The structures of 11 smectites and 2 interstratified mica/smectites containing mainly Ca2+ and Na+ as exchangeable cations in variable ratio were studied under a relative humidity of about 40%. Observed X-ray powder diffraction patterns were compared with diagrams calculated from interstratification models containing 15.2-Å Ca-smectite layers (C), 12.4-Å Na-smectite layers (N), and 10.0-Å mica layers (M) in various combinations. The smectites appear to be a random interstratification of component layers C and N, and display a tendency towards segregation. One of the interstratified minerals studied is a regular interstratification of C and M layers; the other is a regular interstratification of C, N, and M layers, in which N and C layers are randomly distributed in equal proportion and show a tendency towards segregation.

The i.r. spectra of interlamellar kaolinite complexes with formamide, N-methylformamide and dimethylformamide have been examined. The spectra show that the amides hydrogen-bond, through the C=O group of the amide to the inner surface kaolinite hydroxyls and decrease the intensity of the kaolinite ν(OH) bands. Hydrogen-bonded kaolinite hydroxyl bands appear at lower frequencies and these have been correlated to the original kaolinite ν (OH) bands. Other kaolinite bands in the complexes show smaller perturbations of the kaolinite vibrations. Each amide hydrogen-bonds to different groups of hydroxyls. Formamide hydrogen-bonds to the 3690 and 3664 cm−1 hydroxyls, N-methylformamide to the 3690 and 3648 cm−1 hydroxyls. The interpretation for the dimethylformamide complex is less clear. The ν(NH) frequencies of formamide and N-methylformamide in the complexes are intermediate between that in dilute non-polar solution and in the liquid. This could arise from either or both a degree of intermolecular association of the amide when between the kaolinite lamellae, or to weak N—H … O hydrogen bonds to the tetrahedral oxygen sheet of the lamellae.

Adsorption isotherms of 1-n-alkyl pyridinium bromides on Na-montmorillomte, and in addition of cetyl pyridinium bromide on Ca-montmorillonite, have been determined. For up to eight carbon atoms in the alkyl chain adsorption has a limit close to the exchange capacity of the clay. With larger ions adsorption occurs beyond this and is accompanied by adsorption of the bromide ion. Adsorption of the cetyl pyridinium ion beyond the exchange capacity is greater on Na- than on Ca-montmorillonite. Replacement of the cation initially present is incomplete. X-ray diffraction analysis shows that the adsorbed ions normally lie flat on the clay surface, but cetyl pyridinium ions may stand up in a plane at right angles to the surface. Interlamellar separations somewhat less than the minimum molecular thicknesses, found for the methyl and ethyl pyridinium ions, are attributed to a combination of (1) “keying” of the alkyl groups into the clay surface, and (2) the effect of the attractive forces between the clay and the pyridinium ring. It is concluded that adsorption is due to ionic and dispersion forces between the pyridinium ions and the clay. For the cetyl compound the dispersion forces are larger than ionic forces. The exchangeable cation initially present influences the adsorption by its effect on the exchange reaction and probably also by its influence on the domain structure of the clay and hence the accessibility of external surfaces of the crystallites.

As the water content is increased, the consistency of a fine-grained soil changes from a semi-solid state to a plastic state and finally to a liquid state. The plastic limit (PL) is the point at which the consistency, caused by the soil water content, is transformed from a semi-solid state to a plastic state. The liquid limit (LL) is the point at which the consistency is transformed from a plastic state to a liquid state. The plastic limit and liquid limit are often collectively referred to as the Atterberg (or consistency) Limits. Although the liquid and plastic limits are easily determined, fundamental interpretations of the limits and quantitative relationships between their values and compositional factors are more complex. Previous studies examined artificially-prepared soil samples that contained monomineralic clays and a non-clay substance(quartz sand). These studies have shown that in soils without expandable clays the PL and LL water contents were mostly related to surface area and clay content. For soils that contain expandable clays, the PL and LL values are also dependent on interlayer water content. Hence, expandable clay mineral contents are needed to calculate PL and LL values. These relationships have been presented in a general analytical form. The aim of these investigations was to identify practical applications. Mineral compositions and surface areas of five randomly selected natural soil samples were used to estimate PL and LL values. The estimated values were compared to experimentally measured liquid limits (by the ‘fall-cone’ test) and plastic limit (by the ‘rolling thread’ test) values. The measured PL values ranged from 18.77 to 44.92% and the LL values from 31.19 to 82.10%. The differences between estimated and measured Atterberg Limits were 3.0–7.1% for thePL and 2.7–7.8% for the LL. Minor differences in measured and estimated Atterberg Limits were probably due to soil organic matter (1.2–2.7%).

