A clay mineral that in its natural state expands to 15Å with water and to 17 Å with ethylene glycol was treated with various concentrations of KCl. At the highest KC1 concentration all the material was rendered nonexpanding. There was a threshold KC1 concentration at which potassium ions were absorbed in sufficient quantities to prevent expansion of the clay in water. At concentrations less than the threshold the material is characterized by a random interlayer mixture of expanding and nonexpanding layers. The sequence produced with increasing KC1 concentration is: expanding clay → interlayer mixture → nonexpanding clay.

Solvation with ethylene glycol is more effective than solvation with water for much higher potassium ion population densities in the interlayer space. At potassium ion population densities intermediate between those at the concentration thresholds for water solvation and for ethylene glycol solvation, there are layers that will expand with glycol and not with water.

Low potassium ion population densities correspond to low surface charge densities of potassium saturated clays, and the clays expand like montmorillonite. The high potassium ion population densities correspond to high surface charge densities of potassium-saturated clays and illite and the clays do not expand. With intermediate potassium ion population densities corresponding to intermediate surface charge densities for potassium-saturated clays, the clays expand with ethylene glycol but not with water.

An order of magnitude calculation is made to determine the activation energies involved in the recrystallization of serpentine to forsterite. The so-called “activation energy spectrum” showing the proportion of material with different activation energies is estimated.

Some investigntors have used petrographic methods as the sole means of making clay mineral analyses, whereas others have considered petrographie metliods to be useless for materials as fine grained as clays. The value of the method lies between these extremes. It has consideralde value, but it has limitations and must be used with cantion.

By the use of varions auxiliary techniques it is usually possible to obtain fairly precise values for the indices of refraction and birefringence of the clay mineral components of a clay material. Frequently an interference figure can be obtained which yields farther data on the optical characteristics. The presence of very fine non-clay minerals, such as quartz and carbonate, and organic material and iron oxide or hydroxide may prevent the making of satisfactory optical measurements.

It is necessary to decide if the optical data obtained arc influenced by contamination with nonclay minerals, and if they indicate a single clay mineral or mixture of clay minerals. Fortunately the optical values themselves and the character of the particles on which they were determined give good clues regarding purity and monomineral characteristics.

Optical data in general will not permit the detection of relatively small amounts of a clay mineral in a clay mineral mixture. Also such data may l)e very misleading in studies of mixed-layer clay minerals.

In addition to optical data, petrographic studies of clay materials yield other important information. They are of value in determining the texture of the rock and the relative abundance and size of the nonclay minerals. In general microscopic studies are easy to perform and the probable value from them is so great, that they should be made in all clay material researches.

Tuffs of the Tertiary Colbún Formation near Quinamávidain central southern Chile have been mapped and their mineralogy analyzed. The pyroclastic rocks present a maximum outcropping thickness of 120 m and are dominated by vitreous lapilli and minor lithic tuffs, the products of active volcanism nearby. About 10% of the tuffs consist of lenses of fine banded tuffs with a high leaf content that were deposited in shallow lakes during quiescent periods between periods of volcanic activity. This tuff sequence is pervasively transformed to clinoptilolite/heulandite and mordenite with variable amounts of plagioclase, minor quartz and smectite. Factors thought to have influenced this conversion to zeolites are a humid climate following deposition combined with a slightly elevated heat flow. Local hydrogeological conditions have modified the cation-hydrogen ion ratios across the study area favoring the formation of clinoptilolite/heulandite and mordenite with medium-minor smectite in the center and south, and a more abundant presence of smectite in the north of the study area.

Hydrophobicity, high viscosity, and dispersion are important properties for organo-montmorillonites, and all organo-montmorillonite configurations have yet to be fully characterized with respect to this property. High-viscosity montmorillonite (Mnt) is useful in gels and as an adsorber. The current study focused on modifying Mnt using organic cations and anions of various chain lengths in batch experiments with various concentrations and ratios. The viscosity of organic Mnt reached up to 395 mP.s. Molecular dynamics simulations and X-ray diffraction (XRD) were used to identify the conditions and arrangement of organic cations and anions in the Mnt interlayer area. The intercalation mechanism of organic cations and anions was also determined, providing a theoretical basis for the preparation of high-viscosity Mnt.

