Hypothetical model structures for magadiite and sodium octosilicate, based on the structure of the zeolite dachiardite, are proposed that consist of layers of 6-member rings of tetrahedra and blocks containing 5-member rings attached to both sides of the layers. The infrared (IR) and nuclear magnetic resonance spectra of magadiite and sodium octosilicate have features in common with spectra of zeolites in the ZSM-5 and mordenite groups. A peak at 1225 cm-1 in the IR spectra of magadiite and sodium octosilicate is characteristic of zeolites containing 5-member rings, such as ZSM-5- and mordenite-type zeolites. The defect structures of pentasil zeolites may therefore be akin to layered alkali metal silicates containing zeolite-like domains, in which part of the silanol groups from adjacent silicate layers are condensed (cross-linked) forming siloxane linkages.

Area-weighted thickness distributions of fundamental illite particles for samples of illite and illite-smectite from seven locations (including bentonites and hydrothermally altered pyroclastics) were measured by Pt-shadowing technique, by transmission electron microscopy. Most thickness distributions are described by lognormal distributions, which suggest a unique crystallization process. The shapes of lognormal distributions of fundamental illite particles can be calculated from the distribution mean because the shape parameters α and β2 are interrelated: β2= 0.107α − 0.03. This growth process was simulated by the mathematical Law of Proportionate Effect that generates lognormal distributions. Simulations indicated that illite particles grow from 2-nm thick illite nuclei by surface-controlled growth, i.e., the rate of growth is restricted by how rapid crystallization proceeds given a near infinite supply of reactants, and not by the rate of supply of reactants to the crystal surface. Initially formed, 2-nm thick crystals may nucleate and grow within smectite interlayers from material produced by dissolution of single smectite 2:1 layers, thereby transforming the clay from randomly interstratified (Reichweite, R = 0) to ordered (R = 1) illite-smectite after the smectite single layers dissolve. In this initial period of illite nucleation and growth, during which expandable layers range from 100 to 20%, illite crystals grow parallel to [001]* direction, and the dimensions of the (001) plane are confined to the size of the original smectite 2:1 layers. After nucleation ceases, illite crystals may continue to grow by surface-controlled growth, and the expandable-layer content ranges from 20 to 0%. This latter period of illitization is characterized by three-dimensional growth. Other crystal-growth mechanisms, such as Ostwald ripening, supply-controlled growth, and the coalescence of smectite layers, do not produce the observed evolution of α and β2and the observed shapes of crystal thickness distributions.

This work investigates unit cell dimensions, crystal size and specific surface area of aluminous goethite that was progressively dehydroxylated to form hematite. Goethite synthesized from the ferrous system altered to hematite with DTGA maximum increasing from 236° to 273°C for 0 to 30.1 mole % Al-substitution. Unit cell dimensions of goethite and hematite decreased as Al-substitution increased and increased as excess OH increased. The crystallographically equivalent a axis of goethite and c axis of hematite were more sensitive than other axes to the presence of excess structural OH associated with Al-substitution. Specific surface area increased from 147 to 288 m2/g for goethite and from 171 to 230 m2/g for hematite as Al-substitution increased. An increase in specific surface area on heating goethite at temperatures between 200° and 240°C is related to a decrease in the size of coherently diffracting domains of goethite crystals and to the development of pore and structural defects associated with the formation of hematite. The decrease in specific surface area for heating temperatures above 240°C is attributed to the growth of hematite crystals by diffusion.

This work presents the water retention curves obtained for two natural bentonites compacted at different dry densities. The density of the bentonite was kept constant during the determination, for which specific methodologies were developed. The materials tested are the FEBEX and the MX-80 bentonites, in the first of which divalent cations (Ca and Mg) predominate in the exchange complex; MX-80 is mainly sodic. The water retention capacity of the FEBEX bentonite is greater, although the difference between both bentonites becomes smaller towards low suctions. The effect of dry density on the water retention curve is very small or imperceptible for suctions >10 MPa, and below this value the lower the density of the bentonite, the greater its water content. The basal spacing of the samples equilibrated at different suctions has been measured and found to be in the order of those measured by other authors in powder samples equilibrated to the same suctions. The study was performed in the framework of projects concerning the engineered bentonite barrier of high-level radioactive waste repositories.

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.