The effect of phosphate on the formation of Fe oxides from Fe(II) salts is important because phosphate is a ubiquitous anion in natural environments. For this reason, the products formed by oxidation of phosphate-containing Fe(II)SO4 solutions neutralized with bicarbonate were characterized. The rate of oxidation of Fe(II) increased with increasing P/Fe atomic ratio to 0.2 in the initial solution. Goethite (α-FeOOH) or lepidocrocite (γ-FeOOH) or both were produced and identified by powder X-ray diffraction (XRD). The ratio between lepidocrocite and goethite increased with increasing P/Fe. In the 5–8.5 pH range, the formation of goethite predominated at P/Fe < 0.005, but only lepidocrocite was detected by XRD for P/Fe > 0.02. Thus, phosphate favors lepidocrocite formation because lepidocrocite has (1) a layered structure (like its precursor green rust), and (2) a structure less dense than that of goethite, thereby requiring less complete removal of the green-rust interlayer phosphate to form. The lepidocrocite crystals were platy, with prominent {010} faces and the thickness of the plates decreased with increasing P/Fe from >25 nm for P/Fe < 0.005 to <5 nm for P/Fe > 0.1. The solubility of lepidocrocite in acid oxalate was nearly complete for P/Fe > 0.03. The lepidocrocite contained occluded phosphate, i.e., phosphate that could not be desorbed by alkali treatment. The decrease in the b unit-cell length with increasing P/Fe suggests that lepidocrocite may contain structural P.

High-resolution transmission electron microscopy (HRTEM) has shown regions of crystallites within noncrystalline matrices of three types of glass (volcanic glass, alkalic igneous glass, and synthetic, nuclear-waste-form glass) The volcanic glass fragments showed domains having 3-Å spacings. About 30% of the fragments of this glass showed localized lattice images, having spacings of 5, 7, 8, 10, 13, 14, 16, 19, and 20 Å, which also contain regular fringes having 3.3-Å separations. In the alkalic igneous glass fragments 3-Å domain structures were also noted as were localized lattice images having 7- and 12.5-Å spacings. Well-developed hollow spheres of primitive clays were present in both the volcanic and alkalic igneous glasses. Synthetic, nuclear-waste-foTm glass, fused at 1400°C and annealed at 550°C, showed locally ordered regions having 3.3-Å spacings. Low-angle X-ray powder diffraction showed major reflections at 8.5, 15–16, and 19 Å, which agree with some of the HRTEM measurements. These observations of domain structures, localized lattice images, primitive clays, and 14-Å clays in such noncrystalline glass matrices may contribute to an understanding of the growth of clay minerals. Such domains can apparently trigger the growth of clay products on the glass substrate.

High-resolution transmission electron microscopy (HRTEM) examinations have indicated that three types of surface layers may exist in natural kaolinite crystals. Type 1 has the expected 7-Å surface layer as terminations. Type 2 has one 10-Å pyrophyllite-like (or low-charge beidellite-like) layer as the surface layer on one side of a kaolinite particle (i.e., the layer sequence is TOTOTO … TOTOTOT, where T stands for tetrahedral sheet, O for octahedral sheet). Some industrial-grade highly-ordered kaolinites have such a 10-Å 2:1 surface layer on one side of the crystal. The spacing between the 10-Å layer and the adjacent 7-Å layer is not expandable. Type 3 kaolinite has one or several 10-Å collapsed smectite-like layers at one or both sides of a stack, i.e., (TOT)TOTO … TOTOTOT(TOT), forming a special kind of kaolinite-smectite interstratification. This type has only been recognized in some poorly-ordered kaolinites. The surface smectite layer(s) contribute to higher cation exchange capacity (CEC) values. These 10-Å surface layers were not detectable by X-ray diffraction (XRD). HRTEM and electron diffraction examination also revealed the structural features of individual kaolinite crystals. All kaolinites (from various origins and sources) studied show C-face-centering Of non-hydrogen atoms. Defects within the layer structure are common in both well-ordered kaolinite and poorly-ordered kaolinite.

