In the chemical system Na2O-Al2O3-SiO2-H2O, the stability field of Na-beidellite is presented as a function of pressure, temperature, and Na- and Si-activity. Na0.7-beidellite was hydrothermally synthesized using a stoichiometric gel composition in the temperature range from 275° to 475°C and at pressures from 0.2 to 5 kbar. Below 275°C kaolinite was the only crystalline phase, and above about 500°C paragonite and quartz developed instead of beidellite. An optimum yield of 95% of the Na0.7- beidellite was obtained at 400°C and 1 kbar after 20 days. Gels with a Na-content equivalent to a layer charge lower than 0.3 per O20(OH)4 did not produce beidellite. They yielded kaolinite below 325°C and pyrophyllite above 325°C. With gels of a Na-content equivalent to a layer charge of 1.5, the Na-beidellite field shifted to a minimum between temperatures of 275° and 200°C. This procedure offers the potential to synthesize beidellite at low temperatures. Beidellite synthesized from Na1.0-gel approach a Na1.35 composition and those from Na1.5- and Na2.0-gels a Na1.8 composition.

Factors that are potentially important in the pulmonary pathogenesis of asbestos and other mineral particles are: 1) morphology, 2) Fe-content, 3) solubility under intraphagosomal conditions, 4) value and sign of the surface potential of the particle, 5) hydrophobicity or hydrophilicity, 6) capacity to activate phagocytic leukocytes, and 7) duration of exposure to the particles. The order of importance of these factors in causing severe or fatal pulmonary pathogenicity is estimated to be: 1 > 3 > 7 > 6 ≫ 5 > 4 > 2. The order of pathogenicity of the minerals is estimated as: amphibole asbestos: crocidolite, tremolite, amosite > erionite > serpentine asbestos: chrysotile > talc > silica > simple metal oxides. Particle length, duration of exposure to the particles, and pre-treatment of the particles may however enhance the pathogenic potential of any of the lower-ranked particles.

Hydrothermal synthesis experiments were conducted to study the transition from smectite to corrensite. A mixture of oxides with the bulk composition of corrensite—Na0.4(Si6.4Al1.6)(Mg7.8Al1.2)-O20(OH)10—was sealed in platinum capsules with 29–37 wt. % water. One set of samples was treated in cold-seal vessels at 500°C and 2 kbar for durations of 2, 3, 6, 12, and 24 h; the other set was treated at 350°C and 2 kbar for periods of 12 to 89 d. X-ray diffraction patterns (XRD) of oriented aggregates from treated products were obtained from ethylene glycol-solvated and air-dried preparations. Samples were also heated to 350°C either in a calibrated muffle furnace, removed and quickly placed in a nitrogen filled chamber on the diffractometer, or were heated at 350°C by using a calibrated heating stage mounted on the diffractometer.

Initial mineral assemblages at both temperatures contained only saponite and serpentine. In experiments at 500°C, saponite transformed to corrensite within 6 h; in experiments at 350°C, the transformation occurred as early as 22 d. Increased experiment times at both temperatures produced increasing amounts of well-crystallized corrensite, as indicated by several well-defined XRD peaks. No evidence of a randomly interstratified chlorite-smectite (C-S) precursor to corrensite was found. The identification of pure smectite, as opposed to highly-expanded randomly interstratified C-S, was possible only when clays were dehydrated on a heating stage on the diffractometer.

These results call for a new examination of hydrothermally-altered basalt that has been reported to contain randomly interstratified C-S as an intermediate step in the reaction of smectite to corrensite or chlorite. These results also strengthen the view held by increasing numbers of investigators that corrensite should be regarded as a single phase, not as a mixed-layered phyllosilicate.

