limited size which contain hematite and maghemite, and are probably due to local fire.

The four more extended (several hundred m2) red sediments (Salten Skov, Salten, Pot Molle and Laasby) all occur at the feet of slopes and formed from Fe2+-containing seepage water. They contain 25 – ∼100% Fe oxides, originally consisting of ferrihydrite. The well-drained parts of the deposits are at present all dominated by goethite. Hematite and maghemite were also identified at two sites in the top ∼25 cm, one site containing goethite and hematite and probably a little maghemite, and the other goethite and probably hematite. The presence of hematite and particularly maghemite in the surface sediments could be explained by heating of goethite. However, there is no historic or prehistoric evidence of heating activity, and the spatial extension is much wider than that of normal human events. In contrast to the burned soil site, goethite is still present in the upper layers together with a high content of organic matter. Thus, although the present belief is that the deposits formed by heating, site evidence is to the contrary.

Fe3+-doped K10 montmorillonite combined with 2,6-di-tert-butyl-4-methyl-phenol is a potent catalytic system for trans-2-methylene-1,3-dithiolane 1,3-dioxide as a dienophile. Cycloaddition occurs with cyclopentadiene and furan as a diene at room temperature in short time and with good yields (64% overall).

Clay mineral analysis of Spodosols collected from the Adirondack Mountains reveals that smectite is common in the forest floor and uppermost soil horizons (the O, A and E horizons) and probably forms from the transformation of vermiculite via a low-charge vermiculite intermediate. The conversion of vermiculite to smectite occurs in the upper part of the soil profile where organic acids and strong inorganic acids (derived from atmospheric deposition) combine to create an intense weathering environment. X-ray diffraction (XRD) and chemical data for the clay fraction indicate that both the smectite and the low-charge vermiculite are Al-rich and dioctahedral. The smectite appears to be a beidellite. Transformation of vermiculite to smectite may have progressed in these acidic horizons by net layer-charge reduction resulting from the progressive substitution of Si for Al. The parent material for the soil clays was probably biotite, but little remains in these soils.

Halloysite in El-Gideda iron mine occurs as very soft, light and white-to-pinkish white pockets and lenses ranging in diameter from 50 cm to 1 m within the iron ore. Highly hydrated halloysite is the main constituent of these pockets beside some kaolinite and alunite. The diffraction pattern of the clay fraction (<2 mm) shows a rather broad and diffuse 001 reflection spread between 10.3 and 13.6°2θ. Upon treatment, the 001 reflection of halloysite expands up to 10.94 Å and 11.9 Å corresponding to ethylene glycol and dimethyl formamide treatment, respectively. After these treatments, kaolinite appeared with its characteristic basal spacing (~7 Å). The percentage of halloysite in halloysite-intercalated kaolinite ranged between 80 and 90%. Heating to 350°C, produces a kaolinite-like structure (~7.1 Å) that developed to a metakaolinite-structure when heated to 550°C. Morphologically, halloysite appears as well developed tubes composed entirely of SiO2 and Al2O3, while kaolinite is characterized by very fine platelets arranged in book-like or rosette-like shapes. A differential thermal analysis curve of the studied halloysite showed an endothermic peak at ~138°C due to the dehydration of interlayer water of halloysite. The small shoulder at ~540°C and the endothermic peak at ~593°C is attributed to the dehydroxylation of halloysite, kaolinite and alunite. On the other hand the exothermic peak that appeared at 995°C is due to the formation of new phases such as mullite and/or spinel. The infrared vibrational spectrum is typical of highly disordered halloysite and kaolinite.

Halloysite was formed as a result of alteration of the overlying glauconite suggesting intensive chemical alteration during a humid wet period that prevailed in the Bahria Oasis during the late Eocene. Glauconite alteration releases K, Fe, silica and alumina. Iron forms at least part of the iron ore in the El-Gideda mine while alumina forms halloysite as well as alunite when interacted with silica in an acidic environment.

This paper describes the swelling properties of two highly compacted clays, natural, untreated Wyoming montmorillonite (MX80) and Fourges smectite (FoCa7), saturated with Na and Ca, respectively.

