Refluxing chromium (III) acetate with a Na+-montmorillonite suspension gives rise to the intercalation of linear Cr(III) polyhydroxo-acetate oligomers. Thermally stable chromia pillared mont-morillonite materials are obtained upon calcination under ammonia up to 625°C, and basal expansions up to 6 Å are maintained. The porous materials retain high surface areas (366–464 m2 g−1), a micropore volume of 0.1 cm3 g−1 and narrow pore size distributions centered between 7.5 and 12 Å. The most thermally stable materials in air were those prepared under ammonia at 625°C, containing NH4+ as the exchangeable ion.

The lower Permo-Triassic sediments of the Maláguide Complex contain abundant dickite. Whole rocks were studied by optical microscopy, scanning electron microscopy, and X-ray powder diffraction. The 2–20 µm and < 2 µm size fractions were extracted and analyzed by scanning and transmission electron microscopy, X-ray powder diffraction, infrared spectroscopy, differential thermal analysis, and thermogravimetry.

In the coarse-grained samples, the 2–20 µm size fraction consisted of well-crystallized dickite associated with minor quantities of kaolinite, illite, quartz, and hematite. XRD patterns of the fine-grained samples and the <2 µm fractions showed the existence of well-crystallized minerals in which several reflections of dickite (11l, 02l) were absent and the 132/13$\bar 2$ reflections were shifted. These patterns suggest the presence of an intermediate member between well-crystallized dickite and well-crystallized kaolinite. Only locally high-order reflections are present at 10.5 Å and 18–22 Å. DTA and IR data agree with those from XRD.

The observed compositional and structural variations are a function of the lithology and the particle size of the sample. The sequence kaolinite → kaolinite/dickite → dickite is proposed for the development of these materials during Alpine metamorphism.

Kaolinite: alkali halide intercalates have been successfully prepared by grinding the salt with kaolinite in the absence of water. Rate of intercalation is shown to correlate negatively with melting point of the salt. The basal dimensions of the intercalates increase with increasing size of the ion. As shown recently for kaolinite: NaCl intercalate, the layered structure survives the dehydroxylation of the kaolinite at 500°–600°C, at which point the excess alkali halide can be removed by rinsing to give an XRD-amorphous material. This amorphous material, of approximate stoichiometry MAlSiO4, reacts at surprisingly low temperatures to give crystalline phases, apparently of the same stoichiometry, with structures closely related to eucryptite (M = Li), carnegieite (M = Na), kalsilite (M = K), and leucite (M = K, Rb, Cs). The relationships between the structures of the reaction products are discussed.

Hydroxy-chromium solutions were prepared from chromium nitrate solutions by adding NaOH with OH/Cr = 2.

The solutions were treated at 20°C and 60°C. The hydrolysis times were from 1 to 100 days. Polymeric species in hydrolyzed chromium solutions were followed by visible absorption spectra within the range 325–800 nm and by pH measurement. OH-Cr-smectite with high d(001) spacing (2.07 nm) was obtained when hydroxy-chromium solution was prepared at 60°C and with 1-day hydrolysis. When this sample was heated up to 350°C the basal spacing collapsed at 1.8 nm.

The samples were characterized by X-ray diffraction and N2 adsorption-desorption isotherms.