A hydrothermally altered rhyolitic hyaloclastite from Ponza island, Italy, has four alteration zones with unique clay assemblages: (1) a non-pervasive argillic zone characterized by smectite; (2) a propylitic zone with interstratified illite-smectite (I-S) containing 10–85% illite (I); (3) a silicic zone composed of I-S with ≥90% I and pure illite; and (4) a sericitic zone with I-S ranging from 66% I to pure illite. Atomic force microscopy reveals abrupt changes in particle morphology with illitization, including initial changes from anhedral plates to laths and then to euhedral plates and hexagonal plates. I-S particles progressively thicken with illitization and mean particle area (basal plane) remains constant from pure smectite to I-S with 80% I. However, particle area increases from 90 to 100% illite. Computer modeling of I-S structural forms indicates octahedral cation ordering progressively changes from cis- vacant smectite to interstratified cis- and tnuis-vacant I-S, and then to trans-vacant illite. In addition, polytypes progressively change from 1 Md to 1M, and then to 2M, illite. Electron-microprobe and X-ray fluoresence analyses show that I-S chemistry progressively changes during illitization, evolving toward a phengitic composition with ∼0.89 fixed interlayer K+ per O10(OH)2. Octahedral Mg2+ shows little change with illitization, varying from 0.3 to 0.5 cations per O,10(OH)2. The layer charge of smectite is ~0.38 equivalents per O10(OH)2.

On the basis of abrupt changes in morphology and progressive changes in polytype and chemistry, smectite illitization on Ponza involved a dissolution and recrystallization mechanism with multiple stages of nucléation and crystal growth. In this multi-step model, temperature of alteration provided the major control for the layer composition, polytype, and morphology of I-S crystallites. Other factors that may play a secondary role include: K+ availability, water-rock ratio, and permeability. Alternatively, the mechanism of I-S and illite formation at Ponza and other hydrothermal environments may occur by direct precipitation of I-S crystallites from rhyolite glass and may not involve progressive reactions of smectite precursors.

The surface charge characteristics of a range of synthetic amorphous aluminosilicates, hydrous alumina, hydrous silica and two allophanic soil clays were determined by the retention of Na+ and Cl− as counter-ions from 0.1 M NaCl solution. In the pH range investigated (3–9), only negative charges could be detected in the hydrous silica and the most siliceous aluminosilicate [Al/(Al + Si) = 0.29], and only positive charges were detected in the hydrous alumina; whereas both positive and negative charges were detected in the more aluminous aluminosilicates and the soil allo-phanes. In all cases, the surface charges were pH-dependent and in the aluminosilicate series negative charge decreased and positive charge increased with Al/(Al + Si). Consequently, the point of zero charge increased with Al/(Al + Si).

The charge characteristics of the amorphous aluminosilicates could be explained by current models of their structure. Negative charge can be attributed to isomorphous substitution of Al for Si in the silicate structure and to the dissociation of silanol groups in structural and adsorbed silicate. Positive charge is attributed to protonation of hydroxy-aluminum species occupying cation exchange sites.

An electron-microscopic and Mössbauer spectroscopic study of a range of kaolinites has revealed three distinct types of iron contamination within these minerals: a) Ferric ion may substitute for aluminium and be evenly distributed throughout the lattice, b) Ferric ion may be present as a crystalline coating of goethite, as indicated by lattice-imaging studies, or c) as an amorphous coating. The distribution of the iron in the groups b and c is non-uniform and is highest at the flake surfaces. Ferrous ion, when detected, is thought to be evenly distributed throughout the lattice. The size of the contaminating goethite crystallites and the observed Mössbauer spectra of these samples suggest that such particles are super-paramagnetic. All kaolinites can be cleaned by acid treatment except those having iron substituting for Al3+.

As shown by scanning and transmission electron microscopy, halloysite in three rhyolitic tephras occurs as squat and elongate ellipsoids. Both morphologies are presumed to result from a similar lattice building mechanism. The squat ellipsoids form from allophane; the elongate ellipsoids form from feldspars. The squat ellipsoids do not possess flattened faces or spaces between books of layers at field moisture levels. Outgrowths from the squat ellipsoids are possibly due to inclusions of allophane, glass, ferrihydrite, or feldspar crystallites. Possible spiral growth of halloysite, giving curved surfaces, may be due to a continuous distribution of crystal dislocations.

The low-temperature alteration of a rhyolitic rock from Kimolos Island, Aegean, Greece, yielded an alteration profile characterized by gradual transition from fresh glass to bentonite containing homogeneous Chambers-type montmorillonite and then to a mordenite-bearing bentonite. Both mordenite and smectite were formed from poorly crystalline precursors, which probably had compositions comparable to that of the crystalline end-product. However, their composition may have been modified to some degree after reaction with the fluid phase. Particle length and width measurements of smectite crystals yielded lognormal profiles, which suggest supply-controlled crystal growth in an open system or random ripening in a closed system. The former mechanism is in accordance with the observed sustained supply of Mg and Fe by the fluid phase throughout the alteration profile and is believed to be the dominant formation mechanism of smectites in bentonites in general. In the mordenite-bearing zone, random ripening is expected in domains with low permeability, in which the system was essentially closed, favoring the formation of mordenite. The level of supersaturation with respect to smectite was probably lower in the mordenite-bearing zone. Smectite probably affected pore-fluid chemistry either through ion exchange or via dissolution of initially formed K-bearing smectite. The latter process raised the K+/(Na+ + Ca2+) activity ratio of the pore-fluid favoring K-bearing mordenite.

