The most common means of reducing the particle size of solids is by grinding, a process which can affect the surface properties and the behavior of the solid in later stages (granulation, compaction, etc.), and which can influence the end-use properties of the final product. Inverse gas chromatography (IGC) measurements were used here to evaluate the influence of grinding, in a ball mill, on attapulgite. The milling experiments were performed in dry media for various periods. After 30 min of grinding, significant decreases in the particle size and specific surface areas were observed when calculated using different probes. No noticeable variation in the surface properties was observed by IGC either at infinite dilution or at finite concentration, however. In particular, the distribution functions of the adsorption energies (DFAE), giving information about the surface heterogeneity for both an apolar probe (octane) and a polar probe (isopropanol), remained unchanged, regardless of the grinding time. The stability of the surface energy with respect to the grinding process was seen to be related to the particular fibrous structure of the attapulgite clay.

Electro-osmotic chemical treatment is an innovative method to improve the strength of soft clays for geotechnical engineering purposes; the effectiveness of the treatment may be related to treatment time, the concentration of the solutions injected, and to variation of pH in the clay. The objective of this study was to investigate the relationship between the above-mentioned factors and the improvement in strength when calcium chloride solution was used as an injection material. A series of tests was carried out by injecting different concentrations of calcium chloride solution into a kaolin suspension, for different treatment times, during electro-osmosis. After the tests, the pH, cone resistance, water content, and concentration of Ca2+ in the kaolin at different locations were measured and analyzed. The results show that the concentration of Ca2+ in the kaolin, the pH, and the strength were increased near the cathode with increases in concentration of CaCl2 and treatment time. An insignificant increase in strength, due to ion exchange over the entire specimen, for short treatment times of 2 to 24 h, was observed because of a small increase in concentration of Ca2+ and in pH. During long-term treatment (120 h), a considerable increase in concentration of Ca2+ (137.0 mg/g) and pH (pH = 10) was observed near the cathode. This led to a pozzolanic reaction, which in turn caused a significant increase in the mechanical strength of the kaolin.

The placement of metal oxide pillars between clay mineral layers modifies their physical-chemical properties, including surface area, acidity, and catalytic activity. Aluminum is the most commonly used pillar cation, but the use of Fe offers a distinct opportunity to expand the range of catalytic behavior. The purpose of this study was to prepare Fe-pillared Laponite and montmorillonite and to characterize the resulting Fe phase(s). Laponite or montmorillonite suspension was mixed with different pillaring solutions containing Al oligomer and/or Fe oligomer with Fe:(Al+Fe) percent ratios ranging from 0 to 100%. The Al oligomer was obtained by hydrolysis of A1C13·6H2O with NaOH at pH 4.4 and the Fe oligomer was prepared by FeCl3 hydrolysis with Na2CO3 at pH 2.2. The pillared clay was obtained by adding the oligomer to the clay suspension, then heating to 300°C for 3 h. The Fe oligomer and the pillared clay minerals were characterized by variable-temperature Mössbauer spectroscopy, X-ray powder diffraction, and chemical analysis. The unheated Fe oligomer was akaganeite, an Fe oxyhydroxide phase. Heating the Fe oligomer to 300°C transformed the akaganeite to hematite, but heating it in the presence of the clay protected it, at least partially, from this transformation, creating instead a phase which resembled a more poorly ordered akaganeite or a mixture of akaganeite and poorly ordered hematite. Mixing of Al and Fe oligomers in the pillaring solution had no effect on the magnetic hyperfine field of the Fe pillars, indicating that Al forms separate pillars rather than substituting for Fe in the pillar. A small fraction (4%) of the Fe pillar resisted reductive dissolution by citrate-bicarbonate-dithionite.

