Titanium dioxide (TiO2, rutile) nanoparticles, inorganic ultraviolet absorbers, are used extensively in sunscreen cosmetics as an inorganic ultraviolet (UV) absorber to prevent skin damage; because of their nanotoxicity, use in combination with a support, such as montmorillonite (Mnt), rather than alone, is suggested. Mnt-supported TiO2 composites (Mnt-TiO2) for sunscreens are most suitable when the particles are spherical and of relatively uniform size, which are normally accomplished by spray drying, but this is difficult to achieve because of the naturally layered structure of Mnt. The objective of the present study was, therefore, to find the ideal characteristics of spray-drying nozzles to produce the desired spherical shape and size distribution of the Mnt-TiO2 composite particles. The starting Mnt was extracted from natural bentonite by particle-size separation. An ultrasonic nozzle in the spray dryer was selected for use in the synthesis of Mnt-TiO2 composites based on the particle-size distribution (PSD) of Mnt prepared using a two-fluid nozzle and an ultrasonic nozzle at 453 K. The incorporation of TiO2 in the final Mnt-TiO2 composites was examined by X-ray powder diffraction (XRD) and elemental analysis. With increasing TiO2 concentration, the TiO2 content and average particle size of the Mnt-TiO2 composites increased. Scanning electron microscopy (SEM) images showed that all samples prepared had uniform and nearly spherical shapes. Absorbance of UV by Mnt-TiO2 (5:1) composites was greater than that by either purified Mnts or pure TiO2. The present study demonstrated a simple method, using a spray dryer with an ultrasonic nozzle, to synthesize Mnt-TiO2 composites of uniform size and shape suitable for cosmetic application.

Several procedures for hydrothermal synthesis of saponite can be found in the literature. They differ in terms of the preparation conditions of the precursor and of the synthesis temperature. The objective of the present study was to investigate how these two parameters influence the structure of the final synthesis product. The precursor was prepared from Mg(NO3)2, Al(NO3)3, and Na4SiO4 in three different ways: as a gel, a dried gel, and a calcined gel. The influence of the synthesis temperature on the structure of saponite was investigated in the range 90–200°C. The results showed that the use of a calcined precursor yielded a single mineral phase, saponite, with up to 90% aluminum in tetrahedral configuration. In comparison, the use of a gel precursor resulted in a product with only 60% aluminum in the tetrahedral configuration. The synthesis temperature had no significant effect on the saponite structure. The reported synthesis method showed the possibility of obtaining saponite with superior characteristics, in terms of crystallinity, surface acidity, and thermal stability compared to the natural mineral, even at 90°C, and thus with greater potential for industrial application.

Hydrothermal alteration led to development of the Yarıkçı clay deposit within the Mesozoic chlorite-, muscovite-, chlorite-muscovite-schist, and garnet-graphite phyllite units along NW–SE- and N–S-trending faults in Mihalıççık in western central Anatolia. The geological, mineralogical, and geochemical characteristics and genesis of this economically important clay deposit have not been examined in detail previously. The present study has attempted to fill this gap. Green smectitic and cream kaolinitic claystones are abundant with smaller amounts of gray illite, dark brown Fe oxides, and silica phases occurring as stockwork/fracture infill and stain/coating. These units are covered by a dark, hard, sharp-edged, and thick silica cap. Metamorphic units exhibit cataclastic texture due to tectonic activities. Muscovite is mostly degraded to kaolinite, and feldspars show sericitization and argillization. Kaolinite typically has a platy form with irregular margins and locally sub-rounded, book-like texture suggesting hydrolysis during the hydrothermal injections. The association of Fe oxides, cristobalite/tridymite/quartz, gypsum/anhydrite, and jarosite are indicative of intense hydrothermal activities and development of kaolinite under acidic geochemical conditions. The local enrichment of SiO2, Fe2O3, S, Cu, and Au also supports this suggestion. The leaching of Sr, Rb, Ba, and Zr, and the slight increase in LREE/MREE+HREE ratios together with the negative Eu and Ce anomalies suggest the selective dissolution of muscovite, garnet, feldspar, and pyroxene by the hydrothermal fluids. Thus, abundant claystones of smectite and kaolinite were formed via the increase in Al+Fe+Mg/Si and Al±Fe/Si ratios in the alkaline and acidic environment, respectively, under the tectonic control of hydrothermal activity as seen in the alteration of chlorite, muscovite, and feldspar in metamorphic units.