Competitive adsorption between phosphate, tartrate and oxalate was studied on two hydroxy aluminum montmorillonite complexes (AlMt1.6 and AlMt6), which were prepared by adding a base to pH 5.5 to samples containing 1.6 and 6.0 mol Al per kg clay. The quantities of phosphate, tartrate and oxalate adsorbed were more closely related to the amount of OH-Al species coatings on the montmorillonite than to the surface area of the complexes. The adsorption capacity of phosphate was much greater than that of tartrate or oxalate for both samples. Adding molar amounts of oxalate and tartrate resulted in an oxalate/tartrate adsorption ratio (Rf) of ∼1. However, in the presence of phosphate, Rf values were <1.0, and the Rf values decreased with increasing amounts of added phosphate, indicating that tartrate competed with phosphate more effectively than oxalate. The presence of tartrate also reduced phosphate adsorption by the complexes. The efficiency of tartrate in reducing phosphate adsorption increased by increasing the initial tartrate/phosphate molar ratio and by adding tartrate 2 h before phosphate addition. Tartrate and oxalate added as a mixture in equimolar quantities were much more effective in inhibiting phosphate sorption than tartrate alone under the same organic ligand concentrations, probably because more sites with high affinity for both the organic ligands were occupied by tartrate and oxalate than by tartrate alone. The efficiency of tartrate alone, or combined with oxalate, in preventing phosphate adsorption was greater for the complex containing a lesser amount of OH-Al species coating the montmorillonite surfaces. This result may be attributable to a greater proportion of sites specific for organic ligands present on AlMt1.6 compared to AlMt6 complex.

Ce/Al- and La/Al-pillared smectites were prepared by cation exchange of bentonite, saponite and laponite with hydrothermally treated (130–160 °C for 16–136 h) solutions containing mixtures of aluminumchlorohydrate (ACH) and Ce3+-/and La3+-salts. After calcination at 500 °C, the pillared products are characterized by basal spacings between 24.8 and 25.7 Å and surface areas of approximately 430 m2 g−1. The products are hydrothermally stable at 500 °C after 2 h in steam. The large basal spacings are due to the formation of a large Ce/La-bearing Al-polyoxocation, whose formation is favored by initially high Al concentrations ≥3.7 M and an OH/Al molar ratio of approximately 2.5. The Ce/Al or La/Al molar ratios can be as low as 1/30. 27Al nuclear magnetic resonance (NMR) spectroscopy has shown that the polyoxocation has a higher Altetrahedral/Aloctahedral ratio than the Keggin structure Al13, which may partly explain the higher stability compared to normal Al-pillared clays. Hydroconversion of n-heptane indicated that the activity of the Pt-loaded pillared products is higher than that of a conventional Pt-loaded amorphous silica-alumina catalyst. Selectivity is strongly dependent on the type of starting clay and its acidity. In industrial hydrocracking of normal feedstock, a Ni/W-loaded Ce/Al-pillared bentonite catalyst showed rapid deactivation due to coke-formation reducing the surface area and the pore volume. Additionally, coke-formation is facilitated by the relatively high iron content of the pillared bentonite (3.43 wt% Fe2O3).

Smectite and mixed-layer illite/smectite (I/S) in Triassic heulandite-rich bentonite from Kaka Point, New Zealand, have been investigated by scanning electron microscopy (SEM), transmission electron microscopy/analytical electron microscopy (TEM/AEM) and X-raydiffraction (XRD) for comparison with matrix phyllosilicates in closely associated siltstones and analcimized tuff. Samples that were treated to achieve permanent expansion showed that some smectite in bentonite occurs as curved packets of wavy 10.5- to 13-Å layers enveloping relict glass shards, the centers of which consist of an amorphous clay precursor. The dominant clay minerals in bentonite are smectite-rich randomly disordered (R0) I/S with variable proportions of 10-Å illite-like interlayers, only locally organized as 1:1 ordered (R1) I/S. R0 I/S was also observed in separate packets retaining the detailed texture of packets that replaced shards. Such relations are consistent with a “solid-state”-like, layer-by-layer replacement of original smectite layers by illite-like layers with partial preservation of the primary smectite texture, in contrast to textures observed elsewhere, such as in Gulf Coast mudstones. The smectite, as in other examples in marine sediments, has K as the dominant interlayer cation, suggesting that precursor smectite may be a major K source for reaction to form illite.

Only a small proportion of illite (35%) occurs in mixed-layer smectite-rich I/S in bentonite and the dominant trioctahedral phyllosilicate is disordered high-Fe berthierine, implying that little mineralogical change has occurred with burial. This contrasts with observations of closely associated siltstones and analcimized tuff, which contain well-defined packets of illite and chlorite but which have no detectable matrix smectite component. These data imply that the rate of transformation of smectite to illite is much slower in bentonites than in associated sediments of the same burial depth and age. Such relations emphasize the significance of factors other than temperature, (e.g., organic acids, permeability and pore fluid compositions) in affecting the rate and degree (and perhaps mechanism) of transformation of smectite to illite.