In order to obtain nanopatterned surfaces, natural allophane particles originating from Japanese soils were immobilized as single particles on Si wafer substrates.When derived from aqueous suspensions, only a few nanoparticles were deposited and detected on the surface due to the weak adsorption of allophanes on the substrate. The amount of immobilized allophane was increased significantly, however, by using an organic solvent in combination with a micelle-based technique to suspend the allophane particles. The micelles were formed from a tailored, aliphatic diblock copolymer that was dissolved in toluene and contained several allophane particles. A cleaned silica chip was used as a substrate on which a monolayer of micelles was immobilized equidistant from each other by dip coating. To remove the polymer from the substrate and to produce free, single allophane nanoparticles, ultraviolet (UV) irradiation was used. After UV treatment, single allophane particles formed ring-shaped deposition patterns with a high surface density. Transmission electron microscopy (TEM) was used to verify the presence of single allophane nanoparticles in the Japanese samples which came from natural sources. The single allophane particles as well as the allophane-containing di-block copolymer micelles, both immobilized on Si substrates and TEM sample grids, were imaged by atomic force microscopy and TEM. In this way, the diameters of the single allophane particles, as well as the distances between the immobilized micelles and the particles and their topography on the substrates, were determined.

A Georgia kaolinite, at water contents from 55 to 95 per cent, was tested by means of a Weissenberg Rheogoniometer under conditions of pure shear with sinusoidally varying deformation over a frequency range of 3 decades. The results, including time-dependent effects, are expressed in terms of the magnitude of the complex modulus and the phase angle, as developed in the theory of linear viscoelasticity, and stress-strain hysteresis curves. The complex modulus is a two-component quantity, which has a real part associated with the elastic or energy storage characteristics of the material and an imaginary part associated with its viscous or energy dissipation characteristics. Although the complex modulus interpretation is very good for linearly viscoelastic materials, its applicability and usefulness diminishes as the material departs from linear viscoelastic behavior. On the other hand, the determination of energy dissipation from stress-strain hysteresis curves does not depend on any assumption concerning material behavior, because the area enclosed by the curve gives a direct measure of the energy dissipated in a single cycle of deformation. The dissipation characteristics obtained by the two methods are compared and used to illustrate the degree of validity and some limitations of linear viscoelasticity theory.

Natural smectites bind aflatoxins from water effectively, but the complex chemical environment in the guts of mammals and other animals can limit binding of aflatoxins. Many efforts have been made to enhance the adsorption capacity and affinity of smectites for aflatoxins in the presence of biological compounds. The main objective of the present study was to modify smectite structures by pillaring and cation exchange to enhance aflatoxin B1 adsorption capacity and selectivity. Smectite was pillared with Al and Al-Fe polycations or saturated with Ca, Mg, Zn, or Li. Structural changes in smectites with or without heat treatment were determined using X-ray diffraction and Fourier-transform infrared spectroscopy. Equilibrium aflatoxin B1 adsorption to the smectites was measured in aqueous solution and in simulated gastric fluid. Pillaring with the polycations expanded smectites in the z-direction to 18.6 Å and the expansion was stable after heating at 500°C. Changes in the Al–OH–Al infrared bands in the stretching region supported the formation of pillared clays. Migration of Mg, Zn, and Li into the octahedral sites of the smectite was observed as Mg and Zn saturation yielded a d spacing of 15 Å at 200°C which collapsed to 9.6 Å at 400°C. The 14.6 Å peak of the Li-saturated smectite collapsed to 9.6 Å at 200°C while the 15 Å Ca-saturated smectite peak was stable up to 400°C. The unheated Al- and AlFe-pillared smectites adsorbed significantly more aflatoxin B1 from an aqueous suspension than did unpillared clay. In both water and simulated gastric fluid, heat treatment decreased aflatoxin B1 adsorption to pillared smectites, but heat treatment increased aflatoxin B1 adsorption to unpillared smectites. Without heat treatment, smectites saturated with divalent cations (Ca, Mg, Zn) adsorbed more aflatoxin B1 from an aqueous suspension than the smectite saturated with a monovalent cation (Li). Ca-saturated smectite showed the greatest aflatoxin B1 adsorption, 114 g kg–1, from aqueous suspension after 400°C heat treatment. The Zn-, Mg-, and Li-saturated smectites showed maximum aflatoxin adsorption of 107, 93, and 90 g kg–1, respectively, after 200°C heat treatment. From simulated gastric fluid with pepsin, the 200°C heated, Zn-saturated smectite had maximum aflatoxin B1 adsorption of 68 g kg–1. Pillared smectites effectively adsorbed aflatoxin B1 from aqueous suspension, but Ca- and Zn-saturated smectites after heat treatment might improve the selectivity of smectites for aflatoxin B1 over pepsin and enhance the efficacy of smectite as a feed additive.