Sepiolite from Vallecas-Vicálvaro, Spain, contains 1.3% fluorine. Laser microprobe mass spectrometry of this sepiolite suggests the presence of fragments of (SiO2)nOMgF and (SiO2)nOMgOH, which are typical of the sepiolite structure. During thermal dehydroxylation, the fluorine in this sepiolite is removed simultaneously with OH groups at about 750°C. Nuclear magnetic resonance spectroscopy (NMR) of 19F indicates that the fluorine is located in the interior of the sepiolite structure, probably substituting for OH groups, and is homogeneously distributed. In the Vallecas-Vicálvaro sepiolite, about one of every four OH groups bound to Mg2+ is substituted by fluorine. The kinetics of extraction of Mg2+ and F- ions by acid treatment (1 N HCl) shows a more rapid extraction of Mg2+, with a monotonous decrease of the Mg/F ratio as the extent of extraction increases. These results support the internal location of the fluorine, as suggested by the NMR data.

Prograde evolution of illite/smectite occurring in an unusually-thick (8000 m) sequence of Mesozoic-Cenozoic sediments in the Basque-Cantabrian Basin, Spain, has been studied using XRD and TEM/AEM. The sediments, which are only slightly tilted, cover the range from smectite to illite, and the most deeply buried ones are unique in that they span the range from diagenesis through low-grade metamorphism (anchizone), with no apparent overprinting due to tectonic deformation.

Pelites are absent from the shallow section, but smectite occurs in marls as high-charge, K-dominant and low-charge, K-poor anastomosing arrays of layers. At intermediate depths, authigenic clay is identified largely as R1 I/S, coexisting with packets of R≫3 I/S (nearly pure illite), where illite-like and smectitelike layers can be identified by contrast in TEM images, which is consistent with XRD data. The authigenic clay of the deepest samples consists of illite with no or almost no expandable layers, which occurred as packets with layers largely subparallel to bedding, K-deficient composition in comparison with muscovite, 1Md-like SAED patterns, and 100 Å mean packet thickness. There is no evidence of deformation stress-induced, non-bedding-parallel clays in the deepest samples. Detrital micas with either a phengiterich or a phengite-poor composition range dominate the phyllosilicate fraction of all the samples. Detrital micas show no changes over the diagenesis/metamorphism range and appear to have behaved as if isolated from authigenic clays.

Authigenic clays occur as bedding-subparallel packets that evolved during passive burial metamorphism through dissolution/crystallization of less-evolved clays. Where illite-like and smectite-like layers can be identified, TEM images imply a discontinuous series in which packets of R1 I/S (50% I) transform to packets of nearly-pure illite, that is, an Ostwald-step-rule-like sequence. Such immature illite remains unmodified with further burial, and is apparently the potential predecessor of stress-induced, highly-evolved mica of higher-grade, tectonically-deformed pelites.

Wyoming montmorillonite, <2-µm particle size, saturated with Na, K, Mg, Ca, and Ba ions, was reacted with uranyl nitrate solutions in the concentration range 1–300 ppm uranium. With constant amounts of clay and solution volume, the adsorption isotherms of uranyl ions on the clay followed Langmuir-type curves with increasing concentration of uranium. The maximum adsorption derived from linear Langmuir plots corresponds to the exchange capacity of the clay. Experiments with solutions of constant volume and constant ionicity, but with variable proportions of uranyl and other cations, showed that uranyl ions were strongly preferred by the clay to Na+ and K+, but less strongly than Mg2+, Ca2+, and Ba2+.

Chemical analyses of uranyl montmorillonites prepared with nitrate solutions, 0.05 M and pH ≃ 2.0, gave interlayer cations (UO2)0,094H0,12. Addition of NaOH to the uranyl nitrate solution to increase the pH to 4.0 gave a montmorillonite with interlayer cations (UO2)0,083Na0,12H0,04. A fully exchanged uranyl montmorillonite was prepared with 0.05 M uranyl acetate solution, pH ∼ 4.0, followed by further treatment with 1.25 × 10−5 M solution, pH ∼ 4.5. The resulting interlayer composition was (UO2)0,19(H2O)1.15 which corresponds with the hexahydrate ion, [(UO2)−6H2O]. X-ray powder diffraction and thermal data are recorded for the fully exchanged uranyl montmorillonite.

Nontronite and microbes were detected in the surface layers of deep-sea sediments from Iheya Basin, Okinawa Trough, Japan. Nontronite, an Fe-rich smectite mineral, was embedded in acidic polysaccharides that were exuded by microbial cells and electron microscopy showed that the nontronite layers were apparently oriented in the polysaccharide materials. We propose that the formation of nontronite was induced by the accumulation of Si and Fe ions from the ambient seawater and that extracellular polymeric substances (EPS) served as a template for layer-silicate synthesis. Experimental evidence for this hypothesis was obtained by mixing a solution of polysaccharides (dextrin and pectin) with ferrosiliceous groundwater. After stirring the mixture in a sealed vessel for two days, and centrifuging, Fe-rich layer silicates were identified within the precipitate of both the dextrin and pectin aggregates, whereas rod-shaped or spheroidal Si-bearing iron hydroxides were found in the external solution. Microbial polysaccharides would appear to have affected layer-silicate formation.

