Compositional data for 464 clay minerals (2:1 type) were analyzed by statistical techniques. The objective was to understand the similarities and differences between the groups and subgroups and to evaluate statistically clay mineral classification in terms of chemical parameters. The statistical properties of the distributions of total layer charge (TLC), K, VIAl, VIMg, octahedral charge (OC) and tetrahedral charge (TC) were initially evaluated. Critical-difference (P = 1%) comparisons of individual characteristics show that all the clay micas (illite, glauconite and celadonite) differ significantly from all the smectites (montmorillonite, beidellite, nontronite and saponite) only in their TLC and K levels; they cannot be distinguished by their VIAl, VIMg, TC or OC values which reveal no significant differences between several minerals.

Linear discriminant analysis using equal prior was therefore performed to analyze the combined effect of all the chemical parameters. Using six parameters [TLC, K, VIAl, VIMg, TC and OC], eight minerals groups could be derived, corresponding to the three clay micas, four smectites (mentioned above) and vermiculite. The fit between predicted and experimental values was 88.1%. Discriminant analysis using two parameters (TLC and K) resulted in classification into three broad groups corresponding to the clay micas, smectites and vermiculites (87.7% fit). Further analysis using the remaining four parameters resulted in subgroup-level classification with an 85–95% fit between predicted and experimental results. The three analyses yielded D2 Mahalanobis distances, which quantify chemical similarities and differences between the broad groups, within members of a subgroup and also between the subgroups. Classification functions derived here can be used as an aid for classification of 2:1 minerals.

Very unusual rocks consisting of natrolite (>95 vol.%) ± pargasite (<5 vol.%) and rarealbite (<1 vol. %) have been discovered in the Kop mountain range, eastern Turkey. We propose to call these rocks ‘natrolitite’ and ‘pargasite natrolitite’. They were produced by Na Si metasomatism of dikes and stocks of diorite through replacement of the intermediate primary igneous plagioclase to produce natrolite. The metasomatic alteration produced concentric elliptical zones characterized by distinct mineral assemblages centered on intrusions of diorite. The Central Zone 1 consists of variably albitized diorite with preserved magmatic textures (albite ± andesine ± pargasite ± quartz). Transition Zone 2 comprises natrolite-bearing diorite (natrolite ± albite ± andesine ± pargasite ± calcite ± quartz). Marginal Zone 3 is a rock made up almost entirely of natrolite (natrolite ± pargasite ± albite ± calcite ± chlorite). Outer Zone 4 occurs along the boundary between the natrolitite and the surrounding serpentinite and consists of listvenite, a rock which comprises magnesite, quartz, calcite, mica, talc, and hematite, indicating a role for CO2 in the metasomatic reactions, consistent with the presence of calcite in the alteration zones. Zone 5 consists essentially of brecciated serpentinite with numerous hydrothermal quartz veins and calcite veins. Whole-rock compositions document an increase in Na2O, Al2O3, and H2O from the core (central zone) to themargin while CaO, MgO, and SiO2 decrease. Plagioclase abundance and composition also varies outwards from the central core rocks where it occurs as a primary magmatic phase (∼95 vol.% An41−38) to the alteration zones (<5 vol.% An32−37) due to partial to complete replacement of plagioclase by natrolite with or without rare albite. The natrolites exhibit little variation in Si/Al ratios, ranging between 1.45 and 1.61, and are similar in composition to those reported in the literature. Accompanying pargasitic amphibole also becomes progressively more sodic in composition from the core rocks to the marginal zone rocks. Our analysis indicates that albitization preceded the formation of natrolite and that the formation of natrolite, instead of other more typical alteration minerals (e.g. analcime and paragonite), reflects Na metasomatism at lower chemical potentials for Al2O3 and SiO2. Potential sources of Na could be hypersaline brines or leaching of country rocks, such as trondhjemites. The fluids were driven in hydrothermal convection cells set up by theintrusion of thediorites.

Homoionic samples of four montmorillonite clays, selected on the basis of the properties which control their economic uses, were prepared by treating with two normal neutral solutions of ammonium acetate, lithium, sodium, potassium, calcium, and magnesium chloride. Atterberg plastic and liquid limits, slopes of the liquid limit curves, and water sorption curves were determined. Among the results suggested, the following are particularly considered:

1. 1. The plastic state is reached when enough water is put into the system to fill all the pore space and to supply all the montmorillonite layers with water adequate for rigid layers plus a slight additional amount.