Analytical data from aqueous dissolution studies of minerals, mineral systems, and naturally equilibrated solutions such as surface waters and groundwaters provide the basic ingredients necessary to calculate comparative solubility (or activity) products (CKs) and comparative free energies of formation (CΔGf0) of possible minerals or hypothetical minerals. Using a thermodynamic approach, quasi-thermodynamic values are obtained which can help in understanding the relative stabilities of different but similar materials and changes in reacting systems. Illite equilibrated solutions demonstrated that: 1) there is a 5 kcal spread in comparative free energies of formation of the five illites used, 2) the comparative stabilities remain about the same when highly simplified but similar hypothetical mineral formulas are considered, and 3) some of these illites are probably not the most stable phase in a closed chemical system at standard temperature and pressure.

A “mineral index system” composed of common rock-forming minerals, products of chemical weathering and perhaps hypothetical minerals is proposed, which offers a means of studying naturally equilibrated solutions. Such a system can show changes with respect to CΔGf0 of these minerals at a particular site through time or in relationship to spatial distribution and geologic changes through synchronous sampling at different sites.

2-Phenethylamine 13C-enriched in the beta position was adsorbed on four different aluminum-exchanged clays: hectorite, Barasym, Laponite RD, and lithium taeniolite. The sites for adsorption were characterized by 13C high-resolution cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS-NMR) spectroscopy. Using differences in chemical shift values and linewidths, three different types of bound ammonium compounds and a motionally restricted bound compound were identified. Correlation with charge effects indicated that one of the clay sites was extremely acidic.

The important catalytic sites for the different clays, the edge or platelet face, interlamellar and some combination of both, were probed by using the trimethylsilyl group as a clay-blocking agent. Silylation of aluminum-exchanged Laponite RD and Li taeniolite had little effect on amine adsorption. This indicates that, for these clays, amine adsorption occurred mainly at interlamellar sites. For hectorite, amine adsorption occurred at both surface and interlamellar sites, and silylation had the effect of reducing surface adsorption. Silylation of Barasym resulted in a very interesting shift of adsorption from one kind of surface site to a more acidic surface site.

The basal Cretaceous beds of the area are subdivided into three units: the Cape Fear formation, Middendorf formation and Bladen member of the Black Creek formation. Stratigraphic position and lithology indicate that the Cape Fear is the oldest and the Middendorf is in part the landward facies of the Bladen. The Middendorf sediments are fluviatile and the Cape Fear and Bladen sediments are probably marine.

The Cape Fear and Bladen contain abundant montmorillonite, some kaolinite and lesser amounts of illite. In the Middendorf kaolinite predominates, although a few samples have small amounts of montmorillonite and illite.

Preliminary data indicate that in the Cretaceous-Tertiary sediments of the Atlantic Coastal Plain, montmorillonite occurs in abundance in the marine beds and kaolinite in the nonmarine sediments. The basal Cretaceous beds of the area studied fit into this scheme of clay mineral distribution.