Theoretical models of the mechanical properties of hydrated smectites, saturated with a variety of cations, are of much value in determining the potential for their use in various applications, including clay-polymer nanocomposites, but the development of such models is still in its infancy. The purpose of this study was to calculate the effects of divalent cations on the structural and mechanical elasticity of montmorillonite under different degrees of hydration. A theoretical study of the swelling and hydration behavior of montmorillonite was, therefore, undertaken using density functional theory (DFT) to investigate the basal spacing behavior of the homoionic montmorillonite with varying amounts of water in the interlayer space. The effect of the degree of the hydration of divalent interlayer cations (Mg2+/Ca2+/ Sr2+/Ba2+) on the structure expansion of the interlayer space was analyzed. In addition, the results obtained were compared to calculations performed on the montmorillonite model with a monovalent cation (Na+). The basal spacing (d001) is governed by the size and the degree of hydration of the countercations. The structures containing divalent cations are more compact than structures with monovalent cations. Ba-exchanged montmorillonite was found to have the largest d001 value for any degree of hydration (‘dry,’ one water layer, or two layers). The basal spacings of ‘dry’ montmorillonite exchanged with small cations, Mg2+ and Ca2+, are very similar. In hydrated models, the d001 expansion correlates with the ionic radius of the interlayer cation. The dependence of the total electronic energy on the volume expansion was calculated. From the energetic curves, bulk modulus (B0) was obtained by fitting in order to show how the compliance of the material depends on the type of interlayer cation and on the degree of hydration. With increasing water content in the interlayer space, the bulk modulus decreased, suggesting that the c-axial compression becomes easier with increasing hydration of the clay mineral. The values of the bulk modulus in hydrated systems are less sensitive to the type of the interlayer cation.

In cases where the provenance of raw materials used in the manufacture of local archeological ceramics is of interest, a detailed study of thermal transformations of minerals may be useful. The purpose of this study was to measure mineralogical transformations of different types of clays obtained during experimental firing runs, carried out at different temperatures, with the main goal of establishing Algarve reference groups based on the composition of raw material and high-temperature mineralogy, which may be compared with ceramics in studies of provenance. Eleven samples of clay-rich raw materials from the Algarve Basin (southern Portugal) were fired to temperatures ranging from 300 to 1100°C in increments of 100°C under oxidizing conditions. These were chosen to have variable chemical and mineralogical compositions, representing the main compositional range of the clay deposits from the region. Mineralogical and geochemical characterizations of the original clays were carried out by X-ray diffraction (XRD) and X-ray fluorescence (XRF), respectively. Mineral transformations on the fired products were also studied by XRD.

Three groups of clays were distinguished according to the type of neoformed high-temperature minerals: (1) non-calcareous clays; (2) clays containing calcite as the only carbonate; and (3) clays with dolomite or dolomite + calcite. Firing of non-calcareous clays produced mullite at 1100–1200°C. Gehlenite and wollastonite formed by firing calcite-rich clays above 900°C, accompanied by anorthite or larnite in samples with small or large calcite contents, respectively. Firing of dolomite-rich clays at temperatures >900°C yielded a member of the gehlenite-åkermanite group and diopside. Anorthite, enstatite, periclase, forsterite, and monticellite may also form in the firing products.

The origins of dolocrete and associated palygorskite in the Çanakkale region of Turkey have been little studied, but are of fundamental importance for a more complete understanding of the mineralogy of this region. The present study was undertaken in order to narrow this gap. Siliciclastic red mudstones within alluvial-fan deposits of the Middle Miocene Sariyer Formation locally contain dolocretes in various forms (powdery, nodular, and fracture-filling) and scarce matte-brown, authigenic clay lenses. The mineralogical characteristics of dolocrete and authigenic clay lenses were examined using polarized-light microscopy, X-ray diffraction, differential thermal analysis and thermal gravimetry, scanning-electron microscopy, and infrared spectroscopy, as well as by chemical and isotopic methods. These analyses indicate that the dolocretes are indeed predominantly dolomite, coexisting with variable amounts of palygorskite. The authigenic clay lenses are composed mainly of palygorskite. Dolomite appears as euhedral crystals, whereas palygorskite developed authigenically as interwoven fibers on and between resorbed dolomite crystals, rimming euhedral crystals, and as fiber bundles (where dolomite ± magnesite is absent). The stable-isotope values and some petrographic features, such as alveolar texture and dolomite needles, support a pedogenic origin for the dolocretes. In the initial stage, dolomite formed by replacement of siliciclastic red mudstones and/or by precipitation from percolating soil-derived water in a near-surface setting. Subsequently, palygorskite either precipitated on the dolomite crystals from relatively more evaporative water, replaced the host-rock mudstone in the presence of Al + Fe, or formed directly from solution where the Ca/Mg ratio decreased and the Al + Fe increased. In view of the large Cr and Ni contents of the bulk-rock samples, the elements required for the crystallization of dolomite and palygorskite (namely Mg, Ca, Si, Al, and Fe) may have been supplied by weathering of ophiolitic rocks that crop out in the area.