2. 2. The type of cation is not the only factor which controls the properties of montmorillonite.

3. 3. The structure of the lattice also appears to determine the properties of montmorillonite.

Imogolite is a hydrous aluminium silicate mineral (Cradwick et al., 1973) with a fibrous morphology and low degree of structural order, which, since first described by Y oshinaga and Aomine (1962), has been reported to occur as a weathering product of pyroclastic materials in many localities. However, Wada et al. (1972) have recently drawn attention to the fact that imogolite occurs in gels derived from massive, though jointed, basalt in Hawaii. The purpose of the present note is to describe the identification of imogolite in some very young volcanic ash soils from New Guinea-a finding that has important genetic implications.

The rates of K exchange of untreated and peroxide-treated micaceous clays from five Podzol soils of increasing degrees of weathering were determined using sodium tetraphenyl boron. In addition, the amounts of K fixed against NH4 were measured. The Ae horizon clays of these soils contained mainly interstratified mica-vermiculite-montmorillonite whereas the C horizon clays contained mica of a more discrete nature.

As was expected, there was an inverse relationship between rates of K exchange and degrees of weathering of the Ae horizon clays. However, in the samples from each of these soils except in those of the most weathered one, the K exchange rate of the interstratified mica from the Ae horizon was higher than that of the less weathered, more discrete mica from the corresponding C horizon. The abundance of hydrated edges and layers exposing K exchange sites in the Ae horizon micas probably contributed to their higher rates of K exchange. Amounts of K fixed in the Ae horizon clays were not related to degrees of weathering.

Removal of organic matter from the Ae horizon clays by peroxide considerably increased both the rates of K exchanged and the amounts of K fixed. These increases were attributed to the elimination of a blocking effect of adsorbed organic matter on K exchange and fixation.

Injured bone tissues can be healed with bone grafts, but this procedure may cause intense pain to the patient. A slow and localized delivery of nonsteroidal anti-inflammatory drugs (NSAIDs) could help to reduce the pain without affecting bone regeneration. The objective of the present study was to use [Mg-Al]-layered double hydroxide (LDH) as a matrix for controlled release of sodium naproxen (NAP). This system could be applied in biomaterial formulations (such as bone grafts) to achieve a local delivery of naproxen. [Mg-Al]-LDH successfully incorporated up to 80% (w/w) of naproxen by the structural reconstruction route, with the [Mg-Al]-LDH interlayer space increasing by 0.55 nm, corresponding to the drug molecule size. The evaluation of the naproxen release kinetics showed that 40% of the drug was delivered over 48 h in aqueous medium (pH 7.4 ± 0.1), indicating the potential of [Mg-Al]-LDH/NAP for local release of naproxen at adequate concentrations. Kinetic modeling showed that the naproxen release process was closely related to the Higuchi model, which considers the drug release as a diffusional process based on Fick’s law. The chemical stability of NAP after the release tests was verified by 1H NMR. The [Mg-Al]-LDH/NAP also exhibited low cytotoxicity toward fibroblast cells (L929 cell line), without modifications in their morphology and adhesion capacity. These results describe a suitable approach for preparing efficient systems for local delivery of nonsteroidal anti-inflammatory drugs for biomedical applications.

The organization of organic species on the ordered structures of clays and clay minerals is one way to produce inorganic-organic hybrids with controlled microstructures and properties. The reactions of the adsorbed species and their arrangement on the clay surfaces can be guided by the choice of clay and of adsorbed species. The purpose of the present study was to intercalate alkylammonium ions into a Thai bentonite and to study the effect on dye-adsorption efficiency. A series of alkylammonium ions, CnH2n+1NH3+ (n = 8, 10, 12, or 18), was incorporated into the interlayer spaces of a natural bentonite by mixing an aqueous dispersion of bentonite with an aqueous solution of protonated alkylamines at room temperature. The basal spacings of the intercalation compounds varied depending on the alkyl chain lengths and the amount of alkylammonium ions. The alkylammonium ions adsorbed formed lateral monolayer, bilayer, pseudo-trimolecular layer, paraffin-type monolayer, and/or paraffin-type bilayer structures. The adsorption efficiency of alkylammonium-bentonites was determined using batch adsorption experiments of rhodamine 6G from a water-ethanol solution; the greatest efficiency was 87% while that of the bare bentonite was 47%. The loading amount and the arrangement of the intercalated alkylammonium ions in the interlayer spaces, as well as the specific surface area and pore volume, played important roles in the adsorption efficiency of alkylammonium-bentonite. The adsorption equilibrium data for rhodamine 6G on the best adsorbent were interpreted using the Langmuir isotherm model and a pseudo-second order kinetics model. The adsorption efficiency of the adsorbent decreased by only 17% after five runs.