The origin of the clay minerals of the Cretaceous formations studied is approached from sedimentary and empirical standpoints. The montmorillonite-marine and kaolinite-nonmarine associations strongly suggest that the montmorillonite has formed by marine diegenesis, whereas the sedimentary evidence suggests that the montmorillonite of the Cape Fear formation is detrital and the kaolinite of the Middendorf formation has formed by prolonged postdepositional weathering of a more varied clay mineral assemblage. The sediments of the Bladen unit in themselves offer little evidence as to the origin of their clay minerals. However, the predominance of kaolinite in the contemporary deltaic Bladen suggest that kaolinite was the only clay mineral supplied to the depositional area, and that in the marine part of the sedimentation area part of this kaolinite was changed to montmorillonite by marine diagnetic processes.

The present study deals with accurate identification of polytypes, twins, and allotwins – oriented crystal associations of more than one polytype. The trioctahedral 1:1 layered silicate cronstedtite was studied using single-crystal X-ray diffraction data collected with a four-circle diffractometer equipped with a CCD detector. The sample from the skarn occurrence, Ouedi Beht, El Hammam, Morocco, was explored. It contains cronstedtite in fibrous massive aggregates in the central part, and euhedral crystals in surrounding veinlets and druses. The reciprocal space (RS) sections created by the diffractometer software and presented here were used to determine the OD (ordered-disordered) subfamilies (Bailey’s group A, B, C, D) and to identify polytypes. The chemical compositions of some crystals were determined thereafter by electron probe microanalysis (EPMA-WDS). Some crystals studied are more or less complicated allotwins. Polytypes were thus separated by cleaving crystals into smaller parts in many cases. All polytypes found belong to subfamilies A or D. The following polytypes of the subfamily A were identified: 2M1 (a = 5.49, b = 9.51, c = 14.40 Å, β = 97.30°, space group Cc), 1M (a = 5.51, b = 9.54, c = 7.33 Å, β = 104.5°, Cm), 3T (a = 5.51, c = 21.32 Å, P31), 6T2 (a = 5.50, c = 42.60 Å, P31). 2M1 and 3T were present as isolated crystals or separated by cleaving, otherwise all these polytypes are parts of allotwins. The 2M1 polytype is sometimes twinned by reticular pseudo merohedry with twin index n = 3 and 120° rotation about the chex axis as the twin operation. Allotwins of 1M + twinned 2M1 polytypes are also present. Another kind of twinning, with rotation by (2n+1)×60° about chex is rare. The subfamily D is represented mostly by 2H1 and 2H2 polytypes, a = 5.50, c = 14.25 Å, space groups P63cm (2H1), P63 (2H2). In addition, several six-layer (a = 5.49, c = 42.80 Å), mostly non-MDO polytypes were separated from allotwins by cleaving. In order to identify them, 24 possible stacking sequences were modeled, diffraction patterns calculated, graphical identification diagrams constructed, and comparisons made with actual RS sections. This simulation revealed that five pairs of sequences provided identical diffraction patterns. Polytypes actually found correspond to the following sequences: 1 (6T1), 5 (proposed Ramsdell’s symbol 6T3), 8+10 (6T5), 11+12 (6T4), 24 (6T6, trigonal polytypes, space group type P3), 22 (6R1), and 23 (6R2, rhombohedral polytypes, space group type R3c and R3, respectively). The RS section corresponding to the hexagonal polytype 6H2 (sequence 14) was also found. However, diffraction patterns geometrically indistinguishable can be produced by the twin with rotation by 180° about chex as a twin operation of the rhombohedral polytype 6R2 (sequence 23). Several aggregates with fiber texture of polytype 2H2 were separated from the central part. Use of EPMA-WDS revealed Fe and Si along with significant amounts of Mn and Mg. Crystals from veins were more Mn- and Mg-rich than these from the central part. Traces of Cl, S, and Al are present also.

The interaction of telone with acid and base saturated montmorillonite furnished adsorption isotherms which possessed combined features of H (high affinity) and C (linear rising) class isotherms; a fall in pH, an increase in electrical conductivity and formation of chloride ions. The observations were indicative of a process of chemisorption, both at the planar and lateral sites of montmorillonites, followed by penetration and swelling of the substrate micropores with telone. A reaction mechanism for the process of chemisorption has been proposed.