The occurrence of halloysite and/or kaolinite in clay-rich, vein-like zones in saprolites in Hong Kong has provided the opportunity to examine the conditions determining the formation of one kaolin mineral or the other and also the nature of their particles. Clay-rich zones within tuffaceous or granitic saprolites from six different hillside sites have been examined in replicate samples by optical and scanning electron microscopy, X-ray diffraction, and thermal analysis. Kaolin minerals, sometimes together with Mn oxides and Fe oxides/oxyhydroxides, have formed within discontinuities within the altered host rocks. The fabrics of kaolin infills generally indicated several generations of kaolin formation and that shear and deformation have commonly occurred within the infills. The infills were either light or dark in color. Light-colored infills often comprised pure, or nearly pure, halloysite or kaolinite. Dark Mn- and Fe-rich infills all contained kaolinite, while including some halloysite. The very halloysitic, light-colored infills occurred in saprolites in both granite and tuff as long tubular shapes in parallel bunches. The light-colored, very kaolinitic infills occurred in tuff only, in large platy or near-platy shapes within vermiform packets. In dark-colored infills, early kaolin mineral crystallization was limited by impurities from the breakdown of primary minerals leaving dissolved and re-precipitated compounds of Mn and Fe within the infill. Kaolin minerals in infill at all the sites except one are considered to have formed as a result of weathering. The exception comprises white infills in tuff that are composed of extremely small, closely packed particles, suggesting formation by hydrothermal action. Generally, the kaolin minerals have formed by neogenesis out of solution in the discontinuities. Drying, with the formation of Mn and/or Fe oxides/oxyhydroxides, had occurred several times, indicating enhanced drainage. Where drying had occurred, kaolinite had formed. Where indications of drying in infills were absent, halloysite was predominant.

In spite of decades of research on the subject, the crystal structure of illite is still poorly understood. The purpose of this study was to address this problem by investigating the nature of the interlayer content in illite IMt-2 from Silver Hill, Montana, using analytical transmission electron microscopy (ATEM), thermogravimetry (TG), and X-ray powder diffraction (XRPD) analyses. The ATEM data, together with literature and TG results, yielded the formula K0.70a0.01(H2O)0.42 (Al1.53Fe2+0.06Fe3+0.19Mg0.28)Σ−2.06(Si3.44Al0.56)O10(OH)2 or, assuming the presence of H3O+, K0.69Na0.01(H3O)+0.28(Al1.47Fe2+0.06Fe3+0.19Mg0.28)Σ−1.99(Si3.40Al0.60)O10(OH)2. The first formula indicates surplus interlayer and octahedral species, whereas the second shows no excess. The XRPD data were refined by Rietveld techniques, down to an Rp factor of 10.48–13.8%. The mineral composition consists largely of illite-2M1, illite-1M, and minor quartz. Although the refinement accuracy is limited by the intrinsic poor quality diffraction of the illites, the partially refined model is consistent with the chemical composition; in particular, attempts to introduce octahedral cations in excess of 2 were fruitless. All the results support the simple structural model, by which the illite structure strictly corresponds to a dioctahedral mica with H3O+ replacing K. As a consequence, the crystalchemical formula of illites should be calculated on the basis of six tetrahedral plus octahedral cations.

The fertility of soils with respect to K+ and NH4+ is often difficult to measure, but is essential for achieving effective agronomic practices. This problem is especially important in the Vertisols of Thailand. The purpose of the study reported here was to characterize the composition and layer-charge behavior of Thai Vertisols in order to understand better their K+ and NH4+ fertility. Topsoil and subsoil clay of 12 representative highly smectitic Vertisols from Thailand were studied. Interlayer swelling of smectite with alkylammonium cations, cation exchange capacity (CEC), and chemical composition were determined. These data and the re-expansion on glycerol treatment of Li-saturated, heated smectite demonstrated that high-charge, Fe-rich beidellite is the major clay mineral in these soils. The beidellite has a heterogeneous layer-charge distribution as measured by the alkylammonium method, with mean values ranging from 0.43 to 0.62 charges per half unit cell. The layer charge determined by CEC and structural formula methods for some almost pure smectites is smaller (0.32–0.54) and greater (0.46–0.69), respectively, than determined by the alkylammonium method. The structural formulae of beidellite confirm that the layer charge originates mostly in the tetrahedral sheet.

