Infrared spectra of nontronite reveal shifts to lower wave, number in peaks located at 3570, 1030, and 821 cm-1, which are assigned to vibrational modes for O-H stretching, Si-Ob (basal oxygens) tetrahedral vibrations, and FeO-H deformation, respectively, as the Fe2+ content increases upon reduction. A pleochroic shoulder at 1110 cm-1 resulting from Si-Oa (apical oxygens) interactions appears to be unchanged with reduction. The absorption band at 848 cm-1 shifts to higher energy with reduction of structural iron, and persists at 840 cm-1 after complete deuteration of structural hydroxyls. The band is assigned to a Fe-OH mode where the OH moves as a unit. The shift in the Si-Ob mode to lower vibrational energy with reduction may indicate a decrease in stress forces between the tetrahedral and octahedral sheets.

The kaolinite crystallization by homogeneous precipitation with previous hydrolysis of the feldspars added has been followed by pH and potassium concentration measurements. The synthesized products were studied by X-ray powder diffraction and electron microscopy and consist of kaolinite and mica, accompanied occasionally by traces of smectite. The relative quantities of the synthesized minerals depend fundamentally on the supply rate of the alkaline ions.

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.

The extent of protonation of organic bases in clay—water systems depends upon the adsorptive properties of the organo-clay species involved, and upon the structure and degree of hydration of the clay system. Organic molecules that can disperse cationic charge over two or more condensed aromatic rings give rise to greater surface-induced protonation than do single-ring organic molecules with similar solution pKa. Protonation in clay suspensions is frequently far in excess of that predicted on the basis of electrolytic suspension pH and solution pKa of the organic base. For a given organic base, protonation in a clay film exceeds that in the suspended clay system. Protonation in an organo-clay film increases as the film moisture content decreases. The extent of protonation in organo—clay systems varies with cationic species, cationic saturation, and clay type.

Solubility diagrams defined by log [Al3+] and log [H4SiO4] are given for hydrous alumina or aluminum silicate minerals which appear in bauxite, kaolin and pyrophyllite-diapore deposits. They are constructed based on thermodynamic data of relevant reactions both at the room temperature and at elevated temperatures.

An aqueous solution reacts to a mineral, in this case K-feldspar, and, by dissolving it, becomes saturated with respect to a certain mineral. This mineral begins to be precipitated and the solution changes its composition as a result of the precipitation as well as further dissolution of the original mineral. Then, it attains saturation with respect to another mineral, which is precipitated thereafter. Thus, different minerals are precipitated in turn.

The sequences of precipitation of minerals can be shown on the diagrams under different conditions. A sequence, aluminum hydroxide → kaolinite or pyrophyllite → silica mineral plus kaolinite or pyrophyllite is expected in a weakly acid solution. In contrast, a sequence, silica mineral → silica mineral plus kaolinite or pyrophyllite is expected in a strongly acid solution. The possibility of application of the sequence of precipitation thus expected to alteration zoning is also discussed.

Determinations of the molecular orientation of ornithine and 6-aminohexanoic acid on the surface of vermiculite using polarized i.r. attenuated total reflectance have shown that the ornithine molecules lay almost flat on the clay surface, except for a C–N bond projecting towards, and hydrogen bonded to, the surface. Ornithine formed two adjacent layers in the interlayer space, whereas 6-aminohexanoic acid formed only one layer. The terminal C-N bond of 6-aminohexanoic acid was at 46° to the surface, the plane of the carbon chain having a tilt of 34°, and the molecular axis sloped at 36° to the surface. The amino acids, thus orientated, were positioned in the interlayer space using van der Waals contact distances and hydrogen bond lengths obtained from i.r. spectra. The i.r. results agreed with two dimensional electron density projections. In the ornithine complex, some of the methylene groups were so close to the clay surface that interaction may have caused the marked reduction observed in the intensity of the C–H stretching vibrations.

Well developed smectite “crystals” up to 10 mm long, which probably are pseudomorphic after titaniferous hornblende phenocrysts, are present in a weathered dike in a Melbourne clay pit. The pseudomorphs contain 77 per cent of montmorillonite as determined by X-ray powder diffraction, differential thermal analysis, thermo-gravimetric and chemical analysis. The pseudo-hexagonal shape of the pseuodomorphs probably reflects the original crystal habit of the hornblende. The mechanism of alteration of an amphibole to a smectite is discussed.

