A comprehensive study of clay minerals should include determination of the vacancy pattern of the dioctahedral sheet. The purpose of this report is to consider the advantages and limitations in various diffraction and non-diffraction methods for the determination of the layer types in clay minerals. Identification of trans-vacant (tv) and cis-vacant (cv) clay minerals reported here is based on powder X-ray diffraction (XRD) patterns calculated for different polytypes consisting of either tv or cv layers, on the simulation of experimental XRD patterns corresponding to illite or illite fundamental particles in which tv and cv layers are interstratified, and on the semi-quantitative assessment of the relative content of the layer types in the interstratified structures by generalized Méring’s rules. A simple and effective method for identification of tv and cv layers in dioctahedral 2:1 layer silicates employs thermal analysis and is based on different dehydroxylation temperatures for tv and cv illite and smectite layers.

Crystal chemical analysis of various dioctahedral 2:1 layer silicates consisting of tv and cv layers indicates that compositional control is present in the distribution of octahedral cations over trans- and cis-sites. In dioctahedral smectites the formation of tv and cv layers is related to the layer composition and local order-disorder in the distribution of isomorphous cations. Dioctahedral 1M micas with abundant Fe3+ and Mg occur only as tv varieties. In contrast, 1M-cv illite, as well as cv layers in illite fundamental particles of I-S, can form only as Fe- and Mg-poor varieties. In illites and illite fundamental particles of I-S consisting of tv and cv layers, cv layers prevail when the amounts of Al in octahedra and tetrahedra are >1.55 and >0.35 atoms per O10(OH)2, respectively.

The main factors responsible for the stability of cv and tv illites have been established. Monomineral cv 1M illite, its association with tv 1M illite, and interstratified cv/tv illite occur around ore deposits, in bentonites, and in sandstones mostly as a result of different types of hydrothermal activity. The initial material for their formation should be Al-rich, and hydrothermal fluids should be Mg- and Fe-poor.

Tv and cv smectites of volcanic origin differ in terms of octahedral cation composition and distribution of isomorphous octahedral cations. Mg-rich cv smectites have random distribution of isomorphous octahedral cations, whereas in Mg-bearing tv smectites octahedral Mg cations are dispersed so as to minimize the amount of Mg-OH-Mg arrangements.

Micaceous layer silicate clay minerals are attractive materials for applications involving non-linear optics because of their low cost and ability to form well ordered, platy aggregates, but such applications require precise knowledge of the dielectric behavior of the clay. The purpose of the present study was to use Terahertz time-domain spectroscopy (THz-TDS) to determine the dielectric properties of certain cleavable layered clay minerals, including muscovite, vermiculite, phlogopite, and biotite. The samples were characterized by X-ray diffraction and Fourier transform infrared spectroscopy as well as chemical analysis by Energy dispersive X-ray spectroscopy. The THz frequency window investigated was the far-infrared region of 3.3 to ∼40.0 cm−1 corresponding to 0.1 and 1.2 THz, respectively. The samples were selected so that the hydrated form of the interlayer cation, e.g. Mg2+ present in the interlayer gallery of vermiculite, could be compared to species such as phlogopite, biotite, and muscovite with the dehydrated form of interlayer cations such as K+ or Na+. The frequency-dependent complex index of refraction of these natural materials was determined to vary between 2.50 and 2.80. The presence of water in the interlayer space of vermiculite was reflected in the detection of increased values of the absorption index in comparison with the muscovite, phlogopite, and biotite.

