An X-ray powder diffraction study of a vermiculitized chlorite in an amphibole schist near Limoges, France, shows the following weathering sequence: chlorite → ordered interstratified chlorite/vermiculite → vermiculite. Mössbauer spectroscopy indicates that vermiculitization proceeded by the release of ferrous iron from the 2:1 mica layer of the chlorite. The ferric iron content of the vermiculite product is almost the same as that of the initial chlorite. Infrared spectroscopy and chemical microprobe analyses show that Mg was preferentially extracted from the hydroxide sheet of the chlorite, whereas the Si and Al contents progressively increased to the point of the formation of a pure dioctahedral aluminous vermiculite. The Si, Al, and Mg removal processes support currently accepted vermiculitization mechanisms, but the behavior of Fe is slightly different. In this weathering sequence, vermiculitization does not appear to have taken place by the oxidation of Fe2+, but rather, by the simultaneous leaching of Fe2+ and Mg.

This paper describes the relationship between the micro-structure and hydraulic conductivity of simulated sand-bentonite mixtures (SSBMs) prepared with powdered and granular bentonite. Glass beads were used to simulate sand grains because of their superior optical properties. The micro-structure of SSBMs was observed using optical micrography and scanning electron microscopy. For mixtures prepared with powdered bentonite, the indications are that bentonite coats the particles. As the bentonite content increases, the thickness of bentonite coating increases and reduces the area available for flow. For mixtures containing granular bentonite, the dry bentonite granules occupy the space between the particles and then swell to fill the void space. As the bentonite content increases, the number of granules increases, leading to more void spaces being filled with bentonite. At higher bentonite content (>8%), flow paths devoid of bentonite are unlikely, and the hydraulic conductivity appears to be controlled by the hydraulic conductivity of bentonite. The changes in micro-structure that were observed are consistent with the decrease in hydraulic conductivity that occurs with increasing bentonite content. However, the relationship between hydraulic conductivity and bentonite content differs depending on whether a mixture contains powdered or granular bentonite.

In this investigation fabric-property relationships were studied in a silty fine sand sized crushed basalt—an artificial ‘soil’ that has previously been used to simulate lunar soil. The fabric was characterized by measuring preferred orientations of grains, and pore size distribution was determined by mercury intrusion porosimetry. When deposited by pouring, the grains acquired strong preferred orientations in the horizontal direction and formed pores between 1 and 30 μm dia. Densification by static or dynamic compaction resulted in near random grain arrangement and pore sizes between 0·1 and 10 μm dia.

Strength in direct shear and one-dimensional compressibility with the associated lateral stresses were measured. The strength was up to 30 per cent higher when the sample was sheared normal to the preferred orientation of grains than when the shearing was parallel to the orientation direction. This is to be expected, as shearing across the preferentially oriented grains should involve breakage or reorientation of many grains. At a given initial void ratio the compressibility of statically compacted specimens was larger (up to 30 per cent higher axial strain) than that of dynamically compacted specimens at very low stresses. At higher stresses both samples exhibited equal compressibility, suggesting that the grains become more randomly arranged at low void ratios (comparing samples of equal initial void ratios).

The use of glycerol retention measurements to calculate surface areas of clay minerals is described. Assuming that the glycerol retained on external surfaces is monomolecular in thickness, and that both this layer and the monomolecular glycerol layers adsorbed on internal surfaces of montmorillonite, vermiculite, and halloysite are of the density of liquid glycerol, it is calculated that each percentage of glycerol retained corresponds to an area of 17.6 square meters per gram on external surfaces and 35.3 on internal surfaces. The corresponding figures for ethylene glycol retention under these conditions are 22.3 and 44.6, respectively. For nonexpanding clays, surface areas calculated from glycerol retention values agree well with published figures derived from Brunauer, Emmett, and Teller (B.E.T.) gas adsorption measurements. For montmorillonites, surface areas agree reasonably well with published determinations based on B.E.T. treatment using polar adsorbates. Values of surface area are also presented for samples of vermiculite and endellite and for the nonexpanding clay minerals—illite, kaolinite, halloysite, and allophane.