Highly significant differences are observed between the methyl derivatives of attapulgite, produced when this mineral is reacted with (CH3)2Si(OC2H5)2, in the presence or in absence of HCl. In the first case, the corresponding infrared spectra show characteristic absorption bands due to the Si(CH3)2 radicals at 1260, 850 and 800 cm−1 as well as a shoulder at 960 cm−1, the latter assigned to silanol groups. The 850 cm−1 frequency which is usually exhibited by trimethylsilicon compounds is also detected when —O—Si(CH3)2 radicals are grafted in the silicates, but only if HCl is present in the reaction. Neither this band nor the 960 cm−1 shoulder appear in the spectrum of the derivative synthetized in absence of HCl. A comparative study by both i.r. spectroscopy and X-ray diffraction does not reveal structural modifications in attapulgite after it has been methylated in absence of HCl. However, although the i.r. spectra of the HCl-methylated derivatives, prepared at different periods, do not indicate substantial structural perturbations, X-ray diffraction patterns show a gradual weakening of the peaks due to attapulgite, as reaction time increases; the intensity of the (110) order reflection is drastically reduced after a 165 hr attack. The most viable mechanism for the grafting of the dimethylsiloxy units in attapulgite is through the HCl induced silanol sites. When the reaction is taking place in anh. benzene medium (absence of HCl), dimethyldiethoxysilane may be hydrolyzed by a fraction of water contained in attapulgite; the hydrolysis products which do incorporate on the surface of the silicate are identified by i.r. spectroscopy.

Analyses of samples of the Havensville Shale, collected from six localities in Kansas and northern Oklahoma, showed that the distribution of clay minerals and chemical variations in the clay minerals were related to changes in the sedimentary facies. The major clay minerals assemblages were: (1) illite, mixed-layer illite—montmorillonite, and regularly interstratified chlorite-vermiculite in the shaly facies of northern and central Kansas, (2) montmorillonite, illite and mixed-layer illite-montmorillonite in the calcareous shale and algal limestone facies of southern Kansas, and (3) kaolinite, illite and mixed-layer illite—montmorillonite in the sandy facies of northern Oklahoma. Differential settling and transportation of clay detritus were the major factors in the pattern of distribution of the clay minerals. Regional differences were noted in the abundance of 2m illite polymorphs, the K/Rb ratio and the illite 001/002 intensity ratio. Some structural variations and chemical differences among the clay minerals were consequences of modifications during deposition in different environments and diagenesis.

The electron structural analysis of a Madagascar sepiolite (Ampandrandava) was carried out by selected area electron diffraction obtained from monocristals. Fourier projections, derived from the experimental intensity of Okl, hOl and hkO reflections, show that the Mg2+ cations on the edges of the sheets are distributed between two sites. Correlatively the water molecules bound to these Mg2+ occupy two distinct positions. These principal structural differences with the Brauner and Preisinger model explain details of the i.r. spectra during the desorption of water or the adsorption of polar molecules. The differences between the two models can be considered as a consequence of treating the mineral in vacuum.

The reaction of hexamethylene diisocyanate with the surface of heat-activated vermiculite parallels the reactions with the oxides SiO2, Al2O3, MgO considered individually, which a number of authors have already described. The fixation ratio is about 5 molecules per 100 Å2 area. Nearly one half of the grafted molecules retain a “free” isocyanate function, which is requisite for a subsequent polyaddition of the processed mineral. The interaction with vermiculite occurs according to three principal processes; (i) formation of a surface urethane, (ii) formation of a surface carbamate, (iii) fixation by hydrogen bonds.

For very small crystallites diffraction theory shows not only broadening of powder lines, but generally also a shift of the line position, depending on the change of the structure factor over the range of broadening. For decreasing thickness of kaolinite crystals (less than 50 layers) an increasing shift of reflections is found: the lines (001), (002), (004) and (006) are shifted to apparently larger spacings, the lines (003) and (005) to smaller spacings, resulting in a nonintegral series. Presuming a known crystallite size, tables are given for evaluating true spacings from measured values of 2θ.

The influence of geomorphological site characteristics on soil clay mineral stability of montmorillonite-containing horizons of a southern Wisconsin soil catena was interpreted in terms of the solute activity function values of pSi(OH)4, pH-1/2pMg2+ and pH-1/3pAl3+ in suspensions of the separated clay fractions. Montmorillonite stability and/or formation vs that of kaolinite for the soil clays was evaluated by a plot of the solute activity functions on a three dimensional diagram derived for montmorillonite, kaolinite, and gibbsite at constant temperature (25°C) and constant pressure (one atm.). Although all the soil clays contained both montmorillonite and kaolinite, the position of the soil clay solute activity functions in the stability diagram clearly reflected the influence of the geomorphological—geochemical site conditions in which each soil horizon was developed, with corresponding differences in the SiO2/Al2O3 molar ratio of the reactive fraction. Montmorillonite stability positions of the solute activity functions were induced by soils (clays with reactive fractions with SiO2/Al2O3 molar ratios = 3–4) from calcareous or poorly drained horizons, while kaolinite stability positions of the functions were induced by soils (clays with reactive fractions of SiO2/Al2O3 molar ratios = 2) from acid, freely drained horizons.

Fourier syntheses have been used to establish the arrangement of organic molecules in the interlamellar regions of a 16.10 Å phase of ornithine-vermiculite and a 16.92 Å phase of 6-aminohexanoic acid-vermiculite. The organic cations form two layers parallel to the silicate surfaces in ornithine-vermiculite and in 6-aminohexanoic acid-vermiculite the organic cations form ascending and descending “stairs” from the silicate sheets.