The Crystal Packer module in the Cerius2 modeling environment has been used to study the structure of montmorillonite intercalated with Al(OH)3-fragment (gibbsite-like) polymers. Basal spacings in gibbsite-like polymers arranged in 2 layers in the interlayer of montmorillonite varied in the range 19.54–20.13 Å, depending on the type and arrangement of Al(OH)3 fragments. The inhomogeneous distribution of intercalating species in the interlayer and, consequently, the turbostratic stacking of layers has been found for gibbsite-like polymers as well as in the case of Keggin cations (Čapková et al. 1998). The dominating contribution to the total sublimation energy comes from electrostatic interactions for both intercalating species, gibbsite-like polymers and Keggin cations.

Ludox SiO2 sols with a reasonably uniform size of 12 nm and in the high concentration of 10 to 40 wt% were transformed to gels by lowering the pH. The process from sol to gel, followed by light scattering, did not show a sign of fractal growth within the length scale of observation (>0 nm). Rather, a density fluctuation due to a dynamic (non-equilibrium) disorder was apparent. Together with the results of viscosity measurements, it was concluded that the process consists of 3 stages: 1) A dynamic (non-equilibrium) density fluctuation grows rapidly. 2) Such density fluctuation acquires some order. 3) The entire bulk loses fluidity and becomes a macroscopic gel.

This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays.

The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley” clay).

The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality.

The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay.

Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

A model describing the electric double layers in clay-electrolyte systems containing particles with different surface charge densities was developed and used to calculate the film thickness of water present in a clay paste. The average water film thicknesses (~18 Å) calculated by considering the clay to contain 9 groups of particles of different charge densities did not differ from those calculated by assuming one average charge density; provided the minimum potential between particles remained constant. These values, however, were higher than those obtained from gravimetric water determinations by about 30%. The overestimation of the average thickness of the water films by the theoretical model is most likely due to the assumption of a complete parallel arrangement of particles in the paste and the validity of the Gouy theory for double layers on clays.

The aim of the aqueous electrokinetic experiments in the present study was to assess the relative contribution of the conducting polyindene (PIn) and inorganic colemanite components to the zeta (ζ) potentials of the composite particles, thus providing further insight into their surface composition in the dispersed state and establishing colloidally stable conditions for potential rheological, industrial applications. For this, PIn and a PIn/colemanite composite (containing 5 wt.% colemanite) were synthesized by chemical oxidative polymerization using FeCl3 as an oxidizing agent. Colemanite, PIn, and PIn/colemanite composite samples were characterized by Fourier-transform infrared spectroscopy, elemental analysis, conductivity, dielectric constant, magnetic susceptibility, density, particle-size measurements, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction analysis, and scanning electron microscopy methods. The electrokinetic properties of colemanite and PIn/colemanite composite dispersions were determined by ζ-potential measurements in aqueous medium, taking into account the effects of time, pH, various electrolytes, surfactants, and temperature. The pH was observed to have a greater effect on the ζ potentials of colemanite in water but caused only slight changes in the presence of cationic (NaCl, BaCl2, AlCl3) and anionic (NaCl, Na2SO4) electrolytes. Increased pH values shifted the ζ potentials of PIn/colemanite composite dispersions to more negative values. The most effective surfactant acting on the ζ potentials of colemanite and PIn/colemanite composite dispersions was cetyltrimethylammonium bromide (CTAB), which shifted the ζ potentials to more positive regions. Elevated temperatures caused almost no change to the ζ potentials of either the colemanite or the PIn/colemanite composite dispersions.