Calculations of the surface area as a function of particle size for montmorillonites of hypothetically uniform particle sizes show that montmorillonites dispersed into very thin flakes must have an appreciable external surface. The ratio of internal to total surface is shown to furnish an estimate of the thickness of the individual montmorillonite flakes. Glycerol retention data for a Wyoming bentonite saturated with a number of different cations are interpreted as indicating particle thicknesses varying from 3 unit cells (about 30A) for Na+ saturation to about 20 unit cells for saturation with a number of polyvalent cations.

The Kübler Index (KI) is defined as the full width at half-maximum height (FWHM) of the 10-Å X-ray diffraction peak of illite-smectite interstratified (I-S) clay minerals. The only parameters controlling the Kübler Index are assumed to be the mean number of layers (N) in the coherent scattering domains (CSD), the variance of the distribution of the number of layers of the CSD, the mean percentage of smectite layers in I-S (%S), and the probability of layer stacking (Reichweite).

The Kübler-Index measurements on air-dried (KIAD) and ethylene-glycolated (KIEG) samples were compared to N and %S using the NEWMOD computer program to simulate X-ray diffraction patterns. Charts of KIAD versus KIEG corrected for instrumental broadening were made and isolines were mapped for constant N and %S. Isolines allow a direct and rapid determination of N and %S from KI measurements.

The method allows quantification of the metamorphic anchizone limits by considering mean thickness of fundamental particles in MacEwan crystallites. The transition from diagenesis to the anchizone and from the anchizone to the epizone of low-grade metamorphism corresponds to thicknesses of 20- and 70-layer fundamental particles, respectively.

Imogolite was synthesized at 25°C by aging partially neutralized solutions containing monomeric silicic acid and polymeric hydroxy-aluminum ions for 7 years. Solutions having an initial Si/Al molar ratio of about 0.5 and pHs of 4.0–4.5 produced the largest yields of imogolite, followed by those having an initial Si/Al ratio of about 1, although imogolite was not the principal product. Electron microscopic examination showed a small amount of imogolite fibers embedded in a noncrystalline gel-like substance. Traces of imogolite were detected in solutions having an initial Si/Al ratio of about 2, but no imogolite was found by electron microscopy in products from solutions having an initial Si/Al ratio of about 4. Only gibbsite formed from solutions having initial Si/Al ratios of <0.27. The diameter of the tubular structural unit of the imogolite produced in these experiments was 23 ± 2Å, close to that of natural imogolite.

Nineteen drill core samples of lower Dogger opalinum shale from wells drilled in connection with a tunnel project near Brugg, northern Switzerland, were investigated. The shale is a well known swelling rock that has caused problems in underground construction work. Swelling pressures determined under constant volume conditions to obtain maximum values were 0.7 to 2.2 N/mm2. The samples contained 37–59% clay-size material and about 35% quartz, 7–18% carbonate minerals, and about 5% feldspar, pyrite, and organic matter. In addition to kaolinite, illite, and chlorite, the clay-size fraction also contained mixed-layer illite/smectite with about 30% swelling layers. The specific surface area of the clay fraction was 135 m2/g. The specific surface charge of the clay (6.7 × 104 esu/cm2), the ion concentration in the pore fluid of the specimen after the swelling test (10−2 mmole/cm3), the valence of the ions in the double layer of the clay particles (+1), and the half distance between the clay plates in the specimen (8–15 Å) allowed the calculation of the swelling pressure for each sample according to the Gouy double layer theory.

The mean value of the calculated swelling pressures was found to be of the same order of magnitude as the measured values, indicating that the technique can be used where cylindrical or rectangular specimens are not available for direct measurement.

Glauconite pellets in the Cambrian of the central U.S.A. frequently contain two textural forms of glauconite–aggregate and oriented—which differ in both mineralogy and chemistry. The aggregate glauconite composes the bulk of most pellets and consists of crystals in a nearly random arrangement. The oriented glauconite occurs primarily as rims on the periphery of pellets. It has a honeycomb-like structure—the crystals are oriented with their c-axes tangent to the aggregate-textured cores. Scanning electron photomicrographs show that the aggregate and oriented textures grade one into the other.

The aggregate glauconite has a 1 M structure and less than 5% expandable layers, whereas the oriented form has a 1 Md structure and ∼ 10% expandable layers. The aggregate glauconite contains 5–8% more total iron oxides and 2–3% less Al2O3 than the oriented glauconite. The b-cell dimension of individual samples increases nearly linearly with increasing octahedral Fe3+ + F2+ + Mg content. Chemical and crystallographic variations among various samples are, for the most part, related to the ratio of aggregate to oriented glauconite.