The harm caused by mine tailings has become increasingly problematic in recent years, so efforts are needed to dispose of or reutilize them in environmentally friendly ways. The objective of the present study was to find out if the hydration properties of muscovite contained in mine tailings are suitable for it to be used as a pozzolan in cement, after undergoing mechanical activation. Aqueous suspensions of mechanically activated muscovite were blended with 10, 20, or 30 wt.% calcium oxide and then allowed to harden. The hardened paste samples were analyzed by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS) techniques. The results revealed that the mechanically activated muscovite exhibited pozzolanic reaction activity in the alkaline environment provided by calcium oxide, and the activated muscovite possessed a capacity to react with calcium hydroxide to form hydration products. The calcium oxide content affected significantly the quantities and kinds of hydration products, non-evaporable water content, and the compressive strength development of the paste samples. The hydration products of the 10% calcium oxide-activated, mechanically activated muscovite pastes were Al-containing hydrated calcium silicate (C-A-S-H) gel, stratlingite, and, upon addition of 20% and 30% calcium oxide, Ca-Al hydrotalcite-like (Ht) phases. The present study was helpful in evaluating the hydration properties of the mechanically activated muscovite and also provided a research basis for evaluating the hydration properties of mine tailings containing muscovite after mechanical activation. The results provided a theoretical basis for muscovite-containing mine tailings to be used as a cement additive, and was conducive to the large-scale utilization of mine tailings.

The dispersive behavior dynamics of clay determine soil characteristics such as permeability and aggregate stability, and, consequently, crop productivity. Soil dispersion is heavily influenced by the ionicity of clay–cation bonds and has been shown to be related to the net negative charge and pH of the system. Little work has been done, however, which considers these factors together, especially for K and Mg clays. The objective of the present study was to investigate the effect of changing pH on the dispersive behavior of Mg and K homoionic clays, in comparison to Ca and Na clays under equivalent pH conditions. The clay fractions used here were extracted from three soils and have distinctly different mineralogies. These clays were treated to become homoionic with regard to Na, K, Ca, and Mg. Excess salts were removed by dialysis and pH was adjusted to 3, 4, 5, 6, 7, 8, 9, 10, and 11 for all clays, except Mg (pH range 3–7). Clay dispersion-flocculation dynamics were investigated, and the net negative charge, pH, electrical conductivity (EC), and turbidity were measured. Mg has a similar but less flocculative effect than Ca, while K has a similar but less dispersive effect than Na, under similar pH conditions. The dispersive behavior of Na, K, Mg, and Ca homoionic clays was correlated well with the ionicity of clay–cation bonds at equivalent pH, with the degree of clay dispersion being explained by the pH, EC, ionicity, ζ-potential, and mean particle size of the clay–cation system. A predictive model for dispersion was developed with its applicability and limitations discussed.

Modification of the surfaces of montmorillonite (Mnt) by organic molecules is an effective method for improving their affinity toward non-aqueous substances, and has resulted in extensive industrial applications as rheological control agents, drilling fluids, and other functional materials used in applications ranging from environmental remediation to coatings. The present study reviewed recent progress in organo-modification of Mnt, and provides state-of-the-art insights into proposed modification mechanisms and the peculiar functionalities of the resulting organo-montmorillonite (OMnt). Several routes have been employed to modify Mnt, including ion exchange with organic ions, surface adsorption, and grafting of organics. Commonly used organic modifiers include cationic, anionic, zwitterionic, non-ionic, and polymeric species. Organo-modification is driven by multiple interactions: van der Waals forces, cation exchange, electrostatic interaction, hydrogen bonds, and ion–dipole interaction. OMnt, in general, exhibits synergistic and/or antagonistic effects when used in oil-based drilling fluids, environmental remediation, or layered silicate/polymer nanocomposites. The detailed mechanisms of non-ionic and zwitterionic modification of Mnt remain unclear. This literature survey suggests that future work should emphasize deeper understanding of interactions between the Mnt and the organic modifiers, and meanwhile expand the applications of OMnt into catalysis, drug carriers, and the biomedical field.