Layered double hydroxides (LDHs) are often used as precursors for mixed-oxide catalysts and the deposition of a LDH layer on supporting materials would be advantageous because of better utilization of active components. The purpose of the present study was to investigate the formation of LDHs on Al2O3/Al supports prepared by the anodic oxidation of aluminum foil in dilute aqueous solutions of Co, Mn, and/or Ni nitrates. The LDH deposition was carried out under hydrothermal conditions at 80–180°C for periods ranging from 8 h to 7 days. In the initial stages of the reaction, a surface alumina hydration was observed. The LDH phase was detected after long-term deposition (3–7 days) at 120–160°C and only a small amount of Mn was incorporated in the LDHs deposited. In solutions containing only Co and Mn cations, scanning electron microscopy (SEM) images show a gradual growth of platy crystals resulting in the formation of discrete bulky aggregates with sizes up to several tens of micrometers. The adhesion of aggregates to the support probably decreased with increasing size and oversized aggregates fell away; none was found in SEM images of the samples obtained after prolonged reaction times. When Ni cations were present in the solution, they were incorporated preferentially into the LDH phase; an homogeneous layer was formed, with single platy crystals oriented perpendicular to the support. After calcination at 500°C, the products formed on Al2O3/Al support exhibited a shift of reduction maxima to higher temperatures in comparison with mixed oxides obtained by thermal decomposition of coprecipitated LDHs.

Pillared clays (PILCs) with magnetic properties are materials with potential for wide application in industry and the environment, but only a few studies of these types of materials have been carried out. The purpose of this study was to advance knowledge of the preparation and magnetic properties of pillared clays by examining in detail a series of magnetic Ti-pillared clays (Ti-M-PILCs). Samples were synthesized at ambient temperature by sodium borohydride reduction of ferrous ions added by ion-exchange to Ti-pillared montmorillonite (Ti-PILCs). The properties of the Ti-M-PILCs were investigated using a superconducting quantum interference device (SQUID) and Mössbauer spectroscopy. Hysteresis, zero-field-cooled (ZFC), and field-cooled (FC) regimes were measured on different precursor materials prepared by calcination of Ti-PILCs at temperatures between 200 and 600°C. Hysteresis loops, recorded between −7 and 7 T in the temperature range 200–300 K, were observed in most samples depending on the preparation of clays. The ZFC/FC measurements were made after heating from 2 to 300 Kunder an applied magnetic field of 39.8 kA m−1. The influence of the calcination temperature of the starting Ti-PILCs on the structural and magnetic properties of the Ti-M-PILCs was examined. The presence of two different Fe-alloy distributions was found; a dispersed one for the less-calcined Ti-PILCs and clusters for the more-calcined ones.

Enhancement of the physico-chemical properties of elastomers can be achieved by the addition of fillers, such as silica, but the search for less expensive alternative materials continues. The objective of this study was to investigate natural or organically modified clay minerals as such an alternative. Organo-clays modified by quaternary ammonium cations with three methyl groups and longest alkyl chains of different lengths were prepared by ion-exchange reaction of the commercial product JP A030 (Envigeo, Slovakia) based on Jelšový Potok bentonite with organic salts: tetramethylammonium (TMA) chloride, octyltrimethylammonium (OTMA) bromide, and octadecyltrimethylammonium (ODTMA) bromide. Physico-chemical characterizations of the organo-clays used as fillers in rubber nanocomposites and their mechanical properties were measured using Fourier transform infrared (IR) spectroscopy, which provided information on the chemical composition of the mineral and on the amount of organic moieties adsorbed. X-ray diffraction analysis (XRD) was used to monitor the arrangement of organic chains in galleries of montmorillonite and showed that the longest-chain alkylammonium ODTMA+ ions were intercalated between layers, adopting a pseudotrimolecular conformation, while OTMA+ and TMA+ were in monomolecular arrangement. Surface areas were measured by sorption of N2 and ethylene glycol monoethyl ether. Natural rubber-clay nanocomposites were prepared by melt intercalation, in some cases also with addition of silica, a conventional reinforcing filler. The microstructure of montmorillonite in these composites was characterized by XRD analysis. The effect of clay and organo-clays loading from 1 to 10 phr (parts by weight per hundred parts of rubber) on stress at break, strain at break, and Modulus 100 (M100) was investigated by tensile tests. Filler ODTMA-JP A030 appears to be the most effective among the organoclays; surprisingly similar values of composite elongation and strength were obtained with unmodified bentonite JP A030.