The transition between the texture of the aggregate and oriented glauconite suggests that some glauconite pellets may form by concretionary growth. It is proposed that Cambrian glauconite pellets grew through the repetitive development of a smectite-like clay at the margin of pellets. The smectite was later altered, both chemically and texturally, first to the oriented and then to the aggregate-textured glauconite.

Kaolinite is often used as a base for the synthesis of new organo-mineral nanomaterials designed for applications in industry and in environmental protection. To make the mineral structure more likely to interact with organic molecules, a kaolinite-methanol complex (KM) can be used. In the present study, different experimental procedures were tested to investigate the formation of the KM. The kaolinitedimethyl sulfoxide intercalation compound (KDS), either wet or dried, was used as a pre-intercalate. The samples obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, CHNS elemental analysis, 13C CP-magic angle spinning nuclear magnetic resonance (MAS NMR), and 27Al and 29Si MAS NMR techniques. The method of density functional theory with dispersion corrections (DFT-D2) was used to explain the structure and to simulate the vibrational spectra of KM. Theoretical results were compared with experimental data. The most effective formation of the KM (d001 = 11.1 Å — wet; d001 = 8.7 Å — dried) was observed when the dried KDS precursor was used. In such conditions the degree of intercalation reached ~98% after 24 h of reaction time. As indicated by the CHNS elemental analysis, ~1/6 of the inner-surface OH groups were grafted by OCH3 groups. The esterification reaction was less efficient at higher temperatures or when wet KDS was used. In the latter case, the excess of very polar dimethyl sulfoxide molecules prevented intercalation of methanol and further grafting. Detailed analysis of the results of theoretical simulations revealed that the reaction of the KDS with methanol led to the formation of kaolinite with both grafted methoxy groups and intercalated methanol, and water molecules in the interlayer space. The spectra calculated revealed the contribution of individual vibrational modes into the complex bands, i.e. the energy of C-H vibrations was in the order: νasCHmet > νasCHmtx > νsCHmet > νsCHmtx.

Mineralogical and 57Fe Mössbauer spectroscopic analyses were made on seven terrae rossae and two terrae fuscae samples of Pliocene to Early Pleistocene age from Slovakia and limestone residues from their parent materials. In most of the samples, no mineral weathering or clay mineral formation could be detected by optical or X-ray powder diffraction investigation, compared with their parent limestone residues; only one terra rossa showed a strong weathering of primary feldspar and phyllosilicates and a high rate of clay formation, especially kaolinite. Mössbauer measurements between 5° and 300°K showed that hematite and goethite are the dominant color pigments in the rubified terrae rossae and their corresponding limestone residues. The mean particle size of hematite and goethite was estimated from Mössbauer effects and X-ray powder diffraction data to be 95 and 250 Å, respectively. Reduced values of the hyperfine fields at 5°K of the soil iron oxides, as compared with those of the pure oxides, indicate a partial substitution of Fe(III) by Al. The hematite content correlates with the Munsell color notation of 5 of the 7 terrae rossae samples and their corresponding limestone residues. All terrae rossae samples showed higher hematite contents than their corresponding limestone residues, indicating that the rubification of such materials is independent of the degree of weathering.

Intercalates of Georgia well-crystallized kaolinite with formamide, N-methylformamide (NMF), and dimethylsulfoxide (DMSO) were prepared at room temperature by dispersing the clay in the organic liquid. Several physical and chemical properties of the intercalated organic molecules and the clay, while intercalated and after de-intercalation, were examined using nuclear magnetic resonance (NMR), infrared (IR), and electron paramagnetic resonance spectroscopy (EPR), and specific heat (Cp) measurements. The chemical bonding between the inner-surface hydroxyls and the organic molecules, as indicated by IR, was strongest for DMSO and weakest for formamide. The distortion of the kaolinite layer, as shown by EPR, also was greatest for DMSO and least for formamide. NMR T1 measurements indicated a relatively strong DMSO-kaolinite surface interaction that slowed down the methyl group reorientation comparable to that in bulk solid DMSO. T1 measurements indicated a weaker interaction for NMF. De-intercalation by mild heating did not return the kaolinite to its original structural state as shown by EPR and Cp. The greatest disorder was found for the DMSO de-intercalate and the least for the formamide de-intercalate. These experiments show that for sufficiently strong bonding between the clay inner surface and the intercalating molecule, the structure of the clay is capable of distortion, which is partly temporary and partly permanent. The permanent changes probably involve the introduction of stacking faults.