Injured bone tissues can be healed with bone grafts, but this procedure may cause intense pain to the patient. A slow and localized delivery of nonsteroidal anti-inflammatory drugs (NSAIDs) could help to reduce the pain without affecting bone regeneration. The objective of the present study was to use [Mg-Al]-layered double hydroxide (LDH) as a matrix for controlled release of sodium naproxen (NAP). This system could be applied in biomaterial formulations (such as bone grafts) to achieve a local delivery of naproxen. [Mg-Al]-LDH successfully incorporated up to 80% (w/w) of naproxen by the structural reconstruction route, with the [Mg-Al]-LDH interlayer space increasing by 0.55 nm, corresponding to the drug molecule size. The evaluation of the naproxen release kinetics showed that 40% of the drug was delivered over 48 h in aqueous medium (pH 7.4 ± 0.1), indicating the potential of [Mg-Al]-LDH/NAP for local release of naproxen at adequate concentrations. Kinetic modeling showed that the naproxen release process was closely related to the Higuchi model, which considers the drug release as a diffusional process based on Fick’s law. The chemical stability of NAP after the release tests was verified by 1H NMR. The [Mg-Al]-LDH/NAP also exhibited low cytotoxicity toward fibroblast cells (L929 cell line), without modifications in their morphology and adhesion capacity. These results describe a suitable approach for preparing efficient systems for local delivery of nonsteroidal anti-inflammatory drugs for biomedical applications.

The present study provides an example of the accurate identification of polytypes of trioctahedral 1:1 layered silicates from single-crystal X-ray diffraction data collected with the aid of a four-circle diffractometer equipped with an area detector. Single crystals of the mineral cronstedtite from the Nagybörzsöny gold ore deposit, northern Hungary, were studied. The chemical composition of some crystals was determined by electron probe microanalysis (EPMA). The precession-like images of the reciprocal space (RS) sections created by the diffractometer software and presented in the study were used to determine the OD (ordered-disordered) subfamilies (Bailey’s groups A, B, C, D) and particular polytypes. With one exception, all crystals studied belong to subfamily A. The rare polytype 1M, a = 5.51, b = 9.54, c = 7.33 Å, β = 104.5°, space group Cm is relatively abundant in this occurrence. Another polytype 3T, a = 5.51, c = 21.32 Å, space group P31 was also found. Both polytypes occur separately or in mixed, mostly 1M dominant crystals. Some 1M polytype crystals are twinned by order 3 reticular merohedry with a 120° rotation along the chex axis as the twin operation. A rare 1M+3T mixed crystal with 1M part twinned also contains a small amount of subfamily C. A possible presence of the most common 1T polytype of this subfamily cannot be confirmed because of overlap of the characteristic reflections with those of 3T. Several completely disordered crystals produced diffuse streaks instead of discrete characteristic reflections on the RS sections. The EPMA revealed Fe, Si, traces of Mg, Al, S, and Cl. One black crystal originally considered to be cronstedtite was identified as (111) twinned sphalerite. Some crystals of cronstedtite are covered partially by a honey-brown crust or small crystals of siderite.

The stability, dispersion, and rheological properties of clay suspensions are important in the process of drilling. Organic clays were obtained traditionally by cation exchange, which is thermally unstable due to weak electrostatic interaction between the cationic surfactant and clay minerals. The purpose of the present study was to yield a stable and well dispersed organic bentonite (OBent) as a rheological additive for oil-based drilling mud. The co-modified method was used to modify bentonite by a cationic surfactant (cetyltrimethoxyammonium bromide: CTAB) and a silane coupling agent (hexadecyltrimethoxysilane: HDTMS). Firstly, the basal spacing of bentonite was enlarged by intercalation of CTAB, and the thermal stability of bentonite was improved by covalent bonds of HDTMS onto the bentonite platelets. The as-prepared OBent was characterized by infrared analysis, X-ray diffraction analysis, thermogravimetric analysis, and scanning electron microscopy. The hydrophobicity, solubility, viscosity, and tribological performance of the OBent were also recorded. The test results showed that the hydrophobicity of the co-modified bentonite was improved significantly, and was greater than that of bentonite modified with single surfactant CTAB or HDTMS. The bentonite modified by the surfactant together with the silane coupling agent had stable rheology and a lower coefficient of friction than the single surfactant-modified bentonite because more HDTMS entered into the interlayer spaces and formed chemical bonds at the inner surface of platelets.