Nontronite is a significant component of commercially important nickel laterite ores. Its behavior during high-pressure acid leaching of such ores may have an impact upon the efficiency of the process. The present study was conducted in order to further investigate the response of this material during high-pressure acid leaching. In situ synchrotron powder X-ray diffraction data were collected from a number of nontronite samples during hydration and leaching reactions at ambient and elevated temperatures. The present study followed previous high-pressure acid-leaching studies of nontronite where unexpected contraction and expansion behavior of the clay was observed by means of in situ X-ray diffraction. In the earlier studies the data sets only extended to ~20 Å so that when the nontronite expanded to greater than 19.5 Å (hydrated) the main 001 peak was only partially visible in the observed d-spacing range. The aim of the current work was to collect similar in situ diffraction data over a greater d-spacing range to observe more fully the movement of the main 001 reflection in order to better understand the changes taking place. This work was undertaken at the powder diffraction beamline of the Australian Synchrotron which was configured such that an upper d-spacing limit of ~34.5 Å could be achieved. Suggestions arising out of the previous work were confirmed along with additional information from testing of samples from the Source Clays Repository of The ClayMinerals Society. These results also show contradictory behavior of clays with the layer charge distributed over tetrahedral and octahedral sheets.

In order to develop high-performance adsorbents to remove toxic methylene blue (MB) from wastewater, palygorskite (Plg) was utilized as a template to prepare palygorskite/carbon (Plg/C) composites by using a hydrothermal reaction in the presence of glucose. The porous Plg/C composites were then activated with ZnCl2. The effects of the dose of the activator and the activation temperature on the crystal structure, micro-morphology, specific surface area, and adsorption performance of the porous Plg/C composites were studied systematically here. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results indicated that the crystal structure of Plg was destroyed during the activation process and irregular porous carbon was closely attached to the residual aluminosilicate skeleton. The activation was optimized at 400°C with a ZnCl2:Plg/C impregnation ratio of 2:1. The sample had a specific surface area of 1497.88 m2/g, together with a total pore volume and micropore volume of 1.0355 and 0.5464 cm3/g, respectively. The MB adsorption capacity was 381.04 mg/g. Such inexpensive, high-performance, porous Plg/C composites could find potential applications in wastewater treatment.

“Chloritized” vermiculite coexisting with kaolin-group minerals, vermiculite, mica, and gibbsite in the 0.2–0.5-µM fraction separated from a Korean Ultisol was studied by ultramicrotomy and high-resolution electron microscopy. The (001) lattice images observed from thin sections showed that the “chloritized” vermiculite was composed of particles which differed in their shape and the stacking of silicate layers. On saturation with K+, the silicate layers had spacings of 14–10 Å, with 14–12-Å layers being dominant. The 8–7-Å layers of a few particles appeared to be segregated close to the basal plane surfaces, but not necessarily close to the edge surfaces. The silicate layers were more or less curved and wavy and were commonly discontinuous. They formed packets (100–500 Å thick) by stacking, which were associated “face-to-face” and/or “edge-to-edge” or stacked parallel or subparallel to form particles of different shapes. The extent of interlayer collapse of the 14-Å layers on heating differed from one particle to the other, but was fairly uniform within a particle. Treatment with hot 1/3 M sodium citrate dissolved the interlayer material and possibly the material present between the packets from the “chloritized” vermiculite and from a few fine plates of kaolin-group minerals. The interlayer material and its chemical composition, therefore, could not be determined.

Large hydrothermal deposits of halloysite clay occur in the Terraced Hills, Washoe County, Nevada and similar bodies probably are present elsewhere in the Basin and Range province. The host rock, an andesitic tuff, is underlain and overlain by volcanic flows; all these rocks are late Miocene to Pliocene in age. The clay bodies are composed mostly of halloysite with some iron oxides, variable amounts of feldspar and quartz, and locally some montmorillonite. Commonly all the pyroclastic unit is altered to halloysite material. In one locality, however, the halloysite body is restricted to the upper part and it is in sharp contact with underlying, partly montmorillonitized tuff. The contact of a clay body with the overlying basalt is distinct. Generally some halloysite is present in the lower part of the basalt and montmorillonite occurs in both materials near their contact. The solutions that altered the tuff were generated during volcanism, rose along high-angle faults, and were restricted to the permeable and otherwise favorable vitric tuff by the capping of relatively impermeable basalt.

