An indirect Fourier transformation applied to small-angle X-ray scattering data has been used to determine the thickness and surface properties of two common clay minerals. For an illite system, the particle density distribution function (PDDF) generated by the analysis gave a correct description of particle geometry, and the calculated electron density profile was in accordance with the theoretical electron density distribution for this mineral. This approach provides the opportunity to determine the thickness of fundamental particles of illite while avoiding the difficulties encountered in other methods. Both the PDDF and the electron density profile accurately predict the thickness of Na-montmorillonite layers, and the results suggest that an electron inhomogeneity exists at the interface of this mineral.

Rheological measurements were used to evaluate the particle-particle associations of Na-rich montmorillonite in suspensions, under various electrolyte concentrations. A 2% free electrolyte clay suspension showed pseudoplastic flow behavior and had a high apparent viscosity, attributed at low shear rates to the high volume fraction of the suspended clay platelets, the flexibility of the platelets, and the presence of edge-to-edge association. The breaking of edge-to-edge associations and the progressive orientation of the individual platelets in the direction of flow contribute to the reduction in viscosity with increasing shear rate.

The compression of the diffuse double layer at a NaCl concentration of 10 mEq L-1 contributes to the free movement of the individual platelets, even at low shear rates. The flow behavior changed from pseudoplastic to plastic at an NaCl concentration of 100 mEq L-1. At this electrolyte concentration, face-to-face associations of specific junction points at certain areas of the planar surface are probably occurring.

The apparent viscosity of the clay suspension for the two particle-size ranges (<2 and <0.02 μm) at all shear rates converged to a minimum value of 4.5 mPa s at NaCl concentrations of 10–20 mEq L-1. On both sides of the minimum, the lower the shear rate, the greater the slope. The apparent viscosity of a 2% suspension of Na-rich montmorillonite <0.02 μm particles, however, was significantly greater than that observed for a suspension of <2 u,m particles. This high apparent viscosity is attributed to the increase in edge surface area and the number of clay particles in a unit volume.

We suggest that edge-to-edge association between Na-rich montmorillonite platelets prevails when the NaCl concentration is below the electrolyte critical concentration, for which the apparent viscosity of the suspension is at its minimum value, whereas face-to-face association prevails at NaCl concentrations above this critical value.

Nontronite and microbes were detected in the surface layers of deep-sea sediments from Iheya Basin, Okinawa Trough, Japan. Nontronite, an Fe-rich smectite mineral, was embedded in acidic polysaccharides that were exuded by microbial cells and electron microscopy showed that the nontronite layers were apparently oriented in the polysaccharide materials. We propose that the formation of nontronite was induced by the accumulation of Si and Fe ions from the ambient seawater and that extracellular polymeric substances (EPS) served as a template for layer-silicate synthesis. Experimental evidence for this hypothesis was obtained by mixing a solution of polysaccharides (dextrin and pectin) with ferrosiliceous groundwater. After stirring the mixture in a sealed vessel for two days, and centrifuging, Fe-rich layer silicates were identified within the precipitate of both the dextrin and pectin aggregates, whereas rod-shaped or spheroidal Si-bearing iron hydroxides were found in the external solution. Microbial polysaccharides would appear to have affected layer-silicate formation.

The surface microtopographic observations and analyses of Izumiyama hydrothermal illite particles were made by utilizing tapping-mode atomic force microscopy (TMAFM). The Izumiyama illite particles showed platy to lath shapes. Platy particles exhibited various spiral growth patterns, i.e. circular, malformed circular, or polygonal single unit-cell layer spirals, polygonal parallel step spiral, or interlaced spiral patterns. The polygonal parallel step spiral and interlaced spiral patterns are formed by two single unit-cell layers rotated by 180° and 120° arising from a single screw dislocation point, respectively. The spiral patterns indicate that the illite particles have 1M, 2O and 2M1 polytypes. Lath-shaped particles show only interlacing patterns supporting the formation of 2M1 structures.

Particles showing circular or malformed circular spirals were found to be thinner and to have narrower step separations than particles showing polygonal spirals. Polygonal platy and lath-shaped particles showing interlaced patterns tended to be thicker and to have wider step separations than the other polygonal platy particles.

These results suggest that the Izumiyama illites crystallize as the result of a mechanism involving solution-mediated polytypes and spiral-type transformations of illite. The mechanism involves the Ostwald ripening process, i.e. a transformation of the polytype and spiral shape. The sequence of crystallization of the Izumiyama illite is: 1M circular spirals → 1M, 2O polygonal spirals → 2M1 polygonal spirals occurring during crystal growth and sequentially overgrowing on the initial particle surfaces. The super-saturation of the hydrothermal solution probably decreases gradually during the transformation, and this decrease may cause not only the transformation from a circular to a polygonal crystal morphology but also the development of a lath habit due to the inhibition of the growth rate in the [010] direction of the particle.

It is shown that polytypes or stacking sequences of cronstedtite, an Fe-bearing trioctahedral 1:1 phyllosilicate, can be determined using near-atomic high-resolution transmission electron microscopy (HRTEM). By viewing along the [010], [310] and directions (orthohexagonal indexing), the four groups of the standard polytypes can be distinguished. Imaging along the [100], [110] and directions allows determination of the polytypes in each group. The polytypic sequences of groups A and C are intergrown at the monolayer level in cronstedtite from Lostwithiel, England, which is a new insight if compared with previous suggestions that layer stackings characteristic of different groups do not occur together. The HRTEM images also revealed the relationship between the layer polarity and the morphology of the cronstedtite crystals, where the tetrahedral sheet side points towards the top of the truncated pyramidal shape of the crystal.