Adsorptive-type organoclays, where hydrocarbons adsorb directly to the siloxane surfaces, were studied to find new organic cations and to determine the parameters that produce effective sorbents. Organoclays were prepared from hectorite by cation exchange with small, aromatic organic cation salt solutions. Trimefhylphenylammonium (TMPA) chloride was obtained and iodide salts of commercially-unavailable aromatic cations were synthesized and used to prepare organoclays. An aqueous mixture of benzene, toluene, ethylbenzene, and xylenes (BTEX) consistent with the composition of unleaded gasoline was used in sorption isotherms to compare the sorptive properties of the organoclays. Only the TMPA, methylphenylpyridinium (MPPyr), and trimethylammonium indan (Indan) organoclays were effective BTEX sorbents. Organoclays prepared from methylpyridinium (MPyr), trimethylammonium biphenyl (Biphenyl), and trimethylammonium fluorene (Fluorene) were poor sorbents. The MPPyr and TMPA organoclays preferentially sorbed ethylbenzene, whereas the Indan organoclay preferentially sorbed benzene and toluene. Langmuir-type sorption isotherms for the TMPA, MPPyr, and Indan organoclays implied surface adsorption, whereas linear isotherms suggested that partitioning was the sorptive mechanism for the MPyr, Biphenyl, and Fluorene organoclays. Water hydrating the small MPyr cation and the larger bulk of the Biphenyl and Fluorene cations may have blocked BTEX access to the interlayer siloxane surfaces. Although the rather bulky MPPyr and Indan cations produced effective organoclays, compact size and low hydration are organic cation properties that typically yield effective adsorptive-type organoclays.

This review of the literature shows that there have been many attempts to modify or revise the original definition of halloysites as distinguished from kaolinites, which was based on the greater water content of the halloysites. In general, these various attempts have arrived at definitions of halloysites as distinguished from kaolinites that are based on one or more particular instrumental or chemical techniques. Further investigations with almost all of these techniques have shown the apparently clear distinctions of this kind to be misleading. All such instrumentally—or chemically—based definitions were shown to either complicate and confuse the distinction between halloysites and kaolinites or to provide only empirical and subtle distinctions. It is concluded that only the original definition, with slight adaptations, enables clear and unambiguous distinctions to be made between halloysites and kaolinites. It is noted, however, that a distinctive structure for halloysite has been postulated as a result of electron diffraction studies. Further studies of this kind could well establish such a structure as being definitive of the mineral species.

The literature also reveals a long-standing disagreement over the nomenclature of different forms of halloysite and particularly over the nomenclature of and distinction between the two forms of halloysite at the extreme ends of the hydration series. An analysis of experimental studies of the relationship between these two and other hydration states of halloysite reveals that forms of halloysite with all possible interlayer water contents between 0 and 2 molecules H2O per Al2Si2O5(OH)4 unit cell may exist and that the two end members of the hydration series may not be seen as distinct phases. The fully dehydrated halloysite is the only thermodynamically stable form of the mineral. A nomenclature system which was proposed by MacEwan in 1947 is consistent with these results. This system, amended only by the exclusion of the unnecessary term ‘metahalloysite’ should therefore be adopted in all studies of halloysites.

Li-, Na-, K- and Ca-saturated Wyoming montmorillonites have been prepared and used to obtain Li,Na-, Li,K-, and Li,Ca-montmorillonites with a range of Li contents. These were heated at 220°C for 24 hr, causing the Li+ ions to migrate mainly into the layer structure and leaving varying amounts of Li+, Na+, K+, and Ca2+ ions in the interlayer positions as determined by exchange with NH4+ ions. The results are only partially consistent with a migration of the Li+ ions into vacant octahedral sites up to the limit of the octahedral layer charge. Solvation of the resulting clays with water and various organic liquids showed the following results: With water, acetone and 3-pentanone, expansion of the montmorillonites increased in a step-wise manner with increasing numbers of interlayer cations qualitatively in accord with the field strength of the cations and the dipole moments of the molecules. With ethanol, ethylene glycol and morpholine, swelling with each liquid was practically independent of the number of interlayer cations, within the limits of the prepared materials. It is suggested that for the second group of liquids some mechanism additional to cation-dipole interactions, such as hydrogen bonding to silicate oxygen surfaces, may play an important part.