DIFFaX simulations show that the 3R1 and 3R2 polytypes of hydrotalcites (HT) have distinctly different X-ray powder diffraction (XRPD) patterns. The HT samples obtained by coprecipitation as well as those subjected to a subsequent hydrothermal treatment exhibit non-uniform broadening of lines in their XRPD patterns as well as anomalous variation in the intensities of the basal reflections. The reflections appearing in the mid-2θ region (30–50°; 3–1.8 Å) are excessively broadened and do not correspond to either of the 3R polytypes. This broadening is shown to be due to a stacking of layers randomly rotated about the c crystallographic axis by n × 120° (n = 1,2). The intensities of the basal reflections vary due to the departure of the layer composition from the nominal value, essentially due to an increase in the intercalated water content.

Adenosine-5-phosphates (ATP, ADP, AMP) are adsorbed by clay minerals at very low concentrations (≤2 mg/liter). In contrast to quartz, the clay minerals exhibit a strong preference for ATP over AMP. The experimental data are expressed as recovery rates (adenosine-phosphate in solution to total nucleotide added). For example, the recovery rates of ATP, ADP, and AMP in the presence of sodium montmorillonite are 0,17, and 100%; in the presence of quartz 95, 100, and 99%. The recovery rate of AMP on clays is markedly decreased by the presence of ATP, that is, ATP increases the adsorption of AMP by cooperative interactions.

A part of ATP not recovered in the equilibrium solution is dephosphorylated to ADP. For example, 45% of ATP not recovered in equilibrium solution with calcium montmorillonite is recovered as ADP; with sodium montmorillonite only ADP can be recovered in solution.

Infrared spectroscopic, X-ray diffraction and gravimetric techniques were used so study the vapor phase adsorption of ethanol on homoionic Cu-, Al-, Ca,, Na-, and NH4-montmorillonite films. Equilibration of these films with ethanol vapor at a relative pressure of unity reduced the water content to less than 0.7% (300°C). As dehydration proceeded, the infrared absorption bands of the residual water were observed. Apparent differences between different cation saturations are reconciled by a consideration of the different types of ion-dipole interactions involved. Adsorption isotherms and X-ray diffraction results substantiated the interpretations of the infrared data. Prolonged evacuation did not remove all of the adsorbed ethanol as shown by spectroscopic and gravimetric techniques. Cu-, Al- and Ca-montmorillonite retained 4.5, 7.9, and 4.5 molecules per ion, respectively, while Na- and NH4-clays retained less than one molecule per cation. Ethanol loss occurred rapidly at 40% relative humidity except in the Cu-system where 70 hr were required for complete replacement. These differences indicate that the adsorption and retention of alcohol by montmorillonite is affected by the saturating cation and that alcohol and water compete for the same adsorption sites. Ion-dipole type interactions should thus be considered in adsorption mechanisms of alcohol on montmorillonite.

The surface charges and the zeta potential of a Na-montmorillonite (Na-mont) and two pillared montmorillonite (MP1 and MP2) samples with different aluminum contents were determined by Potentiometric titrations and electrophoretic measurements. At pH >9 the two pillared montmorillonite samples showed zeta potentials similar to those of Na-mont, but at pH <8, the negative zeta potential shifted to lower negative values as the aluminum content increased. Sample MP1, which had a greater Al content, showed an isoelectric point (IEP) of 5.0–5.5. Titration curves obtained by acid-base Potentiometrie titration for sample MP1 showed a well-defined cross-over point at pH = 5.0, whereas this point was not observed for sample MP2 in the pH range studied. The results indicate, in principle, that both techniques can be used to characterize surface charges in this type of material. An attempt was also made to relate the data obtained from electrophoretic mobility and Potentiometrie titrations.