The evolution of texture, structure and chemical composition of chloritic clays in coeval pairs of metabasites and metapelites of a prograde sequence from the Bükk Mountains has been investigated using electron microscopy techniques. Samples are from the Bükkium (innermost Western Carpathians, Hungary) that underwent Alpine metamorphism, ranging from late diagenesis to epizone for pelites and from prehnite-pumpellyite to greenschist facies for the metabasites.

Although bulk-rock compositions, textures and primary minerals are different, chlorite evolved at similar rates in coeval metabasites and metasediments, but along different paths. The principal similarities in the prograde sequence are a decrease in the percentage of interstratified material in both dioctahedral and trioctahedral phyllosilicates and increase in thicknesses of chlorite and illite crystallites. The principal difference is in the type of interstratification in chlorite, with berthierine in metapelites, and smectite (saponite) in metabasites, although smectitic mixed layers also occur in the former. The evolution of trioctahedral phyllosilicates is marked by a decrease in the number of mineral species with increasing grade, chlorite, sensu stricto, being the only trioctahedral mineral at higher grades. This is consistent with the trend in reaction progress where both metastable systems (metabasites and metapelites) tend toward the same end-member, thermodynamically stable chlorite, as well as texture (crystal size), and where all intermediate states are metastable, and determined by the Ostwald step rule.

Clay mineral diagenesis in the Niigata basin is documented by mineralogical and chemical analysis of clay minerals from cuttings from the Shinkumoide SK-1D (SSK-1D) well which is characterized by alternating beds containing dioctahedral and trioctahedral smectite minerals with increasing depth. Dioctahedral smectite shows a progressive increase in illite interstratification with increasing depth. The transition of dioctahedral smectite to interstratified illite-smectite (I-S) is supported chemically by an increase in K and Al and a decrease in Si with increasing depth. In contrast, trioctahedral smectite (saponite) reacts to form a 1:1 interstratified chlorite-smectite (C-S) with increasing burial depth and temperature. Considering the geology and the occurrence of smectite, the SSK-1D smectites probably altered diagenetically from two different parent materials: dioctahedral smectite is derived from clastic sediments and transforms to interstratified illite-smectite, whereas trioctahedral smectite is derived from andesitic pyroclastic rocks and transforms to interstratified chlorite-smectite.

The C-S occurs at the same depth of ~3200 m as the conversion of randomly interstratified (R = 0) I-S to (R = 1) I-S. Furthermore, the depth is compatible with a Tmax temperature of 430-435°C, which indicates the starting temperature for oil generation from organic matter. The temperature of the conversion of (R = 0) I-S to (R = 1) I-S and the start of corrensite formation is estimated at 110-120°C based on the time-temperature model suggested by others. The clay-mineral diagenesis in the SSK-1D further suggests that I-S and C-S can act as geothermometers in clastic and pyroclastic sediments provided that the effect of time is considered.

The OH-stretching region in curve-fitted micro-Raman, photoacoustic and transmission IR spectra of St. Claire dickite was investigated. Polarized Raman spectra recorded from th. (001) an. (010) faces of the dickite crystal displayed six prominent OH bands. The relative intensities depend strongly on both the orientation of the crystallographic axes and the direction of the electric vector of the laser beam. Four out-of-plane vibrations, AA, Az, CA and Cz, at ~3710, 3706, 3654 and 3643 cm-1 respectively, predominate when the electric vector is perpendicular to the dickite plates. Two in-plane vibrations, Dz and DA at 3627 and 3623 cm-1, intensify when the electric vector is parallel to the plane. The relationship between band intensity and crystal orientation was interpreted in terms of longitudinal optic (LO) and transverse optic (TO) crystal vibration modes. These LO and TO crystal modes were also observed in curve-fitted photoacoustic and transmission IR spectra of coarse, non-oriented crystals of the dickite.

The Madayi clay deposit consists of a thick sequence of residual white kaolinitic clay underlying the sedimentary Warkallai Formation, which includes gray carbonaceous kaolinitic clays, lignite, ferruginous kaolinitic clays, laterite and bauxite with ferricretes. The conditions of clay genesis and the economic significance of the major residual kaolin seam have been investigated. The raw clay and <2 μm fractions were subjected to X-ray diffraction (XRD), chemical analysis, differential thermal analysis (DTA), Fourier transform infrared (FTIR) spectroscopic and scanning electron microscopic (SEM) studies. The firing behavior of the <45 μm fraction of the major residual clay sequence (L), was investigated systematically to determine the potential industrial use of this kaolin.

Geochemical and morphological studies of different strata indicate the following conditions for clay formation. (1) intense lateritized weathering conditions for kaolinization of the residual white clay from parent quartzo-felspathic mica-gneiss. (2) reducing environment for the gray carbonaceous layers; an. (3) oxidizing environment for the uppermost hematite-rich ferruginous clay. Pyrite/marcasite enriched detrital gray carbonaceous clay shows two distinct environments for in situ kaolinite crystallization. (1) within plant fossils influenced by the high organic content and FeS2 leaching; and (2) precipitation from solution.

Incomplete kaolinization of white residual clay is evident from the presence of pyrophyllite, muscovite with lenticular cleavage void and a lower percentage of fines (<2 μm). The plant fossils from the uppermost portion of residual clay show pyrite mineralization. The Hinckley Index, FTIR and rare earth analysis point towards diverse geochemical environments of deposition and technological evaluation indicates its suitability for application in the ceramics industry.