The importance of precipitation rate as an effective control on illite and kaolanite formation during diagenesis has been examined by measuring precipitation rates, from Al fluid concentration, in a Dickson fluid-sampling vessel at 160°-250° and 500 bars (50 MPa). These experiments are considered to be analogues of the precipitation of clays in sandstones from porewaters containing dissolved carboxylic acids, which have a transient stability and may influence aluminosilicate solubility. Precipitated illite had a lath-shaped morphology and its composition was consistent with authigenic illite in sandstones. Kaolinite formed tabular rather than vermicular shaped crystals. Kaolinite precipitation rate was two orders of magnitude faster than illite precipitation and was rate-limited by the decomposition of oxalate; kaolinite formation should be equilibrium-controlled at virtually all stages of burial. Extrapolation of illite precipitation rate to burial temperatures indicates that the first appearance of illite in a burial sequence may be kinetically controlled. A model of illite precipitation based on these experimental results has been used to predict the time required to precipitate illite during burial of a sandstone, taking into account temperature changes during burial. For northern North Sea examples, a predicted illitization threshold of -60°C occurring at 60–80 Ma corresponds to the observed initiation of authigenic illite precipitation. Times of around 2–5 Ma would be required to reach a 98% approach to equilibrium at this threshold. The main phase of illite precipitation in the northern North Sea basin is a later, hydrologically controlled event (30-50 Ma). Equilibrium would be approached in around 0.1 Ma during this phase, which is consistent with the narrow illite K/Ar age range (1-5 Ma) recorded for some sequences.

The adsorption of the herbicide dimepiperate S-(α;α-dimethylbenzyl)-1-piperidinecarbothioate on homoionic Fe3+-, Al3+-, Ca2+-, and Na+-montmorillonite was studied in aqueous medium. The adsorption is described well by the Freundlich equation. The adsorption capacity decreases in the order Fe3+ > Al3+ > Ca2+ > Na+ clay. The dimepiperate adsorption from chloroform solution was also investigated by analytical, spectroscopic, and X-ray powder diffraction techniques. IR results suggest that the adsorption involves the interaction of the thioester carbonyl group of dimepiperate possibly with the surrounding water of metal ions. On Al3+ and Fe3+ clays, this interaction leads to hydrolysis of the thioester bond and formation of the thiol and carbamic acid derivatives that yield α-methylstyrene and piperidine, respectively.

The stacking order of a bi-ionic K/Mg vermiculite from Malawi (Nyasaland), has been determined from Weissenberg data. The sample corresponds to a K/Mg interstratified vermiculite containing 50% K layers (dK = 1.01 nm) and 50% Mg layers with two layers of water (dMg = 1.44 nm). The observed intensities along (0, 0), (h, 0), (0, k) and (1, k) reciprocal rods were compared to the calculated intensities given by model defect structures. It was found that: 1) The (h, 0), (0, k) and (1, k) rods reveal the interstratification phenomenon which was previously observed on the (0, 0) rod; 2) The exchange of Mg by K does not occur randomly in a single interlayer, but occurs in interlayer domains sufficiently extensive to allow the reorganisation of the layer stacking and development of the ordered K-vermiculite structure from the semi-ordered structure characteristic of magnesium vermiculites; 3) For this sample, the interlayer water of the Mg phase occurs in two coexisting configurations; one configuration has water molecules forming octahedral coordination around the Mg2+, the other has water which is not linked to the Mg2+ cation forming two planes.

A saponite pillared with a single (Al2O3) or a mixed (SiO2-TiO2) oxide exhibited basal spacings of 16–19 and 30–40Å, respectively. The pillared structures were found to be stable up to 700°C. Water, nitrogen, and high resolution argon adsorption were used to study the effect of thermal treatments on surface chemistry, pore structure, and surface area of these pillared clays. The pillared saponites exhibited a hydrophobic behavior at temperatures > 500°C, whereas such behavior was observed at ≥300°C for montmorillonite. Most of the micropores in the Al2O3 pillared clays were < 10 Å, whereas the SiO2-TiO2 pillared clays showed a broad distribution of pores in both micropore and mesopore regions. The SiO2-TiO2 pillared samples possessed higher surface area compared with Al2O3 pillared clays. The percent decrease in surface area was smaller for pillared saponites compared with pillared montmorillonites when calcined from 300° to 700°C, indicating a higher thermal stability of the former. The pillared clays were also characterized by solid state 27Al and 29Si magic-angle spinning nuclear magnetic resonance (MAS/NMR) spectroscopy. There was no direct evidence of cross-linking (covalent bonding between the clay layer and pillar) in montmorillonite irrespective of the types of pillars. In saponite, however, a significant structural modification took place. 27Al spectra of Al2O3 pillared saponite heated at ≥300°C appear to indicate an increase in AlVI as a result, at least in part, of initiation of hydrolytic splitting of Si-O-Al bonds. The actual release of Al from the tetrahedral sheet probably occurred at a temperature > 500°C and completed around 700°C with the formation of Si-O-Si linkages. The decreased intensity of peak due to Si(1Al) in 29Si spectra of the sample heated at 700°C corroborates the 27Al MAS/NMR results. Additionally, the 29Si spectra indicated a cross-linking between SiO4 (clay sheet) with Al2O3 pillars, which could be achieved by inverting some silica tetrahedra into the interlayer. 27Al and 29Si spectra of SiO2TiO2 pillared saponite also showed the trend similar to that exhibited by Al2O3 pillared saponite, indicating that the crystal chemistry of the host may be more important than the nature of pillars in the structural modification and cross-linking behavior of thermally treated pillared clays.