The structure of a highly disordered synthetic birnessite was studied by comparing powder X-ray diffraction (XRD) data with calculated patterns generated by BIRNDIF and WILDFIRE© in an attempt to describe the nature of disorder and to estimate the size of the coherent diffracting domains. The material has a turbostratic stacking sequence and coherent diffracting domains that are 25 to 30 Å on a side in the ab plane (N1 = 5 unit cells, N2 = 10 unit cells) and which average 2.5 unit cells thick parallel to c. Turbostratic stacking probably results because there are few constraints on the relationship between adjacent layers.

In studies on the fate of aluminium in the environment, nontronite and saponite have been obtained by synthesis in reducing alkaline conditions close to those prevailing in poorly drained soils developed from limestones. The two minerals obtained have different structures and organizations corresponding to two different growth and/or maturation mechanisms. High-resolution transmission electron microscopy of ultrathin sections of a synthetic aluminous nontronite embedded in resin showed the presence of crystallites consisting of two to ten co-terminating parallel layers, indicating synchronous growth. Electron diffraction showed that the individual crystallites had hk-ordering, i.e., orientation of layers with respect to the six-fold pseudosymmetry of the unit cell. Deposits of a synthetic saponite included hk-ordered crystallites and crinkled films with turbostratic stacking. The two saponite phases had slightly different b dimensions. Lattice fringe images of sections of saponite embedded in resin showed a high angular disorientation of the layers in the stacking direction, suggesting multiple nucleation and growth of individual layers, subsequently aggregated with imperfect parallelism.

Exploration of the synthetic conditions of the aluminous nontronite indicated that calcium was essential for an hk-ordered product. Syntheses using potassium or sodium hydroxides and carbonates for pH control gave poorly organized nontronites. Hydrazine was not essential for nontronite formation, but better crystallized products—judging by their IR spectra—were obtained in its presence by maintaining reducing conditions in the early stages of synthesis. Attempts to prepare ferruginous beidellites under similar conditions to those in which aluminous nontronites formed were unsuccessful.

The rheological behavior of concentrated lateritic suspensions from Cuba is affected by mineral composition and particle size. Electrophoretic mobility and yield stress were considered. The lateritic samples were found to be mostly composed of mixtures of serepentine and goethite in varying proportions. The flow properties of the lateritic suspensions are strongly affected by the mineral composition and particle size. This result was determined by comparison of flow properties of the bulk sample and the colloidal fraction. The electrokinetic curves suggest that heterocoagulation is present in all samples, with a zeta potential minimum at the isoelectric point (IEP), which varies with the serpentine to goethite ratio. A relationship between yield stress (τ0) and the sample volume fraction (ϕ) and particle size (d) was obtained at the IEP from the expression τ0 = kϕ3/d0.5, with the constant k dependent on the sample serpentine to goethite ratio.

Weathering products formed on the surface of K-feldspar in Yakushima Island, Japan were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS). XRD confirmed that the weathering products were composed mainly of gibbsite and halloysite. SEM, TEM and EDX clearly showed formation of amorphous aluminum hydroxide exhibiting 2 distinct habits: 1) curled fibrous or circular forms less than 0.02 μm in diameter; and 2) a spherical habit less than 1.0 μm in diameter. The fibrous aluminum hydroxide exhibited curled fibrous forms or circular forms less than 0.02 μm in diameter and gave a diffuse electron diffraction halo. EDX indicated that the material consisted mainly of Al and very small amounts of Si and Fe. The spherical aluminum hydroxide also gave similar EDX and electron diffraction characteristics to the fibrous material. These fibrous and spherical aluminum hydroxides must be formed as a metastable phase in the earliest weathering stages, and transformed into a stable phase of gibbsite and halloysite as the reaction proceeded.