An X-ray diffraction study of aqueous emulsions of a Na-montmorillonite shows that: (1) At low water content, the d-spacings of the montmorillonite increased stepwise with increasing water content; (2) At high water content, sharp (001) peaks due to regular stacking of montmorillonite layers were not detectable, but broad, halo patterns were observed in the low-angle scattering region; and (3) The addition of Ca2+ or H+ to the aqueous emulsions caused Ca-montmorillonite or H-montmorillonite crystals to form. A zig-zag column model of montmorillonite layers fits the observed data for aqueous emulsions of Na-montmorillonite.

Infrared absorption spectra show important changes in the positions and form of the absorption bands of a film of attapulgite after it has been pumped out. An attempt to differentiate among some of the multiple frequencies due to OH groups is based on the information obtained from dehydration and deuteration experiments. The 1198 cm−1 shoulder, characteristic of attapulgite, is assigned to a Si-O vibration. When attapulgite is refluxed with 5N HCl for 5 hr the octahedral layer is dissolved. The acid attack causes the disappearance of the Si-O-Si absorption bands from attapulgite giving rise to a characteristic vibration at 1090 cm−1, as well as another absorption at 960 cm−1. The latter indicates the presence of silanol groups.

Tetramethylphosphonium-smectite (TMP-clay) and tetramethylammonium-smectite (TMA-clay), were prepared and characterized as adsorbents for a series of aromatic and chlorinated hydrocarbons. The sorption of benzene, alkylbenzenes, and carbon tetrachloride as vapors and as solutes from water was studied to evaluate the effect of water on adsorption efficiency. Adsorption of organic vapors depended on the N2 BET surface area. TMA-clay was a slightly better adsorbent than TMP-clay, due to its somewhat higher surface area. The Langumir isotherms obtained indicated that adsorption occurred predominantly in the interlayer micropores, apparently on mineral surfaces between onium ions. Adsorption efficiency of both organo-clays decreased, compared to vapor sorptions, in presence of water. Lower sorption was apparently due to shrinkage of the interlayer pore or cavity sizes by hydration of interlayer TMA and TMP cations. Although sorption efficiencies of both organo-clays was reduced in presence of bulk water, the extent of reduction was much less for TMP-clay. Thus, TMP-clay was a better adsorbent than TMA-clay in presence of water, despite its lower surface area, in direct contrast to vapor sorption. The Langumir isotherms indicated interlayer sorption of benzene, alkylbenzenes and carbon tetrachloride from water by TMP-clay. The absence of Langumir isotherms for toluene, ethylbenzene and p-xylene uptake from water by TMA-clay indicated that these bulkier solutes were not adsorbed in the interlayers. These results indicate that hydration of TMA cations causes shrinkage of the interlayer pores to dimensions that exclude these solutes. The lower degree of hydration of TMP cations enables TMP-clay to maintain interlayer pores large enough to accommodate the bulkier alkylbenzenes.

Pyrophyllite is the precursor to other smectite-group minerals which exhibit swelling. The mineral structure of pyrophyllite can lead to other minerals in the smectite group, including montmorillonite, through appropriate isomorphous substitutions. In this work, an atomic model of the pyrophyllite interlayer was constructed. The response of the interlayer was evaluated using steered molecular dynamics simulations. In steered molecular dynamics, external forces were applied to individual atoms to study the response of the model to applied forces. In this work, forces are applied to the surface clay atoms to evaluate the displacement vs. applied stress in the interlayer between clay layers. This paper describes the construction of the model, the simulation procedure, and the results of the simulations which show that under the applied loading, deformation occurs mainly in the interlayer. The clay layers show relatively little deformation. The results show that the relationship between applied stress and displacement of the interlayer is linear. The stress-deformation relationship for the interlayer is presented.

The transformation of sodium and potassium smectite into mixed-layer clay was followed in hydrothermal kinetic experiments. Glasses of beidellite composition and the Wyoming bentonite were used as starting materials. Temperatures ranged between 260 and 490°C at 2 kbar pressure, and run times ranged between 6 hr and 266 days.