Sorption of benzene onto Cu-montmorillonite was characterized by Fourier transform infrared (FTIR) spectroscopy and 13C magic angle spinning nuclear magnetic resonance (MAS NMR). Under anhydrous conditions, chemisorption of benzene in the interlamellar region of Cu-montmorillonite led to the formation of a dark red surface complex that exhibited a vibrational spectrum similar to that of doped poly-p-phenylene. When the benzene sorption reaction was carried out under high relative humidity conditions, polymerization of benzene did not occur. The FTIR spectrum of the surface complex formed under wet conditions exhibited vibrational bands that could not be assigned to those of the parent benzene molecule or to those of previously observed chemisorbed Type I or Type II complexes. 13C MAS NMR spectra of 13C-enriched benzene sorbed onto Cu-montmorillonite powder showed the presence of two groups of peaks that could be assigned to aromatic and aliphatic carbon respectively.

X-ray diffraction, FTIR, and chemical analyses were performed on clay fractions (1–2 µm, <0.1 µm), separated by means of size fractionations and high-gradient magnetic separation techniques, from a Cryorthod developed in a chlorite-mica schist saprolite. Weathering of large phyllosilicates pre-existing in the saprolite involves physical fragmentation and mineralogical transformations. Chloritic minerals in the coarse fractions were the most affected by physical breakdown, while micas were generally preserved. As a consequence, a concentration of mica layers occurred in the coarse clay fraction, while chloritic residues accumulated in the fine clays. These residues exhibited the typical XRD pattern of hydroxy-interlayered intergrade minerals, but the interlayered contaminants were found to be mainly hydroxy-Mg cations. Further mineralogical transformations of the intergrade minerals involved the progressive removal of the hydroxide interlayered sheet and dissolution of chloritic layers. Illite/smectite mixed-layers were formed in the surface horizon of the soil profile. These processes were associated with a strong decrease in Fe and Mg contents in the clay fractions.

During processing of Athabasca oil sands, the finely divided solids form an aqueous suspension, which ultimately stabilizes as a gel-like structure retaining up to 90% of the process water. This gelling phenomenon is believed to be caused by colloidal inorganic components. Kaolinite and mica are the main crystalline minerals in these colloidal solids; swelling clays are present in only trace amounts. Non-crystalline components are more concentrated in the finer fraction of the solids. Although the surfaces of the colloidal solids are virtually free of Fe, some contamination with polar organic matter is observed.

Bulk and size-fractionated kaolinites from seven localities in Australia as well as the Clay Minerals Society Source Clays Georgia KGa-1 and KGa-2 have been studied by X-ray diffraction (XRD), laser scattering, and electron microscopy in order to understand the variation of particle characteristics across a range of environments and to correlate specific particle characteristics with intercalation behavior. All kaolinites have been intercalated with N-methyl (NMF) after pretreatment with hydrazine hydrate, and the relative efficiency of intercalation has been determined using XRD. Intercalate yields of kaolinite: NMF are consistently low for bulk samples that have a high proportion of small-sized particles (i.e., <0.5 µm) and for biphased kaolinites with a high percentage (>60%) of low-defect phase. In general, particle size appears to be a more significant controlling factor than defect distribution in determining the relative yield of kaolinite: NMF intercalate.