An X-ray spectrochemical method is compared with the flame photometer determination of potassium in a series of sixty-five soil clay fractions. Two methods of preparing the clay samples for the X-ray determination were used. In one case a 20 mg sample of clay in suspension was dried onto a plastic disc as a thin film. Potassium was determined by comparing the fluorescence intensity of the unknown with a sample of known composition which was prepared for analysis by the same technique. For the second method a 100 mg sample of dried clay was pressed into a pellet using methyl cellulose as a backing. In this case a National Bureau of Standards sample (NBS-98) was prepared in an identical manner and used as a standard for determining the potassium in the unknown. The results for both techniques were highly significantly correlated with the values as determined by flame photometric analysis. The pellet technique gave a more accurate measure of the potassium content. With the thin films the same sample may be used for X-ray diffraction analysis. In either case the X-ray spectrochemical technique provides a fairly rapid and simple procedure that can be useful for handling large numbers of samples.

Differences in the properties of clay minerals cause formation damage under the condition of thermal production in heavy-oil reservoirs; asphaltenes adsorbed on clay minerals exacerbate the formation damage. The purpose of the present study was to reveal the variation in clay minerals and the adsorption behavior of asphaltenes on clay mineral surfaces under thermal recovery conditions. Volume changes and transformations of typical clay minerals were studied under various conditions (80 and 180°C, pH 9 and 11, aqueous and oven-dry conditions). On this basis, the adsorption behavior and mechanism of asphaltenes on the surfaces of clay minerals in various simulated conditions were investigated. The adsorption mechanism was revealed using kinetics and isothermal adsorption models. The results showed that the volume of montmorillonite expanded by up to 159.13% after water–rock interaction at 180°C with pH 11; meanwhile, the conversion rates of kaolinite and illite to montmorillonite were 6.6 and 7.8%, respectively. The water–rock interaction intensified the volume changes and transformations of clay minerals under thermal conditions. The amounts of asphaltene adsorbed on clay minerals at 180°C were greater than those at 80°C. The adsorption process of asphaltenes was inhibited under aqueous conditions. The abilities of the constituent minerals to bind asphaltenes was in order: montmorillonite > chlorite > kaolinite > illite > quartz sand. The adsorption process of asphaltenes yielded high coefficients of regression with both the Freundlich and Langmuir models under oven-dry (>0.99) and aqueous (>0.98) conditions. At 180°C under aqueous conditions, the water film significantly inhibited the adsorption of asphaltene on the clay minerals. The adsorption process of asphaltenes, therefore, could be regarded as the adsorption occurring at lower concentrations under oven-dry conditions.

Mud shale is characterized by low strength and strong swelling, with rheological effects and deformation caused by drilling fluid and formation water. Establishing a rheological model to characterize the deformation characteristics is key to solving the problem of wellbore stability. The influence of moisture content on rock strength and creep mechanical properties were studied by means of water absorption, uniaxial compression, and creep tests. The tests showed that with the increase in moisture content, the elastic modulus and strength of hard brittle mud shale decreased. Further, under the same load, the instantaneous strain increased with increasing moisture content. Meanwhile, under various loading stresses, rock creep exhibited non-linear characteristics, which can be divided into three different creep stages: attenuated creep, stable creep, and accelerated creep. Starting with a non-linear viscous dashpot, and then introducing aging degradation and water-bearing weakening effects, based on the water-bearing creep characteristics of hard brittle shale as well as the modeling ideas of the classic component combination model, a new improved creep model based on the Nishihara model was established to describe the characteristics of the accelerated creep stage of hard brittle mud shale with various moisture contents. Subsequently, the Levenberg–Marquardt non-linear, least-squares method was adopted to invert the creep parameters. The results showed that the simulated creep curves achieved by employing the new creep model were consistent with the experimental results, thereby confirming the ability of the new non-linear creep model to provide a theoretical reference for the study of wellbore stability of hard brittle mud shale.

Ba-bearing clinoptilolite (with >2 wt. % BaO) occurs in Neogene marine siliceous sediments from ODP Leg 127 Site 795 in the Japan Sea. Ba-bearing clinoptilolite is formed by reaction of volcanic glass and Ba-rich pore water during burial diagenesis.