Palygorskite and sepiolite were digested with large excesses of hydrochloric acid at constant temperature for various periods of time. The reaction was found to be of first order with respect to the magnesium, aluminum and iron components in the clay and also with respect to hydrochloric acid concentration.

The reaction rate constant for Mg is larger than for Fe, which is larger than for Al. Approximately one-third of the octahedral-type cations are extraneous, suggesting that only three of the five octahedral positions are filled. The reaction rate constant of Mg in sepiolite is about 240 times that for palygorskite. This may be an indication that sepiolite is less stable to chemical weathering than palygorskite.

The activation energies for Mg, Al and Fe in palygorskite were found to be the same and equal to about 18·4 kcal per mole.

Treatment of partially acid-digested palygorskite with magnesium ions under alkaline conditions resulted in an increase in the X-ray intensity of the 10·5 Å spacing, suggesting some of the palygorskite was reconstituted.

Aluminum interlayers were synthesized under the same experimental conditions in a number of vermiculites and montmorillonites from different sources to determine the effects of the degree of neutralization of Al solutions, the time of reaction, and the type of structure.

Vermiculite fixed Al as well as hydroxy-Al ions in its interlayers, producing a stable 14 Å spacing and decreasing its cation exchange capacity considerably. Heating the Al-interlayered vermiculite at 300°C produced an interstratified mixture, indicating that some interlayers collapsed while others did not. The different collapse was attributed to different charge on vermiculite layers.

Neither the aging of vermiculite in Al solutions nor their OH/A1 ratios changed the stability of the interlayers appreciably.

Montmorillonites, on the other hand, did not fix Al ions but fixed appreciable amounts of hydroxy-Al ions. In addition, the stability of the interlayers in montmorillonite increased on aging in hydroxy-Al solutions and exceeded the stability of the interlayers produced in vermiculite. To explain the greater stability of montmorillonite interlayers, it was postulated that the more expanded interlayer space in montmorillonite provides a favorable locale for the organization of hydroxy-Al ions into gibbsite structure while the restricted expansion in vermiculite prevents it.

The size distribution of unit particles of two New Zealand allophanes (An and Rh), in dilute (0.8% w/v) aqueous suspensions, has been determined by small-angle neutron scattering (SANS). In addition, the specific surface area of the samples was measured by ethylene glycol retention, and their morphology examined by high-resolution transmission electron microscopy (HRTEM). The SANS data indicate that although both allophanes are somewhat polydisperse, the average diameter of their unit particles is significantly different, being 56 and 43 Å for allophane-An and allophane-Rh, respectively. Consistent with this observation, the specific surface area of allophane-Rh (897 mVg) is appreciably greater than that of allophane-An (638 m2/g). Under the electron microscope, both samples appear as aggregates of hollow spherules but HRTEM did not clearly distinguish between the two allophanes in that the largest population of spherules had diameters near 50 Å. Because of the assumptions and uncertainties involved in the SANS and surface area measurements, the data must be discussed in terms of their respective ratios. On this basis, the spherule diameter ratio is of the same order of magnitude as the inverse ratio of specific surface area. The latter value is also in reasonably good agreement with the corresponding ratios of phosphate adsorption capacity and BET nitrogen areas, derived from earlier studies.

Three methods were developed that allow for the imaging of any clay mineral in aqueous solutions with atomic force microscopy (AFM). The methods involve fixing the particles onto special substrates that do not complicate the imaging process, but hold the particles sufficiently so that they do not move laterally or float away during imaging. Two techniques depend on electrostatic attraction under circumneutral pH conditions, between the negatively charged clay particles and the high point of zero charge substrate (either aluminum oxide or polyethyleneimine-coated mica) whereas the third technique depends on adhesion to a thermoplastic film. The first electrostatic technique involves a polished single crystal α-Al2O3 (sapphire) substrate. This was used successfully as a substrate for clay-sized minerals with high permanent layer charge localized on the basal planes (phlogopite and vermiculite) and when the AFM was operated in TappingMode to limit the lateral forces between the probe tip and the particles. However, electrostatic attraction between the sapphire surface and clay minerals such as smectite and kaolinite (low or no permanent layer charge) is not sufficiently strong to adequately fix the particles for imaging. The second electrostatic technique involves a polyethyleneimine-coated mica surface designed to immobilize a larger variety of clay minerals (phlogopite, vermiculite, montmorillonite, and kaolinite), and in this technique weak bonding between the clay and the organic film is also a factor. The third technique, which does not depend on electrostatic attraction, fixes clay particles into the surface of a thermoplastic adhesive called Tempfix. This has proven useful for fixing and imaging relatively large clay particles with well-defined morphology. The Tempfix mount also requires imaging in TappingMode because the Tempfix is relatively soft.