The course of the reactions was found to be strongly affected by interlayer chemistry. When potassium was the interlayer cation, increasing reaction produced the series: randomly interstratified illite/smectite-ordered interstratified illite/smectite-illite. This sequence is equivalent to that formed in shales during burial diagenesis. With interlayer sodium and temperatures above 300°C, an aluminous beidellite (Black Jack analog)-rectorite-paragonite series was realized. The difference between these two diagenetic families is discussed. Below 300°C, sodium beidellite formed randomly interstratified mixed-layer clay much like potassium beidellite, except that a higher layer charge was required to produce sodium mica-like layers. The higher charge resulted from sodium's higher hydration energy. The difference in hydration energy between potassium and sodium may account for the fixation of potassium rather than sodium in illite during burial diagenesis.

The appearance of ordered interlayering in mixed-layer phases is also related to interlayer chemistry. Ordering formed in sodium clays at high expandabilities, whereas it never appeared in the potassium clays above approximately 35% expandable. The appearance of ordering may be partly related to the polarizing power of the mica-like layers.

Phase diagrams, constructed from the kinetic experiments and from the composition and occurrence of natural clays, are presented for the systems paragonite and muscovite-2 quartz-kaolinite-excess water. This study also reports the first synthesis of a Kalkberg-type mixed-layer clay.

To test the hypothesis that berthierine in oolitic ironstones formed by diagenetic transformation of detrital kaolinite, laboratory experiments simulating the early diagenetic conditions were conducted. Representative sets of the initial sediment were prepared in distilled water and artificial seawater suspensions by mixing 4–13 g/liter kaolinite with Fe(OH)3 precipitated from 0.1-0.3 M FeCl3 solutions. Na2S2O4 was added to the suspensions as a reducing agent, and inert N2 atmospheres were used to maintain the required Eh between +100 and -400 mV. The pH of the suspensions was controlled between 8 and 5 with dilute HCl. Within 300 days, the iron content of the bulk kaolinite in the seawater suspensions progressively increased from 0.18 to 2.44% at pH = 7 and Eh between -250 and -350 mV. Energy dispersive X-ray analyses of individual clay platelets in the final products showed progressive, temporal increase in Fe, and concomitant decrease in Al and Si. X-ray powder diffractometry revealed small d(001)-d(002) shifts, marked intensity reversals o. (001) an. (002) reflections, and the development of additional characteristic berthierine reflections with time. These data suggest progressive transformation of kaolinite to berthierine. Microprobe analyses of natural berthierine in oolitic ironstones also showed parallel patterns, which substantiate such progressive transformation from the margin toward the core of the ooids. The transformation did not take place in distilled water. The addition of Mg2+ to the distilled water suspensions, however, promoted the transformation.

Solid phase transformation and metal solubility were monitored after coprecipitation of Cd2+, Cu2+, Pb2+ and Zn2+ with Fe3+ to form ferrihydrite by titration to pH 6. The (co)precipitates were aged at room temperature for up to 200 d and subsequently heated for 60 d at 70 °C. The mode of (co)precipitate formation, rapid and slow titration, was also investigated. Metal solubility was measured by anodic stripping voltammetry. Surface area, Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analysis were used to follow the transformation of ferrihydrite after initial (co)precipitation. Electron microprobe analysis (EMPA) was used to show the distribution of metals within ferrihydrite aggregates. Thermal treatment produced a reduction in soluble Cd2+ and Zn2+, whereas Pb2+ appeared to be expelled from the solid phase. The more stable coprecipitate (formed by slow titration) maintained a constant Cu2+ solubility after thermal treatment. Characterization of the solid phase by XRD indicated that the presence of low levels of metals did not affect the initial or final transformation products, although metals present during the slow titration seemed to stabilize a higher surface area material. The rapid titration resulted in a less ordered (1-line) ferrihydrite than the slow titration (9-line). Furthermore, FTIR analysis indicated that the presence of metals promoted the formation of mixed (microcrystalline) end-products. The initial coprecipitation products seem to determine the final thermal transformation products. These transformation products include ferrihydrite, hematite (Hm), and goethite (Gt)- and lepidocrocite-like microcrystalline structures. Although experimental conditions were favorable for the homogeneous distribution of metals throughout the coprecipitate, EMPA suggests that Cu and Zn segregation within aggregates of Fe oxides occurs.

The structural damage produced by dry grinding and acid leaching of chrysotile was studied by transmission and scanning electron microscopy, infrared spectroscopy, X-ray powder diffraction, and thermogravimetric analysis. Severe dry grinding converted the chrysotile fibers into fragments having strong potential basic reaction sites. These sites were immediately neutralized by molecules present in the atmosphere (e.g., H2O, CO2). Acid leaching transformed the chrysotile fibers into very porous, non-crystalline silica, which was easily fractured into short fragments. The damage produced in the chrysotile structure by grinding or leaching was assessed by monitoring the intensity of various infrared absorption bands.