Kaolin-group clay minerals can be modified to form nanotubular and mesoporous structures with interesting catalytic properties, but knowledge of the best methods for preparing these structures is still incomplete. The objective of this study was to investigate intercalation/deintercalation as a method for the delamination and rolling of kaolinite layers in relation to structural order. To prepare nanotubular material, kaolinites of different crystallinities and halloysite (all from Polish deposits) were chosen. The experimental procedure consisted of four stages: (1) preparation of a dimethyl sulfoxide precursor intercalate; (2) interlayer grafting with 1,3-butanediol; (3) hexylamine intercalation; and (4) deintercalation of amine-intercalated minerals using toluene as the solvent. Structural perturbations and changes in the morphology of the minerals were examined by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM). The number of rolled kaolinite layers depended heavily on the efficiency of the intercalation steps. An increase in the structural disorder and extensive delamination of the minerals subjected to chemical treatment were recorded. Kaolinite particles which exhibited tubular morphology or showed rolling effects were observed using TEM. The nanotubes formed were ∼30 nm in diameter, with their length depending on the particle sizes of the minerals.

Deep sediments from the Red Sea have been studied extensively and provide a rich resource for understanding mineral transformations under hydrothermal conditions. Interrelationships among various sampling sites, however, are still rather incomplete. The purpose of the present study was to increase understanding of these systems by characterizing and comparing the Fe-Mn oxyhydroxides from the southern Atlantis II, Chain A, Chain B, and Discovery Deeps, using high-resolution transmission electron microscopy. Some of the hydrothermal sediments of Chain A are dominated by Si-associated Fe oxides (ferrihydrite, goethite, lepidocrocite, and short-range ordered, rounded particles) resembling the hydrothermal sediments of the SW basin in the Atlantis II Deep, indicating sub-bottom connections between the Deeps. Although some of the sediments of the Discovery Deep show a similar trend; short-range ordered, rounded particles were not detected in these sediments, implying that crystallization of this short-range ordered phase is sensitive to the Si/Fe ratio in the brine and only at elevated ratios does it crystallize out of the brine. Silicon-associated and Fe-enriched Mn oxyhydroxides such as groutite, manganite, todorokite, and Mn-dominated lathlike layers occasionally contain Ca and Mg impurities. Manganese substitutes for Fe and vice versa, leading to a solid-solution series between goethite and groutite and Mn-enriched ferrihydrite. Hematite is the only Fe oxide in the hydrothermal sediments that is found to be lacking in impurities, which is probably due to its formation by recrystallization from other Fe oxides.

The influence of epigenetic (pre-pedogenetic) alteration of basic and ultrabasic rocks leading to the formation of phyllosilicate mineral associations is not well known. The purpose of this study was to gain further understanding of the processes involved by investigating the mineral associations of shallow soils underlain by amphibolites and metamorphosed gabbro-diabases (East Fennoscandia) and by serpentinous dunites (olivinite) and metagabbro amphibolites (the Ural Mountains). Where phyllosilicates were absent from the bedrock, they were also absent from the sola. The pedogenic alteration of the initial mineral soil matrix was very weak and did not result in a significant accumulation of phyllosilicates in the soils (East Fennoscandia). Pedogenesis enhanced the transformation of phyllosilicates, a process initiated by epigenic rock alteration.

Phyllosilicates in the sola from basic and ultrabasic rocks of the Polar Urals were largely inherited according to their origin. The inherited phyllosilicate association of the sola from ultrabasic rocks included talc, serpentine, and chlorite. Saponite resulted from pedogenesis; its distribution in various thin soils depending on the processes of neoformation and decomposition, the latter probably taking place under the influence of lichens and moss.

Chlorite and illite and products of their transformation, including vermiculite, comprise the phyllosilicate association of a solum from basic rock, and traces of talc were found. The distribution of vermiculite and randomly interstratified chlorite-vermiculite (C-V) depended on the processes of chlorite vermiculitization and vermiculite decomposition.