Ornithine-vermiculite forms a true single layer polytype but by contrast 6-aminohexanoic acid-vermiculite is two-layered and has a true c axis of 34.09 Å. Since a two layered vermiculite was used as a starting material to prepare the organic complexes, exchangeable organic cations affect the stacking sequence of the silicate sheets.

A IIb orthochlorite (brunsvigite), from the chloritic metabasalt in the Middletown Valley of Maryland, was altered to a regularly interstratified chlorite—vermiculite after four months reaction in saturated bromine water on the steambath. The artificial weathering product resembles the regularly interstratified chlorite—vermiculite in a soil in Adams County, Pennsylvania, that has developed in greenstone similar to the chloritic metabasalt in the Middletown Valley of Maryland. The results of this and previous investigations on artificial and natural weathering of chlorites indicate that oxidation of structural Fe2+ is an important reaction in the alteration of chlorites into vermiculitic products. The results also show that IIb orthochlorites, apparently structurally similar but having different Fe2+ contents may react differently under the same weathering conditions. For example the acid oxidation treatment altered a IIb chlorite (diabantite) directly into a vermiculite, whereas the same treatment altered another IIb chlorite (brunsvigite) into a regularly interstratified chlorite—vermiculite. Detailed investigations of the chlorite structures are probably necessary to determine whether or not these alteration processes are structurally controlled.

Tosudite was found in the Hokuno pottery stone mine, Gifu Prefecture, Japan. The pottery stone ore body, altered from the Cretaceous rhyolitic rock, is composed of tosudite, interstratified illite-montmorillonite, kaolinite and quartz. Prepared by normal sedimentation method, the specimen is composed of 75.6% tosudite, 24.0% kaolinite and 0.4% quartz. The chemical composition of the specimen is SiO2 45.09%, TiO2 tr., Al2O3 37.31%, Fe2O3 0.94%, MgO 0.41%, CaO 1.94%, Li2O 0.45%, Na2O 0.09%, K2O 0.44%, H2O(−) 1.50% and ignition loss 12.11%. After subtracting the compositions of the impurities, the structural formula of tosudite is given as; interlayer cations K0.23, Na0.07, Ca0.86 + nH2O; ‘gibbsite’ layer Li0.76, Mg0.35, ${\rm{Fe}}_{0.29}^{3 + }$, Al3.34 (OH)12.00; silicate layer Al8.00 [Si13.83 Al2.17] O40.00 (OH)8.00.

Syntheses of tosudite were made from a starting material which is an interstratified illite-montmorillonite obtained from the same ore body. At 450°C, 400atm., reacting for 5 days, a tosudite-like mineral was synthesized.

Electron spin resonance (ESR) spectroscopy is used to investigate the nature of exchange sites on kaolinite. ESR spectra of exchangeable Cu2+ and Mn2+ on kaolinite indicate that divalent exchange ions are about 11–12Å apart on kaolinite surfaces and that planar Cu (H2O)42+ ions are oriented parallel to the surfaces. Solution-like spectra for exchangeable Cu2+ and Mn2+ are observed at high relative humidities, suggesting a high degree of mobility of exchange cations on kaolinite surfaces. The evidence seems to eliminate edge sites as being active in cation exchange at least in the acidic range of pH. Similar conclusions are derived from ESR studies of Cu2+-saturated talc and pyrophyllite. It is proposed that most exchange sites arise from ionic substitutions or mineral impurities in phyllosilicates.

Halloysite was mechanically ground in the presence of NaCl, KCl, RbCl, RbCl and CsCl, and i.r. spectra were recorded after various periods of grinding, up to 10 min. Changes in the wave-numbers and sharpness of absorption bands were interpreted using assignments accepted for kaolinite. Diminution of absorption bands of OH groups and the appearance of new bands indicate formation of complexes of halloysite with KCl, KBr, RbCl, and CsCl. Water was essential in the complex formation, which may be formulated:

The amount of the complex formed depended on the salt and the time of grinding. Complex formation requires that the cation be large enough to serve as a “structure breaker” of the interlayer water sheet. Complex formation also requires that the cation be a weak electron acceptor. Grinding also led to changes in the fine structure of the tactoid.

The possibility of using the i.r. spectrum of halloysite as a finger print for identification of the mineral is discussed. It was concluded that NaCl is the most reliable dispersing agent to determine whether or not a mineral sample belongs to the kaolinite group. Disks in RbCl may be used to differentiate between kaolinite and hydrated halloysite.

Adsorption of asphaltenes and resins onto montmorillonite occurs rapidly and to a large extent irreversibly under near-anhydrous laboratory conditions. Factors which influence the adsorption are the exchangeable cation on the clay, the basic nitrogen components of the molecules, and the solvent. As a result of this adsorption, the physical and chemical properties of the clay are drastically altered. The fundamental principles revealed in this study lead to a better understanding of the physical and chemical behavior of clays in petroleum reservoirs.