The chemical composition and the thermal behavior of sodium and hydrogen octosilicate was studied by chemical and thermal analysis, infrared (IR), magic-angle-spinning nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray diffractometry. Both compounds are layer silicates with basal spacings of 11.10 and 7.38 Å, respectively. In both forms the ratio of Q4 silicon (connected via oxygen bridges with four silicon atoms) to Q3 silicon (connected with only three other Si atoms) is 1. At least a small part of the Q4 silicon can be substituted by aluminum. Elimination of water coordinated to the cations in sodium octosilicate results in a concomitant structural collapse. Replacement of the sodium ions by protons affects the atomic arrangement in the sheets only to a minor degree, but results in a decrease of the periodicity along the crystallographic c axis. Upon heat treatment an endothermal structural rearrangement occurs at about 360 K as revealed by significant changes of the IR and 29Si MAS-NMR spectra. Reexchange with Na ions largely, but not completely, restores the structure of the parent octosilicate.

The X-ray diffraction pattern of sodium octosilicate was indexed in the monoclinic system with a = 7.345 Å, b = 12.74 Å, c = 11.25 Å and β = 99.3°. Based on conclusions drawn from the results of the present study, the X-ray pattern of hydrogen octosilicate was tentatively indexed in the monoclinic system with a = 7.345 Å, b = 12.74 Å, c = 8.51 Å and β = 119.8°.

Hydrotalcite (HT) interlayered with hexacyanoferrate(II) ions ([Mg4.62Al1.52(OH)12][(Fe(CN)6)0.30-(CO3)0.29]) has been synthesized from the carbonate-HT ([Mg4.52Al1.50(OH)12][(CO3)0.77]) through double ion exchange reactions, and the products have been studied by chemical and physical methods. Mössbauer spectroscopy shows that hexacyanoferrate(II) is held rigidly in the interlayer by electrostatic forces and is characterized by a singlet at 0.01 mm s−1 at 80 K. X-ray diffraction shows an increase of the basal spacing (d003 from 0.78 to 1.1 nm following exchange. Hexacyanoferrate(II) in the interlayer was oxidized to hexacyanoferrate(III) (up to 20%) by dioxygen on dehydrating the interlayer either by drying at 70°C or by washing with nonaqueous solvents like acetone or ethanol. The CN (ν6) band of hexacyanoferrate(II) and (III) is found at 2036 cm−1 and 2112 cm−1, respectively. The presence of an absorption band at 2080 cm−1, assigned to free cyanide anions in the interlayer, suggests that the hexacyanoferrate(II,III) complexes are not inert in the interlayer, cyanide ligands being substituted with either water or hydroxyls. Oxidation and ligand exchange of the hexacyanoferrate(II) are also indicated by Mössbauer spectroscopy.

The Hançılı bentonite from Turkey shows significant changes in surface area, micro- and mesoporosity, surface acidity and acid strength with heating from 100 to 900°C for 2 h. The specific surface area (S) and specific micro-mesopore volume (V) of the original and heated samples were evaluated from N2 adsorption and desorption data, respectively, by standard methods. The adsorption of n-butylamine from the solution in cyclohexane on the samples was used to determine the total surface acidity (nm) and the adsorption equilibrium constant (K) was taken as a measure of the acid strength. S, V and nm having initial values of 98 m2g−1, 0.080 cm3g−1 and 4.8 × 10−4 mol g−1, respectively, stayed approximately constant as the temperature increased to 450°C and then decreased almost in parallel with each other, reaching their minimum or zero at 900°C. The total surface acidity, in general, declines with increasing temperature. The most acidic sites, however, increase with heating, and especially at dehydration and dehydroxylation. Acid strength reaches its maximum during the dehydroxylation phase at ∼600°C. It was concluded that the total surface acidity does not necessarily parallel the strength of the most acid sites.