Members of an alunite-natroalunite solid solution series occur in intimate association with hydrated halloysite in deposits within caves of the Guadalupe Mountains, namely Carlsbad Cavern and Lechuguilla Cave. The alunite and natroalunite crystals consist of cube-like rhombs; crystal diameters range from 0.5 to 8 µm. This mineral association is found in sediments within bedrock pockets, solution cavity fills, floor deposits and wall residues. Sulfur stable isotope values (δ34S, CTD) for cave alunite and natroalunite are negative [+0.1 to −28.9 per mill (‰); n = 12 and mean = 16.8‰] and are comparable to the cave gypsum and native sulfur values reported by other investigators. The association of alunite/natroalunite with hydrated halloysite in these cave deposits suggests that the cave-forming waters contained significant concentrations of sulfuric acid. Formation of these minerals is related to the excavation of the carbonate rocks that formed Carlsbad Cavern, Lechuguilla Cave and other caves of the Guadalupe Mountains. The sulfuric acid-bearing waters, when exposed to clay-rich sediments, converted clay minerals and quartz to alunite/natroalunite and hydrated halloysite.

Formation of Fe-coatings or segregation at the expense of quartz grains is a common process in the tropical environment. Limited information is available about their internal structure at the submicroscopic level. The transmission electron microscope (TEM) and energy dispersive X-ray microprobe analyses (EDXRMA) techniques were used to identify the nature and arrangement of fundamental mineral particles within the Fe-coatings. Chemical and mineralogical studies showed that the coatings were composed of well-crystallized Fe-oxides, quartz and kaolinite. The EDXRMA analyses revealed the presence of linear concentrations (laminae) of nearly pure Fe oxide along the edges and the contact zone with quartz and within the coatings. Similar atomic proportions of Al and Si in several areas within the interior regions of coatings and the XRD pattern of the crushed coatings are supportive evidence for the presence of kaolinite. Under the TEM, the dense laminae (< 10 μm thick) consisted of elongated Fe-oxide particles (< 1.5 μm long and 0.2 μm thick) accommodated in subparallel arrangement. The interior areas had very high porosity and, in addition to Fe-oxides, contained other minerals: mainly kaolinite, quartz and isolated areas of Al-oxides. High amounts of ultramicroscopic pores (<0.5 μm) in the interior region suggested that dissolution of Fe-oxides occurred under reduced conditions, with subsequent reprecipitation of pure Fe-oxides in the laminae. Very low porosity and parallel arrangement of Fe-oxide particles (laminae) provided new surfaces (barrier) for Fe-accumulation when soil solutions provided new influxes of iron, thereby creating a thicker Fe-coating. The size and geometry of the ultramicroporosity were shown to play a significant role in the dissolution and precipitation of soil minerals, especially those involved in redox reactions.

The pink clays from the Tagus basin, Spain, were characterized by X-ray difraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Chemical data were obtained by plasma emission spectroscopy and analytical electron microscopy (AEM), and specific surface and cation-exchange capacity were measured also. The data indicate that these pink clays are primarily stevensite. This Mg-rich smectite is characterized by poor crystallinity, a high degree of structural disorder, trioctahedral character (pure magnesian), a very low cation-exchange capacity, a very small crystal size (which generates an abnormally high specific surface area), and a deficiency of octahedral cations. On the basis of the very small crystal size, a large number of edge dislocations, the lack of periodicity (turbostratic) in the structure, and a cellular (spherical) texture observed by TEM, we consider this occurrence to be an early stage of crystallization. Unlike other precursor clay materials described in the literature, this clay is not an alteration of volcanic ash, but it was generated by precipitation from a Si- and Mg-saturated medium.

A well-characterized kaolinite has been hydrated in order to test the hypothesis that platey kaolinite will roll upon hydration. Kaolinite hydrates are prepared by repeated intercalation of kaolinite with potassium acetate and subsequent washing with water. On hydration, kaolinite plates roll along the major crystallographic directions to form tubes identical to proper tubular halloysite. Most tubes are elongated along the b crystallographic axis, while some are elongated along the a axis. Overall, the tubes exhibit a range of crystallinity. Well-ordered examples show a 2-layer structure, while poorly ordered tubes show little or no 3-dimensional order. Cross-sectional views of the formed tubes show both smoothly curved layers and planar faces. These characteristics of the experimentally formed tubes are shared by natural halloysites. Therefore, it is proposed that planar kaolinite can transform to tubular halloysite.