Because inorganic nanosheets, such as clay minerals, are anisotropic, the manipulation of nanosheet orientation is an important challenge in order to realize future functional materials. In the present study, a novel methodology for nanosheet manipulation using laser radiation pressure is proposed. When a linearly polarized laser beam was used to irradiate a niobate (Nb6O174-) nanosheet colloid, the nanosheet was trapped at the focal point so that the in-plane direction of the nanosheet was oriented parallel to the propagation direction of the incident laser beam so as to minimize the scattering force. In addition, the trapped nanosheet was aligned along the polarization direction of the linearly polarized laser beam.

Illite from Muloorina, just south of Lake Eyre in South Australia, is commonly used as a standard ferric iron-bearing illite which has a cation exchange capacity (CEC) of ~22 meq/100 g, too high a value for this clay to conform to the most recent conclusions about illite composition. The objective of the present study was to reassess the Muloorina illite to determine the reason for this high CEC value. The composition determined by X-ray fluorescence analysis calculated to a cation charge of +22 is K0.68(Mg0.39Al1.02Fe0.543+Fe0.042+)[Si3.59Al0.38Fe0.033+]O10(OH)2. X-ray diffraction of glycolated and heated K-saturated Muloorina illite revealed no evidence of expandable layers. The cell dimensions are a = 5.314(1)Å, b = 9.040(1)Å, c = 10.135(3)Å, and b = 100.97(3)° (3σ in parentheses). Transmission electron microscopy revealed that Muloorina illite has a remarkably fine and uniform particle size in the form of irregularly stepped hexagonal crystals, averaging 60 nm in diameter at their widest, and 35 nm thick, each step being ~7 nm high. At most steps and between many steps defects occur where a 2:1 layer terminates, with a wide interlayer spacing beyond, commonly reaching to the crystal edge. Even though uninterrupted stacking of >10 or so 2:1 layers across one crystal is uncommon, the irregular distribution of the dislocations leaves appreciable structural continuity so that the mean diffracting thickness is of the order of 16 nm. Muloorina illite is not an interstratified illite-smectite, but a mica mineral with low-charge regions associated with terminating 2:1 layer defects. Such regions are wedge shaped at the nm scale and stabilized by the bonding of the illitic remainder of that interlayer. Approximately 17% of the total volume of each Muloorina illite crystallite is occupied by such low-charge 2:1 layers.

Simultaneous X-ray difffraction-differential thermal analysis equipment for an X-ray diffractometer was evaluated. A brief description of the apparatus and of the method of preparing the sample was given.

Simultaneous XRD-DTA was used to study various clay minerals and inorganic hydrates. It was found in the study of clays such as hectorite, montmorillonite, kaolinite, and attapulgite that information concerning the rate of removal of water and hydroxyl units at various temperatures could be correlated to changes in the X-ray diffraction pattern. Various inorganic hydrates such as barium chloride dihydrate, nickel sulfate hexahydrate, and potassium ferrocyanide trihydrate were examined under dynamic and static conditions of analysis along with vacuum conditions. It was found that good correlation could be obtained between the X-ray diffraction pattern and the loss of water from the hydrates as indicated by the DTA curves.

Recent surveys of clay mineral assemblages in argillaceous sediments have indicated that chloritic minerals are of more frequent occurrence and of greater significance than was formerly recognized.

The wide latitude of compositional variations within the chlorite crystallization scheme introduces enough complexity into the x-ray diffraction identification and characterization of these minerals that a detailed description of a few typical clay mineral associations seems justified.

For the simplest cases, in which resolution of diffraction features from entirely chloritic grains can actually be demonstrated, analyses may be highly reliable. Further, for many unresolved instances, simple heat treatments effect reliable identifications.

For more complicated assemblages, in which coherently scattering domains are mixtures within themselves, individually planned heating or swelling reactions may become necessary.

Typical natural examples are illustrated, for which apparently proper distinctions have been made for characterizing associations on mono- and mixed-clay mineral grains.