The initially compacted samples were hydrated by subjecting them to different suction pressures in a range between 100 MPa and 1 kPa. For each equilibrium state, the volume change (swelling) and water content (hydration) were measured. The samples were then studied by X-ray diffraction using a transmission device to determine interlayer distance and particle size, in order to clarify both the swelling and hydration mechanisms. The distances between clay layers ranged between 10 and 21.6 Å , i.e. corresponding to between 0 and 4 water layers. Upon hydration, the particle size decreased from 350 and 100 clay layers per particle to 10 layers per particle when the suction pressure decreased from 100 MPa to 1 kPa for MX80 and FoCa7, respectively. The first swelling stage is described as being an insertion of water molecules between the layers. Then a division of the initial particles into particles of smaller size with increasingly large inter-particle distances was observed. Observations by transmission electronic microscopy confirmed these results.

Kaolinites were modified by controlled hydrothermal deuteration. Both infrared and near infrared vibration spectra of deuterated kaolinite were investigated by Diffuse Reflectance Infrared Fourier Transform spectroscopy. The stretching vibrations (v) of deuteroxyl groups of the kaolinite were observed at 2726, 2709, 2697 and 2667 cm-1, respectively. The overtone bands (2n) of the deuteroxyl groups were visible in NIR regions at 5454, 5419, 5388 and 5342 cm-1, respectively. The lattice vibrations of the kaolinite taking part in deuteration included 937, 915, 792, 751 and 690 cm-1 which are assigned to hydroxyl group-related deformation or translation-vibration mode. The hydroxyl band at 3435 cm-1 with its deuteroxyl band at 2542 cm-1 resulted from unevenly distributed structural defects, either due to the isomorphous substitution of foreign cations or the imperfections of the kaolinite lattice structure.

Bentonite deposits in Basoren Kutahya, West Anatolia, Turkey formed from alteration of perlite and pyroclastic rocks of Pliocene age. The distribution of bentonite deposits along faults in the study area indicates that the alteration solutions were hydrothermal. Although lateral zonation is observed in bentonite deposits in some regions (i.e. Demirli, Akyokus, Seklice- Sarıokuz, etc.), alteration zones are extremely irregular in the Cayırlık bentonite deposit.

X-ray diffraction studies have shown that Basoren bentonites contain dioctahedral Ca-smectite.

The Greene-Kelly test (Li-saturation and heating) showed that the Demirli and Akyokus bentonites consist of montmorillonite and that the Cayırlık bentonite consists of montmorillonite and/or beidellite. Spherulitic or hemispherical ‘crystals’ of opal-CT minerals formed from hydrothermal alteration of volcanic glass. The MgO, CaO and total Fe2O3 enrichment in bentonites, compared to parent rocks, is related to the chemical composition of hydrothermal solutions that passed through the ophiolitic rocks such as serpentinite.

Palaeozoic to early Mesozoic rocks of both autochthonous and allochthonous units of the Eastern Tauride Belt have different textural and mineralogical features related to their varying deposition regimes and thermal histories. The Devonian and Carboniferous formations in the allocthonous units have anchizonal to epizonal grades of metamorphism, whereas those of the autochthon experienced only early diagenetic conditions. A well-developed penetrative slaty cleavage is also found in Devonian formations of the allocthonous units, which is not observed in equivalent rocks of the autochthon. Phyllosilicates of the uncleaved diagenetic assemblages consist mainly of illite, chlorite, kaolinite, mixed-layer illite-smectite, chlorite-vermiculite and chloritesmectite, whereas in addition to these, metamorphic allochthonous units contain some index minerals such as dickite, paragonite, Na and K mica, pyrophyllite, stilpnomelane and chloritoid. These latter assemblages show a higher degree of textural and mineralogical maturation and lower b cell dimensions than the autochthonous rocks, suggesting that they originated in a relatively high heat flow basin such as an extensional setting.

Previous attempts to use illite as a geothermometer have failed: no general relation between the mineral's chemical composition and temperature of crystallization has been found. Here, chemical compositions of 27 illite samples from five different geothermal fields (the data on four of which were drawn from the literature) were compared with their crystallization temperatures. As previously reported by Cathelineau (1988), the K content was found to be the only variable yielding a suitable correlation, but only when applied to one geothermal field; when various geothermal systems were considered, the correlation weakened considerably. Introduction of a correction algorithm to the K content of the illite has made it possible to draw a single line to fit the data from all the studied samples, yielding a good correlation coefficient (r = 0.84).