Retention studies of the cobalt-goethite system were carried out using synthetic, star-shaped and lath-shaped pure, Al-, Cd-, Cu- and Si-associated goethites. Aluminium and Si are commonly occurring foreign elements in natural goethites. The goethites were prepared by coprecipitating Fe and the foreign element under controlled conditions and characterized by X-ray diffraction, transmission electron microscopy, specific surface area determination and 2 M HCl extraction. The foreign-element associated goethites contained ∼3, ∼5 and ∼9 mole % Al, ∼4 mole % Cd and ∼3 mole % Cu incorporated by isomorphous substitution but only ∼0.4 mole % of probably occluded Si. Crystal size and shape but also number of defects and domains, and hence specific surface area, unit-cell dimensions and reactivity towards 2 M HCl, exhibited great variability among the goethites. Accordingly the amounts of Co sorbed from initially 10−7 M Co in 0.1 M Ca(NO3)2 in relation to pH (3–8) and reaction time (2–504 h) were very different for the eight goethites. The affinity of Co is highest for Cd- and lowest for Cu-goethite. These samples also form the extremes regarding time-dependent sorption with Cu-goethite showing the smallest and Cd-goethite the largest increase in sorption with increasing reaction time. The Co uptake was not caused by precipitation Co(III) oxides due to Co(II) oxidation, since oxygen exclusion during sorption had no effect on the amount of Co sorbed. The amounts of sorbed Co extracted by 2 M HCl decreased with increasing sorption time but 40–87% of sorbed Co remained unextracted after 48 h, most in Cu-goethite and least in lath-shaped pure goethite. The strong retention suggests Co uptake by diffusion into micropores and fissures resulting from structural defects and intergrowths. The diffusion coefficients range from 3·10−19 to 6·10−17 cm2/s with the highest values for Al- and Si-associated goethites emphasizing the importance for Co immobilization, and hence availability, of foreign-element associations in goethite.

—The charge of the expandable interlayers in a series of fourteen diagenetic illite/smectites (I/S) from lower Paleozoic K-bentonites was determined by the alkylammonium ion exchange method. The magnitude (<0.50 equivalents per half formula unit) and characteristic heterogeneous distribution of interlayer charges in eight samples with expandabilities from 70% to about 15% confirm the smectitic character of the expandable interlayers in this range. This result coupled with the lack of a correlation between expandability and interlayer charge is consistent with the hypothesis of a layer-by-layer transformation from a precursor smectite to highly illitic I/S clays during K-bentonite diagenesis. The charge of the expandable interlayers in I/S samples with about 10% or less expandabilities have been inferred to be vermiculitic rather than smectitic. The K-fixed interlayers and expandable interlayers in these samples appear to be similar in charge. The significantly higher charges inferred for the highly illitic samples can be consistent both with a layer-by-layer transformation and the neoformation mechanisms proposed in the literature for the formation of illite.

Fine-grained biotite crystals within primary actinolite from a quartz monzonite body of the Bingham Canyon porphyry copper deposit, Utah, consist of 1M, 5M1, and 1Md polytype structures. HRTEM images directly show the stacking sequences of ordered biotite polytypes, stacking faults in ordered polytypes, and stacking sequences in disordered polytypes, if the stacking vectors for the 2:1 layers involve only 0° and ± 120° rotations. The most common type of stacking fault in the 1M biotite is a layer with −120° rotation, followed by a layer with +120° rotation, which corresponds to one unit cell of the 2M1 polytype inserted in the 1M structure. Disordered (or semi-random) biotite is composed primarily of thin domains of the 1M and 2M1 polytypes, with stacking faults. The structure of a new 5-layer (5M1) polytype has been determined from SAED and HRTEM results. The stacking sequence of the polytype is [02022].

A model of structural oscillation among 1M, 2M1, and 3T structural states is proposed to interpret nonperiodic stacking sequences in biotite crystals formed during non-equilibrium crystallization. The model also provides qualitative insights into the structure of complex long-period polytypes and may help to explain intergrowths of ordered and disordered polytypes that form during crystallization far from the equilibrium state.

The correlation between illite/smectite (I/S) diagenesis and mean vitrinite reflectance (Ro) data is examined in mudrocks from a hydrocarbon exploration well (geothermal gradient 35°C km−1) from the Great Hungarian Plain of the Pannonian Basin System. The expandability of I/S decreases with depth and there is a change from random to ordered mixed-layering at about 2500 m depth. At this depth Ro is about 0.6%. Comparison of the correlation of expandability and Ro from this study to published data for the Vienna Basin and the Transcarpathian Basin, sub-basins of the Pannonian Basin System, shows that the correlation is systematically different for each sub-basin, according to their thermal histories. In the Vienna Basin (geothermal gradient 25°C km−1), for any given value of Ro, the expandability of I/S is less than in the Transcarpathian Basin (geothermal gradient 55°C km−1) and the sediments are older and more deeply buried. Data from the present study are intermediate. This variation is believed to be due to the effect of time on the smectite-to-illite reaction. Results of an optimization procedure to calculate the kinetics of the smectite-to-illite reaction, using as input the expandability depth profiles, and thermal histories constrained by comparison of observed and calculated Ro data, showed that I/S diagenesis in the Pannonian Basin System can be modelled by a single first order rate equation:

$-dS/dt=e^{log(A)-E/RT}\cdot S$

Transformation of montmorillonite was experimentally investigated using a model system of montmorillonite-alanine at 100 MPa and up to 500°C. Sodium-montmorillonite changed to a mixed layer mineral of sodium- and ammoniumn-montmorillonites (Na/NH4-Mnt) in the temperature range from 150 to 400°C. Ammonium ions were the decomposition product of alanine above 150°C. The Na/NH4-Mnt transformed to regularly and randomly interstratified minerals of NH4-montmorillonite and NH4-mica (o. NH4-Mnt/NH4-Mic and d. NH4-Mnt/NH4-Mic) at 400°C. These mixed layered minerals transformed to ammonium-mica at 500°C. Ammonium-analcime appeared and coexisted with the smectites at temperatures over 200°C, and with albite for those over 400°C.

In comparison with the results of previous experiments in which there was no organic component, the present results revealed that (1) some uncommon mineral phases appeared by replacement of sodium ions in montmorillonite with ammonium ions, i.e., NH4-Mic, o. and d. NH4-Mnts, o. and d. NH4-Mnt/NH4-Mics, and (2) ammonium-analcime appeared. The mineral assemblages and alteration sequences correspond better with those observed in the natural system than those known from experimental results in aluminosilicate-water system.

The vibrational modes of clay minerals are uniquely accessible to FT Raman spectroscopy, but this potentially powerful technique has found limited application to the study of clay mineral structure. Raman spectra in the 50 to 3800 cm−1 region were obtained for a number of kandite clays. The kandite clay minerals are characterised by relatively intense bands centred at 142.7 cm−1 for kaolinite, 143 cm−1 for halloysite and 131.2 cm−1 for dickite with prominent shoulders at 129, 127, and 120 cm−1 respectively. These vibrational modes are attributed to the O-Al-O and O-Si-O symmetric bends. Differences in the lattice modes for the kandite clay minerals in the 200 to 1200 cm−1 were obtained. Four OH bands were obtained for kaolinite 3621, 3652, 3668, and 3695 cm−1; three OH bands were found for a selection of dickites and halloysites. The San Juan Dickite and the Eureka Halloysite show further resolution of the low frequency 3620 cm−1 hydroxyl band. This splitting is attributed to variation in the position of the inner hydroxyls. Variation in band intensity and position was found to be sample dependent.

This work investigates unit cell dimensions, crystal size and specific surface area of aluminous goethite that was progressively dehydroxylated to form hematite. Goethite synthesized from the ferrous system altered to hematite with DTGA maximum increasing from 236° to 273°C for 0 to 30.1 mole % Al-substitution. Unit cell dimensions of goethite and hematite decreased as Al-substitution increased and increased as excess OH increased. The crystallographically equivalent a axis of goethite and c axis of hematite were more sensitive than other axes to the presence of excess structural OH associated with Al-substitution. Specific surface area increased from 147 to 288 m2/g for goethite and from 171 to 230 m2/g for hematite as Al-substitution increased. An increase in specific surface area on heating goethite at temperatures between 200° and 240°C is related to a decrease in the size of coherently diffracting domains of goethite crystals and to the development of pore and structural defects associated with the formation of hematite. The decrease in specific surface area for heating temperatures above 240°C is attributed to the growth of hematite crystals by diffusion.

Experimental alteration of obsidian with HCl solution was performed to elucidate dissolution mechanism and formation process of clay minerals in acid solution. Reactions were carried out using 0.1, 0.5, and 4.0 g of obsidian to 100 ml of 0.01 N HCl solution at 150° and 200°C for 1 to 60 days. The reaction products were examined by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy (TEM), and energy dispersive X-ray analysis. The surface composition of obsidian before and after alteration was investigated by X-ray photoelectron spectroscopy (XPS). TEM showed that boehmite precipitated at early stage and spherical kaolinite appeared subsequently by 200°C reactions. However, spherical halloysite occurred predominantly with small amounts of allophane, boehmite, and kaolinite by 150°C reaction in which formation process of the halloysite from allophane passing through an intermediate phase of small size rounded aggregate that consists of fine particles of allophane was observed. A boehmite exhibiting hexagonal platy habit with higher degree of crystallinity was formed by 200°C reaction as a stable phase in solution containing lower Si concentration at which the solution composition coincides with the stability field of boehmite on activity diagram for the system Na2O-Al2O3-SiO2-H2O. The fibrous boehmite having lower crystallinity appeared with increasing Si concentration, considered as a metastable phase in the stability field of kaolinite. XPS indicated that dissolution of obsidian in acid solution proceeded initially by cation exchange between Na ions and hydronium ions in solution and subsequently by preferential release of Al ions relative to Si from the Na depleted surface.