Far-infrared (FIR) analysis of synthetic Mg-, Ni-, Co-, and Fe-phlogopites coupled with structural data from X-ray diffraction revealed that the K interlayer environments are directly related to octahedral sheet composition and geometry. The general phlogopite formula, KM32+(Si3Al)O10(OH)2, was varied according to octahedral compositions, where M2+ = Mg2+, Fe2+, Co2+, and Ni2+. Octahedral substitutions have a direct effect on the b lattice parameter, which is related to the tetrahedral-octahedral sheet misfit and manifested by change in the tetrahedral rotation angle (α). The ditrigonal interlayer cavity geometry and the potential for retention of the compensating cations therefore varies according to the ionic size and the types and oxidation state of octahedral cations. These structural features appear as frequency shifts on FIR spectra. When Mg2+ is replaced by a smaller cation, Ni2+, the b parameter decreases and the tetrahedral rotation angle, α, increases, inducing the collapse of the ditrigonal ring. When this happens, the local anisotropy of the interlayer site increases, resulting in every other six out of 12 K-O bonds becoming shorter and the in-plane K-O vibration band shifts slightly to greater wavenumbers. Synthetic phlogopites with octahedral substitutions by cations of larger ionic radii (i.e. Co2+ and Fe2+) exhibit b parameter increases, where in the case of the annite end-member, α decreases to almost 0°. As α decreases, compensating cation sites become more hexagonal like and the nearest K-O bond increases in length. The K-O vibration bands move toward much smaller wavenumbers. Far infrared offers the potential for a new approach to study the retention of interlayer cations in other phyllosilicates and the mechanisms by which they are altered, such as heating or by weathering reactions in the environment.

Proteins and protein-like molecules are abundant in various geochemical environments; they form complexes with mineral surfaces and with dissolved organic matter. To evaluate the effect of proteins on rates of dissolution of minerals, experiments on the dissolution of amorphous silica in solutions containing various concentrations of bovine serum albumin (BSA) were performed in this study. The dissolution experiments were carried out by a batch method using solutions of 0.1 mM NaCl with 0.00, 0.05, 0.1, 0.2, 0.5, and 1.0 mg/mL of BSA at three different pH conditions, 6, 5, and 4. The results of the experiments demonstrated that BSA exhibited strong rate-enhancement effects on the dissolution of amorphous silica and were dependent on BSA concentration and the solution pH. At pH 6, the dissolution rates of amorphous silica appeared to increase successively by ~1.6, 2.2, 2.4, 2.5, and 2.9 times with increasing BSA concentrations of 0.05, 0.1, 0.2, 0.5, and 1.0 mg/mL, respectively. The rates of dissolution increased by greater degrees, ~3.1–5.8 and 4.9–13.0 times at pH 5 and 4, respectively. According to the calculated charge distributions of amino acid residues of the BSA molecule, the dissolution rates of amorphous silica were likely to be enhanced by attractive electrostatic interactions of the positively charged side chains of lysine, arginine, and histidine residues with the negatively charged >SiO− sites on the amorphous silica surface. The negatively charged side chains such as glutamic acid and aspartic acid residues may inhibit the attractive interaction, depending on the degree of deprotonation.

In deep geological repositories for high-level nuclear wastes, interactions between steel canisters and clay-rich materials may lead to mineralogical transformations with a loss of the confining properties of the clays. Experiments simulating the conversion of smectite to Fe-rich clay phases in contact with Fe metal have been carried out to evaluate such a possibility by taking into account the effects of a series of critical parameters, including temperature, pH, and Fe/clay (Fe/C) and liquid/clay (L/C) ratios. The mineralogical and chemical transformations observed in these experiments have been compared with data from the literature, and subsequently used to propose a conceptual model for the main mineralogical transformations which can be expected in clay formations surrounding high-level nuclear waste repositories. In the presence of Fe metal and under low oxygen fugacity (<-40) the main mineralogical sequences are as follows:

1. (1) up to 150°C, under neutral pH, and L/C > 5: dioctahedral smectite (di-sm) → 7 Å Fe-rich phase (berthierine, odinite-cronstedtite) for large Fe/C ratios (>0.5), or di-sm → Fe-rich di-sm + Fe-rich trioctahedral smectite (tri-sm) for small Fe/C ratios (0.1)

2. (2) up to 150°C, under alkaline pH (10–12), and L/C > 5: di-sm → Fe di-sm (±palygorskite) for a small Fe/C ratio (0.1)

3. (3) at 300°C, Fe/C = 0.1, and L/C > 5: di-sm → Fe-rich saponite → trioctahedral chlorite + feldspar + zeolite (near-neutral pH); di-sm → Fe-rich vermiculite + mordenite (pH 10–12).

Low temperatures (<150°C) and large L/C and Fe/C ratios seem to favor the crystallization of the serpentine group minerals instead of Fe-rich trioctahedral smectites or chlorites, the latter being favored by higher temperatures. The role of L/C and Fe/C ratios and the competition between them at different temperatures is a crucial point in understanding the transformation of smectite in contact with Fe metal.