Effects of particle size, crystallinity and the amount of the structural water in kaolinites on their infrared spectra, were studied. The samples were ground in a vibrating ball-mill, and infrared and X-ray spectra, as well as thermal and specific surface area measurements, were taken on the initial and ground samples. Changes of the 3705-cm−1 infrared band intensity and of the absorbance ratio of the A 3630/A 3705-cm−1 bands were determined as a function of the grinding time. Correlation functions between the absorption ratio, calculated from the infrared spectra, and the average particle size, as well as between the amorphism, calculated from the X-ray spectra, and the average particle size, were obtained.

A series of mixed iron and titanium oxide coprecipitates ranging in composition between 0 < Ti/Ti + Fe < 1 was synthesized and aged under varying conditions of pH, temperature and time in order to establish a working model for pedogenic titanium and titano-ferric oxides. X-ray powder diffraction (XRD), selective chemical dissolution, magnetic susceptibility, charge distribution and electron optical data indicate that the freshly prepared Fe-Ti oxides consist of an Fe-rich (Ti-ferrihydrite) phase (Ti/Ti + Fe ⩽ 0.70) having pH-dependent positive charge and a Ti-rich phase (Ti/Ti + Fe ⩾ 0.7) with permanent and pH dependent negative charge.

Synthetic Ti-ferrihydrite and amorphous TiO2 were completely soluble in acid ammonium oxalate (2 hr extraction in the dark) whereas poorly crystalline anatase (width at half height, WHH > 2.0°2θ) was partly oxalate soluble. NH4-oxalate soluble Ti was particularly high in soils developed under a cool montane climate (afro-alpine) and lower in soils of warmer subtropical climate, which contain anatase and rutile.

Several mixed Fe-Ti crystalline phases were identified after aging NH3 coprecipitates of Fe and Ti nitrate at 70°C and pH 5.5 for 70 days:

1. (1) goethite and hematite in the composition range 0 < Ti/Ti + Fe ⩽ 0.20; at low Ti concentrations (<5 mole %) goethite was favored and/or hematite inhibited

2. (2) microcrystalline pseudorutile in the composition range 0.20 ⩽ Ti/Ti + Fe ⩽ 0.70

3. (3) anatase and ferriferous anatase in the range 0.70 ⩽ Ti/Ti + Fe < 1.0; with decreasing proportion of Ti the crystal-Unity of anatase decreased.

The results suggest that secondary or pedogenic Ti-Fe oxides can form by coprecipitation and crystallization in the weathering solution, and emphasize the essential role of water (as opposed to dry oxidation) in the alteration of primary titaniferous minerals.

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.

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 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.

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 effects of Na-citrate-dithionite (NaCD), ammonium oxalate in the dark (NH4Ox-D), and photolytic reaction under ultraviolet radiation (NH4Ox-P) on the mineralogy of <2-µm fractions of selected soils from Virginia were investigated. The NH4Ox-D treatment removed the smallest amounts of Al (<0.22%) and Fe (<0.50%) from all soils, indicating low levels of noncrystalline material in these materials. From the six soils examined, NH4Ox-P treatment extracted 5–62% more Fe and 12–300% more Al than the NaCD treatment. The NH4Ox-D and NaCD treatments revealed no X-ray diffraction detectable alterations to mineral phases present in <2-µm fractions of these soils. The NH4Ox-P treatment, on the other hand, produced considerable degradation of hydroxy-interlayered vermiculites in these soils, as evidenced by a shift of the 14-Å X-ray diffraction maxima to lower spacings with heat treatment of the sample. The NH4Ox-P treatment removed variable amounts of hydroxy-Al material from the interlayers of 2:1 layer silicates, depending on their stability and degree of development.

Inorganic gel and allophane collected from basaltic saprolite on Maui, Hawaii, and studied by Patterson in 1964 were reexamined. The main constituent of the gel is imogolite, and gibbsite and allophane are the minor constituents. Electron and X-ray diffraction patterns, DTA curve, and an infrared spectrum of the gel are characteristic of imogolite. The allophane is virtually noncrystalline to X-rays but contains a small amount of imogolite in relatively short threads. High-resolution electron micrographs indicate differences in structural organization between allophane and imogolite and suggest crystallization of imogolite from allophane.