Intercalation complexes of a Hungarian kaolinite were prepared with hydrazine and potassium acetate. The thermal behavior and decomposition of the kaolinite-potassium acetate complex was studied by simultaneous TA-EGA, XRD, and FTIR methods. The intercalation complex is stable up to 300°C, and decomposition takes place in two stages after melting of potassium acetate intercalated in the interlayer spaces. Dehydroxylation occurred, in the presence of a molten phase, at a lower temperature than for the pure kaolinite. FTIR studies revealed that there is a sequence of dehydroxylation for the various OH groups of intercalated kaolinite. The reaction mechanism was followed up to 1000°C via identification of the gaseous and solid decomposition products formed: H2O, CO2, CO, C3H6O, intercalated phases with basal spacings of 14.1 Å, 11.5 Å, and 8.5 Å as well as elemental carbon, K4H2(CO3)3 · 1.5H2O, K2CO3 · 1.5H2O, and KAlSiO4.

The influence of surfactants on the flow behavior of sodium montmorillonite dispersions (2% w/w) was studied for a cationic (cetylpyridinium chloride, CPCl) and an anionic surfactant (sodium dodecylsulfate, SDS). When the dispersion pHs were >3.5 and <7, CPCl concentrations >10−4 M increased the shear stress but the Bingham yield value remained virtually unchanged (τo ≈ 100 mPa). At pH ≈ 7, the shear stress and yield point decreased with increasing CPCl concentration (τo from 430 to 100 mPa). The flow properties of sodium calcium bentonite dispersions were independent of pH and CPCl concentrations ≤ 10−4 M; they increased modestly at higher concentrations. At pH < 4, SDS addition to the sodium montmorillonite dispersions increased the shear stress and yield value to a maximum value (τo = 2100 mPa) at 10−3 M SDS; higher SDS concentrations reduced the shear stress and yield value. At pH > 4, the flow values decreased to a minimum value at 10−2 M SDS (τo from 430 to 50 mPa). The flow of the sodium calcium bentonite dispersions at pH > 4 was independent of SDS concentrations ≤ 10−3 mole/liter; at higher SDS concentrations, the flow values increased more strongly in sodium calcium bentonite than in sodium montmorillonite dispersions.

Surfactants influence the flow behavior of sodium montmorillonite dispersions by their action on the card-house networks in strongly acidic medium and, at higher pH, by the electroviscous effect. At the highest surfactant concentrations without flocculation, the shear stress and yield value are increased by interacting chains of opposed particles.

Addition of the surfactants increases the salt (NaCl) stability of the dispersions because the adsorbed surface active agents influence the counterion distribution between the Stern and the diffuse ionic layer.

Estimations of the external specific surface areas (S.S.A.) by the N2-BET method of clay separates that were further fractionated by the high gradient magnetic separation technique revealed that the magnetic fractions had consistently lower S.S.A. compared to non-magnetic fractions. This phenomenon has been attributed, in the past, to the intimate association of Fe-oxides with silicate clays. It is the contention of this study that this reasoning is insufficient due to the following reasons. X-ray diffractograms (XRD) confirmed that heavy minerals were abundant in the magnetic fractions of these clays. Total chemical analyses and energy dispersive X-ray analyses showed that these heavy minerals contained Fe and Ti, which were not completely extracted by the dithionite-citrate bicarbonate (DCB) treatments. Crystallinity and quantity of these oxides in the different fractions did not show any relationships with the S.S.A. Lower S.S.A. were found in the magnetic fractions of both coarse and fine clays in the untreated as well as DCB-treated samples. The average particle density of the magnetic fractions was found to be higher than the non-magnetic fractions, resulting in an underestimation of the S.S.A. This underestimation was further proven when clay-sized illmenite (density = 4.79 Mg m−3) was found to have lower S.S.A. than quartz (density = 2.65 Mg m−3) and well-crystallized Georgia kaolinite (density = 2.61 Mg m−3), even though the illmenite particles were smaller in size compared to the kaolinite particles and similar in size compared to the quartz particles. It is, therefore, proposed that the specific surface areas should be expressed either on a volumetric basis or corrected for differences in density to avoid underestimations when heavy minerals are present in the samples.

Using theoretical profiles of diffracted X-ray intensity for interstratification between layers having d-spacings around 14.3 Å and 10.1 Å, a series of diagrams was derived from which the proportion of 14.3 Å layers (W14) and the probability of passing from a 14.3 Å layer to a 10.1 Å layer (P14/10) can be derived. W14 can be derived independently of P14/10 using the angular distance between reflections situated at 18.2° and 25.4° 2θ (CuKα). Once W14 is determined, P14/10 may be obtained using the angular width of the diffuse reflections between 27° and 34° 2θ. In this case, two different diagrams are proposed for P14/10 determination because experimental X-ray patterns show either one or two diffuse reflections. Comparison of five experimental patterns with theoretical patterns calculated using W14 and P14/10 obtained using these diagrams indicates that the method can be useful for determining W14 and P14/10 in unknown samples. Moreover, the method described is independent of the Lorentz polarization factor and the layer type. The d-spacings associated with the two kinds of layers, however, should be similar (± 1%) to those for which the determinative diagrams were calculated.