Alumina-pillared montmorillonite is prepared by intercalation of polyoxyhydroxy aluminum cations (Al137+) of a natural montmorillonite from Dimitrovgrad, Bulgaria. Transmission electron microscopy, powder X-ray diffraction, energy dispersive X-ray spectroscopy, and surface area (BET) methods are used to study the untreated and pillared forms of the montmorillonite. A structural model involving deformed Al13 pillars is proposed. Four pillar types are derived and these pillars are uniformly distributed over the interlayer-cation positions of montmorillonite. Calculated electron diffraction patterns were simulated using the multi-slice method. The structural model explains the increased ordering along the c axis of the pillared form compared with the untreated montmorillonite. The model explains the structure of a pillared montmorillonite with different distributions of the pillars in the interlayer. The proposed model is consistent with the observed data.

The uptake of Sr and Cs by 2 types of aluminum pillared layered clays (Al-PILC), a reference sample (AZA) and a specially tailored sample (FRAZA), were investigated. The AZA sample was prepared from air-dried precursors and the FRAZA sample from freeze-dried precursors. X-ray diffraction (XRD), pore and grain size measurements revealed that freeze-drying leads to a very fine-grained material with substantial mesoporosity. In contrast, air-drying results in coarse grains and an essentially microporous material. Four different methods were tested for restoring the cation exchange capacity (CEC) of the prepared PILCs. The most effective method proved to be exposing the material to ammonia fumes, then soaking it in a NaCl solution at pH =10. Strontium and Cs kinetic experiments were carried out with PILCs after restoring their CEC by this method. The results revealed 1 fast uptake component in both materials but with different relaxation times for each PILC.

Electroacoustic measurements at 1 MHz, using the Electro-Sonic Amplitude (ESA), on a kaolinite suspension provide a ready method for following the adsorption of hydrolyzable metal ions onto the clay surface. Co2+, Cd2+ and Cu2+ ions show similar behavior: The initially negative surface becomes less negative, approaches zero, and may become positive at pH values around neutral, depending on the initial metal concentration. At higher pH, electrokinetic potential goes through a maximum. If the surface has become positive, it becomes less so; and at still higher pH values it may become negative again, depending on the metal ion concentration. The behavior can be interpreted using the model proposed by James and Healy.

The surface microtopography of hematite over the course of dissolution in oxalic and citric acids was examined by in-situ and ex-situ atomic-force microscopy. In-situ imaging of the basal-plane surface of a centimeter-scale natural hematite sample immersed in 2 mM citric acid demonstrated that the basal-plane surface was relatively unreactive; rather, dissolution occurred along step edges and via etch-pit formation. Ex-situ imaging of synthetic hematite particles following batch dissolution in 1 mM oxalic acid showed similar dissolution features on basal-plane surfaces; in addition, etching along particle edges was apparent. The presence of etch features is consistent with a surface-controlled dissolution reaction. The results are in agreement with previous investigations suggesting that the basal-plane surface is relatively unreactive with respect to ligand exchange. Both in-situ and ex-situ imaging of particle surfaces can provide valuable information on the roles of surface structures and microtopographic features in mineral dissolution.

Lath-shaped hydrothermal illite particles in Izumiyama pottery stone were examined by contact-mode atomic force microscopy (CMAFM) and tapping-mode AFM (TMAFM) in air. With CMAFM, the lath-shaped particles showed interlacing patterns on the (001) surface in deflection images, while in height images such patterns were unclear. Also, evidence of artifacts caused by frictional forces between the surface and tip and/or edge effects were found in the CMAFM height images of the particle and Si substrate surfaces. In contrast, TMAFM showed interlacing patterns clearly in both amplitude and height images, and artifacts were barely evident. The TMAFM height images permitted the accurate measurement of 1.0- or 2.0-nm height steps corresponding to single or double mica layers, as well.

Many lath-shaped particles in the Izumiyama hydrothermal illite exhibit interlacing patterns on their (001) surface, as shown by these AFM observations. The interlacing patterns are characterized by polygonal spirals with comparatively wide spacings and steps having a height of 1.0 or 2.0 nm. Generally a single lath-shaped particle has a single spiral center on the (001) surface, and 2 mica layers rotated 120° originate from the dislocation point. These support the view that lath-shaped illites belong to the 2M1 polytype. It is likely that these illite particles were formed by a uniform process of development that is characterized by very slow growth, spiral mechanisms in that growth and low supersaturation conditions.