Smectite was reacted at several temperatures between 200°C and 500°C to produce interstratified illite/smectite (I/S) with different proportions of expandable layers. Dispersed and sedimented products were examined using a transmission electron microscope. Particle size and aspect ratio showed no systematic change as a function of reaction extent during R0 illitization. However, particles exhibited rounded edges during the early stages of the reaction, suggesting some dissolution of primary smectite. Additionally, increasing particle contrast in the electron beam suggests thickening of particles with increasing reaction extent. The thickening of particles is thought to be produced by the nucleation and precipitation of secondary illite layers on primary smectite layers. In the most extensively reacted I/S, particles have become aggregated into clumps or quasicrystals by lateral growth of illite layers. Internal uniformity of crystallographic alignment of individual growing crystals within each aggregate was reflected in the increasing frequency of 60° and 120° interfacial angles within each aggregate. In highly illitic I/S, these aggregates took on an overall euhedral form and became crystallographically contiguous, producing single crystal electron diffraction patterns.

Substantial studies have been carried out to investigate the mechanism of the formation of Al(OH)3 polymorphs. The influence of the nature of Al precipitation products on the formation of Al(OH)3 polymorphs still remains obscure. In this study, X-ray diffraction, infrared and thermal analyses, and electron microscopic observations of the Al precipitates formed at the initial pH 8.2 and at a citric acid/Al molar ratio of 0.01 and aged for 3 hr to 60 days revealed that the transformation from the initially formed noncrystalline materials to pseudoboehmite occurred through the formation of intermediate materials with various degrees of ordering and sizes of particles that apparently had a wide range of solubility. By increasing the pH of the suspension of precipitation products of Al to 10.0 after 3 hr and 3, 11, 31, and 60 days or longer, the crystalline precipitation products were hayerite, nordstrandite and bayerite, nordstrandite and pseudoboehmite, pseudoboehmite and gibbsite, and pseudoboehmite, respectively. This work shows evidence that, as the nature of the starting Al precipitates changed, the rate of their dissolution apparently changed, and various Al(OH)3 polymorphs consequently formed. Therefore, the data substantiate the hypothesis that the mechanism of the formation of an Al(OH)3 polymorph is determined by the rate of its nucleation, which is, in turn, influenced by the rate of dissolution of the noncrystalline or poorly ordered Al-oxides initially formed.

An aluminous Ca-montmorillonite from southern Manitoba, Canada, has been shown to generate very low pH values in clay/groundwater slurries over a range of ionic strength of the groundwater (fresh and saline) and temperatures from 25°–90°C. Dialysis experiments as well as results of X-ray diffraction and FTIR vibration spectroscopy point to an acidification mechanism that involves hydrolysis of exchangeable Al3+ ions, thus releasing protons, and the subsequent intercalation of gibbsite-like hydroxy-Al complexes into the smectite lattice forming a non-expandable “Al”-montmorillonite.

The maximum crystal radius Rn of ice in hollow wet chrysotile tubes is established by thermoporometry to be between 2.8 and 3.2 nm, and the internal pore volume Vn of the tubes to be between 0.008 and 0.02 ml/g. The hollow tubes of chrysotile and, for comparative reasons, small plates of talc, are hydrothermally synthesized at temperatures between 563 and 600 K and at pressures between 75 and 120 hPa. Size and shape of the pores can be varied by changing the Mg/Si molar ratios in steps of 3/1.5 and 3/2 for chrysotile and 3/3.6 and 3/4 for talc. The tubular morphology of the aggregates dried at 393 K is investigated by 1) transmission electron microscopy (TEM), 2) nitrogen adsorption and desorption at 77 K, and 3) diffuse reflectance infrared fourier transformed spectroscopy (DRIFTS). The radius within the hollow tubes, Ri, is between 2.5 and 4.0 nm as measured by TEM, and between 2.8 and 3.2 nm as determined by nitrogen adsorption and desorption. The measured radii agree well with the value calculated from crystallographic data, which is smaller than 5.3 nm. Within the dried aggregates the tubes are clustered in regular patterns, in which each tube is surrounded by six other tubes. The external radius, Ro, between the clustered tubes is from 1.6 to 2.9 nm as observed by TEM, and from 1.8 to 2.3 nm by N2 adsorption and desorption. The external radius is not measured by thermoporometry. Where thermoporometry only measures the average pore size and pore volume within the tubes, TEM and N2 adsorption and desorption additionally provide the corresponding values between the tubes. A third pore radius, 5 to 20 nm between the clusters of chrysotile tubes, is established with N2 adsorption and desorption.