The cation exchange capacity (CEC) is a characteristic property of expandable clay minerals, such as smectites and vermiculites. The aim of this work was to examine the cation exchange behavior of vermiculite using the Cu-triethylenetetramine (Cu-trien) CEC method and the influence of mechanical and chemical pretreatment, with the ammonium acetate method serving as a reference. The Cu-trien method makes rapid and direct CEC measurements possible. Three different kinds of mill were used to grind a vermiculite sample from Russia, in order to reduce the particle size to <10 µm. The Netzsch CGS 10 dry mill reduced the particle size more effectively than the other grinding methods. Chemical pretreatments were used to remove carbonates, organic matter, Fe oxides, and divalent exchangeable cations from vermiculite samples prior to CEC measurements. Subsamples of ground and chemically pretreated vermiculite samples were saturated with Na, Li, Mg, Ca, and Cu cations to determine the effect of exchangeable cations on measured CEC values. Chemical pretreatment, monovalent cation pretreatment, and 48 h of shaking time were needed to measure vermiculite CEC values effectively using the Cu-trien method.

Ecologic building materials such as adobe bricks have become of greater economic importance in recent years. In the present work, the addition of selected materials to improve the compressive and bending strengths of adobe bricks was tested. The raw material (loam UD) was analyzed for its mineralogical and chemical composition. The loam studied consisted of quartz, feldspar, and the clay minerals chlorite, vermiculite, illite, and kaolinite. Prerequisites for using this loam for brick making were its grain-size distribution and the absence of expandable clay minerals.

To optimize the compressive and bending strengths of the adobe bricks, seven natural and ‘eco-friendly’ synthetic additives were admixed with the raw material and homogenized.

From this material, small adobe bricks and bars were made. One series of bricks and bars was made without additives but instead was coated with a hydrophobic impregnation cream. The bricks were stored for up to 20 days at 100 and 75% relative humidity (RH). After 1, 5, and 20 days, the compressive and bending strengths were measured to identify the critical humidity level for brick strength. The compressive and bending strengths of loam UD at dry conditions without additives showed values of 9 N/mm2 and 4.8 N/mm2, respectively. With some of the additives, the strength improved by up to 30%. The greatest increases in strength were achieved by mixing the loam with Acronal S650. Finely ground trass and diatomite also increased the dry strength. After storage at high levels of RH, these mixtures lost >50% strength. In contrast, the loam mixed with blast-furnace slag has a small initial strength but showed the smallest decreases in strength after exposure to high levels of RH.

The transformation of clay minerals into organo-clays by surfactant intercalation is of great environmental and industrial importance because it causes the clay to attract hydrophobic contaminants and other non-polar organic compounds, but a better understanding is needed of the mechanisms by which different classes of surfactants are intercalated. The purpose of this study was to synthesize and characterize an organo-clay comprising triethylene glycol monodecyl ether (C10E3) non-ionic surfactant, which has a lamellar phase at room temperature, intercalated into Ca-montmorillonite from Wyoming (SWy-2). The C10E3 non-ionic surfactant differed from previous non-ionic surfactants used in the formation of a lamellar phase in that it consisted of the stacking of molecules by hydrophobic interaction. C10E3-clay composites were characterized by complementary techniques (adsorption isotherms, X-ray diffraction, and infrared spectroscopy) and were compared to benzyldimethyltetradecyl ammonium chloride (BDTAC) cationic surfactant-clay composites for different loadings of the surfactant. For large loadings, the amount of C10E3 adsorbed, which can be described by the Langmuir equation, seemed to reach a steady state close to that of the cationic surfactant. The adsorption processes of the two surfactants were different. For the cationic surfactant, the adsorption, as described in the literature, was due to ion exchange between organic cations and Ca2+ counterions. The adsorption of C10E3 did not depend on electrostatic interaction but rather was due to several interaction mechanisms (H-bonding, ion-dipole, and hydrophobic interaction). For both surfactants, the expansion was limited to two adsorbed monolayers parallel to the clay surface. The expansion of the basal spacing to 17 Å suggested a complete dissociation of the C10E3 lamellar phase when adsorbed on the Ca-smectite. Organo-clays made using the non-ionic surfactant were stable, changing the chemical nature of clay to hydrophobic, and allowing for other cations to be exchanged, which has importance in the manufacture of new nanocomposites or geochemical barriers.