The occurrence of imogolite as a weathering product has been reported in many localities from pyroclastic materials but not from massive rocks. Probably the exceptionally high rainfall, excellent subsurface permeability of the weathered material, and the low pH and high organic content of the leaching solution provide favorable conditions for formation of imogolite from basalt on Maui.

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%).

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.

The intercalation of formamide, potassium acetate, and hydrazine by halloysite and/or ka-olinite-rich samples, with and without subsequent displacement of the interlayer species by water or glycerol/water, has been investigated. Halloysite, as such, or in mixtures with kaolinite is completely expanded by all the treatments used, thereby enabling halloysite concentrations to be determined from the basal X-ray powder diffraction (XRD) peak ratios of the appropriate complexes. The values so obtained are usually proportional to the abundance of tubes, laths, and spherules in the transmission electron micrographs of the samples. The analysis of kaolin samples (halloysite plus kaolinite) by intercalation methods is less straight forward because a proportion of the kaolinite component in the system may not expand, even after lengthy (≥ 18 days) contact of the sample with the intercalating agent. Only prolonged immersion in hydrazine produces complete or nearly complete expansion of this component. When allowance is made for the presence of non-clay mineral components, kaolin-mineral percentages estimated from XRD peak intensity ratios of the hydrazine complexes generally agree with values derived from differential thermal analysis to within ±10%. Kaolinite in mixtures with halloysite cannot be directly determined by intercalation procedures inasmuch as treatments which result in complex formation with kaolinite also expand halloysite. In such systems, kaolinite can be estimated by difference between the concentration of kaolin minerals and halloysite.

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.

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.

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.

X-Ray powder diffraction and thin section analyses indicate that marginal lacustrine mudstones of the Green River Formation in the south-central Uinta basin, Utah, contain abundant analcime. The analcime has a low Si/Al ratio (<2.31) and occurs as very fine grained disseminated crystals and, to a lesser extent, as coarser-grained pore-filling cement. Analcime-rich mudstones and associated sandstones, siltstones, and carbonates lack volcanic detritus and zeolites other than analcime, thus making it difficult to support the concept that the analcime formed from precursor zeolites derived from volcanic glass altered in saline, alkaline-lake water. Abundant dolomite, syneresis cracks, and the absence of freshwater pelecypods and gastropods suggest that the lake (Lake Uinta) was moderately saline and alkaline. The restricted illite-illite/smectite clay mineral suite in the analcime-rich mudstones suggests that detrital clays significantly altered in a moderately saline and alkaline environment, thereby providing a source of Si and Al for the formation of analcime.

Red mudstones contain twice as much analcime as green mudstones (14 vs. 7 wt. %). Green mudstones have a day mineral suite consisting of illite (44 wt. %), mixed-layer illite/smectite (35 wt. %), smectite (12 wt. %), and minor kaolinite (4 wt. %) and chlorite (5 wt. %), whereas red mudstones have a more restricted day mineral suite consisting ofillite (68 wt. %) and mixed-layer illite/smectite (26 wt. %) with very minor smectite, chlorite, and kaolinite. Periodic minor fluctuations in lake level probably exposed large areas of shallow lacustrine-interdistributary green mud. Evaporative pumping on the exposed mudflats concentrated the moderately saline and alkaline-lake water, thereby producing Na-rich brines that enhanced the formation of analcime by accelerating the alteration of detrital clays and, perhaps, other minerals. Oxidation of iron from altered iron-bearing minerals stained the analcime-rich mud red with iron hydroxide or oxide (perhaps hematite). The overall reaction from green to red mud (mudstones) was probably: detrital phyllosilicates + Na-brine + iron-bearing minerals + oxygen → analcime + iron hydroxide or iron oxide.

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.

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.

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.

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.