Water vapor adsorption isotherms were measured for samples of loessial soil clays modified by removing organic matter and Fe and Al compounds. The isotherms were analyzed by the exponential adsorption isotherm equation. The distribution functions of adsorption energy, average adsorption energies, and surface areas were evaluated simultaneously. The surface areas were the highest for samples after organic matter removal and the lowest when all considered components were removed. Values of the average adsorption energies decreased consecutively after each of the subsequent removal steps while the energy distributions became narrower, indicating in general less variety in surface adsorbing centers.

Chlorite minerals, found in a great variety of rocks and geological environments, display a wide range of chemical compositions and a variety of polytypes, which reflect the physicochemical conditions under which they formed. Of particular importance for studies dealing with ore deposit genesis, metamorphism, hydrothermal alteration or diagenesis is the paleotemperature of chlorite crystallization. However, in order to understand the relationship between chlorite composition and formation temperature and hence use chlorite as a geothermometer, one must determine how other parameters influence chlorite composition. These parameters may include fO2 and pH of the solution and Fe/(Fe + Mg) and bulk mineral composition of the host rock.

Four approaches to chlorite geothermometry, one structural and three compositional, have been proposed in the past: 1) a polytype method based on the (largely qualitative) observation that structural changes in chlorite may be partly temperature-dependent (Hayes, 1970); 2) an empirical calibration between the tetrahedral aluminum occupancy in chlorites and measured temperature in geothermal systems (Cathelineau, 1988), which has subsequently been modified by several workers; 3) a six-component chlorite solid solution model based upon equilibrium between chlorite and an aqueous solution, which uses thermodynamic properties calibrated with data from geothermal and hydrothermal systems (Walshe, 1986); and 4) a theoretical method based on the intersection of chlorite-carbonate reactions and the CO2-H2O miscibility surface in temperature-XCO2 space, which requires that the composition of a coexisting carbonate phase (dolomite, ankerite, Fe-calcite or siderite) be known or estimated (Hutcheon, 1990). These four approaches are reviewed and the different calculation methods for the compositional geothermometers are applied to a selection of chlorite analyses from the literature. Results of this comparative exercise indicate that no single chlorite geothermometer performs satisfactorily over the whole range of natural conditions (different temperatures, coexisting assemblages, Fe/(Fe + Mg), fO2, etc.). Therefore, chlorite geothermometry should be used with caution and only in combination with alternative methods of estimating paleotemperatures.

Saponite, hectorite, and laponite have been pillared with cationic Al clusters, and special attention has been given to the solution chemistry or Al. Pillared saponite is obtained after exchange with refluxed Al solutions; while for hectorite, Al solutions treated with ammonium acetate give a pillared product with 1.8–1.9 nm spacing and thermal stability up to 873 K. In both types of solutions, the Keggin ion Al cluster is a minority species or totally absent. The typical 1.8–1.9 nm spacing is only obtained after washing. The quality of the pillared material can be judged from its thermal stability, its surface area, and the width of the d001 line before and after pillaring. The width should not exceed 0.3 nm before calcination and 0.5 nm after calcination. The latter criterion reflects the importance of the crystallinity of the parent clay for successful pillaring. Pillaring in concentrated conditions occurs by a combination of ion exchange and precipitation of Al and gives materials that exhibit poor thermal stability.

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.