The three-dimensional crystal structure of rotationally disordered illite/smectite (I/S) in K-bentonite samples from the Appalachian basin and neighboring areas is described using the parameters of 1) P0, the proportion of zero-degree layer stacking rotations, such as in the polytype series 1Md-1M; 2) Pcv, the proportion of 2:1 layers with cis-vacant (cv) octahedral sites that are randomly interstratified with trans-vacant (tv) layers; and 3) P60 the proportion of layers with n·60° rotations (as opposed to n·120°) in the rotated layers. These parameters were determined by computer modeling of experimental randomly oriented powder X-ray diffraction patterns.

The proportion of cv interstratification in the I/S increases with A1 and decreases with Mg and Fe content. The proportion of n·60° rotations in the rotated layers increases with Mg and Fe content. The cv 120° disordered structure correlates with tetrahedral A1 for Si substitution and increasing tetrahedral charge. The tv n·60° disordered structures correlate with octahedral Mg for A1 substitution. The data indicate that the type of unit cell and nature of rotational disorder in I/S is controlled by the octahedral Mg content. The three-dimensional structures do not show any systematic correlation with Reichweite and percent expandability as determined from diffraction patterns of oriented sample preparations.

The transformation of ferrihydrite to goethite and hematite in the pH range 9–13 is retarded by the presence of simple sugars (>- 10-4 M concentration). The retarding effect is related to the extent of adsorption of the sugar on ferrihydrite. Maltose and glucose adsorb strongly and inhibit the transformation by preventing both aggregation and dissolution of the ferrihydrite. Sucrose adsorbs to a much lesser extent than the other sugars and appears to hinder the nucleation and growth of goethite in solution.

Hematite formation relative to that of goethite is favored by the sugars in the order: maltose >glucose ≫ sucrose. Maltose and glucose cause hematite to grow as prismatic crystals rather than as hexagonal plates and also lead to a new type of twinned goethite; one with epitaxial outgrowths of goethite on a prismatic crystal of hematite. In alkaline media glucose and maltose are partly transformed into a mixture of different sugars and hydroxycarboxylic acids, and it is probable that modification of the hematite crystal shape is due to the presence of the degradation products rather than to the nature of the original sugar.

The results of this work suggest that cyclic molecules influence the transformation of ferrihydrite to a lesser extent than do acyclic molecules.

Expandable fluorine micas were synthesized using talc and Na2SiF6 at 800°C for 2 hours in air, nitrogen, argon, and under vacuum. Gaseous SiF4, generated from Na2SiF6, and the resultant amorphous sodium silicofluoride formed during the reaction between talc and Na2SiF6 below 900°C are taking active part in the formation of expandable micas because the intensity of the 12.5 Å reflection of expandable micas decreases as the gas flow increases in the furnace. Expandable micas seem to be formed by the transformation from talc taking place without the entire disruption of the original atomic arrangement. This takes place with the loss of one Mg2+ from an octahedral site and by the intercalation of every two Na+ into the interlayer site of talc. Infrared absorption and thermal analyses show that expandable micas include a small amount of OH− in their structures.

Desilication and removal of bases from the basalitic rocks of the Hawaiian Islands produces large amounts of halloysite and gibbsite, together with variable quantities of allophane and nontronite, iron and titanium oxides, and amorphous mineral and gel material.

The nature and relative abundance of intermediate and end products of weathering depend primarily upon the amount of rainfall, angle of slope, and texture of the rock. The formation of clay minerals is the common step in the transformation of primary silicates to oxides and hydroxides, but the amount and relative importance of the clay “stage” depend on the intensity of the weathering process.

Halloysite forms from plagioclase usually by alteration of first the core and subsequently the rim of the feldspar laths. No kaolinite was observed, its absence being attributed to the absence of fine-grained mica as an intermediate weathering product.

Gibbsite is produced by (1) removal of silica from halloysite, (2) dehydration of Al-gel, and (3) precipitation from solution. Although it is possible that the mineral may form directly from feldspar, halloysite is the common crystalline intermediate on both the megascopie and microscopic scales.

An amorphous transition state, probably ranging in composition from allophane to Al-gel, exists as part of the change from halloysite to gibbsite as evidenced by electron microscope and diffraction work on pseudomorphs after halloysite tubes found in certain samples studied in more detail than others.

Volcanic glass is the apparent source of most Al-Fe-Si gel material which upon dehydration becomes allophane, cliachite, or gibbsite depending on the kind and relative proportion of the cations present.