Fe3+ ions in palygorskite occupy sites at the edges and in the interior of the alumino-silicate chains. The Mössbauer parameters of the doublets associated with Fe3+ ions in edge sites indicate that the sites have a regular 6 coordination. Fe3+ ions in the interior of the chains occupy M(1) sites in three of the samples examined and M(2) sites in the fourth. Fe3+ ions in edge positions of palygorskite become 5-coordinated when water is lost on heating. They maintain this coordination on dehydroxylation, probably by cross-linking of the chains. The temperatures at which changes occur in the X-ray powder diffraction patterns and the Mössbauer and infrared (IR) spectra differ from sample to sample. The intermediate stages observed also vary, either due to different reaction paths or to different stabilities of the intermediate phases. The deduced distribution of cations in the octahedral sheets is in good qualitative agreement with the observed IR hydroxyl absorptions.

Four sepiolite deposits of different origin, which occur near Las Vegas, Nevada, are compared and described. They include a playa deposit, a valley terrace deposit, and two types of vein deposits. The physical and chemical characteristics of the four materials are described, the engineering and commercial features are considered, and the varied origins of the sepiolite are discussed. X-ray powder diffraction data, infrared spectra, thermal characteristics, and chemical analyses are given for the Two Crows sepiolite. The vein deposit is proposed for use as a clay mineral reference standard because of its purity and availability. The apparent diverse morphology of the sepiolite deposits is shown with its common, lathlike basic structure.

Hydrothermal reactions in the system sepiolite/H2O have been examined between 149° and 316°C. Approximately 10–20% of the starting sepiolite was converted to a smectite (stevensite) at 204°C within 24 hr. Similar results were obtained when CaCl2, NaOH, Ca(OH)2, or Mg(OH)2 was added to the system. In the presence of NaCl, about 60% of the sepiolite was converted to stevensite, whereas, only 5% stevensite formed in the presence of MgCl2. Greater amounts of stevensite formed at 260°C in these systems. Above 316°C, 60–80% of the sepiolite was converted to stevensite in 24 hr, regardless of the presence or absence of salts. Within the experimental conditions used, temperature is the most important factor in the sepiolite-to-stevensite conversion.

At or below 216°C, sepiolite appears to transform into stevensite by dislocations involving c12 glides that are triggered by the stresses of the hydrothermal conditions. Above this temperature, stevensite seems to form by direct precipitation after dissolution of sepiolite.

The rheological properties of three Na-activated, trioctahedral Mg-bentonites (hectorite clay from the CMS Source Clay Project repository, saponite clay from Spain and stevensite clay from Rhassoul, Morocco) and a sepiolite clay from Greece were examined after dynamic ageing at temperatures up to 230°C. The 5% w/v suspensions were prepared by dispersing the clay mineral samples in distilled water. The suspensions underwent dynamic, thermal ageing for 16 h before determination of the viscosity, filtration loss, filter cake thickness and pH and the concentration of dissolved Na+ and Mg2+. Thermal ageing contributed to the dispersion of clay particles, with a direct effect on plastic and apparent viscosity, introducing pseudoplastic behaviour. With the exception of the stevensite clay at 230°C that displayed limited dissolution at 230°C and partial conversion to kerolite, the clays were stable at high temperatures. The Na-activation of all clays except for stevensite was not adversely affected by thermal ageing. Thermal ageing of stevensite at 230°C facilitated Na exchange and yielded suspension with high viscosity and low filtrate loss. Only the suspensions of hectorite and those of stevensite aged at 230°C met with American Petroleum Institute specifications. The thermal behaviour and rheological properties of the clays might be interpreted according to the intrinsic properties of the clay minerals, such as layer charge and charge distribution.

Natural sepiolite has great potential for application in wound healing, haemostasis and medicines. This paper introduces a versatile solid-state sintering technique for preparing sepiolite-based nanocomposites with enhanced antibacterial properties, and the physical, structural, rheological and antibacterial properties of which were determined to be enhanced. The incorporation of nanosized Ag and metal oxides into sepiolite composites results in a notable improvement in their antibacterial efficacy against Escherichia coli and Staphylococcus aureus in comparison to the unmodified sepiolite. With a low silver content of just 5%, the sepiolite–Ag composite achieves an antibacterial rate of ~100%. Furthermore, the rheological properties exhibited by the sepiolite composites are noteworthy, suggesting their suitability for use in wound-dressing applications due to their exceptional workability. The methodology employed in this research has the potential to offer a viable substitute for the production of economical and effective natural antibacterial nanocomposites.

The role of adsorbed and structural Fe3+ in palygorskite and sepiolite with respect to the oxidation of hydrocortisone in aqueous suspension has been evaluated using electron spin resonance and UV-visible spectroscopy. Natural surface-adsorbed Fe3+ showed an important activity in the oxidation process, although smaller than octahedral Fe3+. The kinetics of oxidative degradation of hydrocortisone by palygorskite appear to be composed of two apparent first order reactions which may be associated with two kinds of sites for Fe in palygorskite. The lower oxidizing power of sepiolite for hydrocortisone degradation is due to its very low Fe3+ content.

The mechanisms of palygorskite and sepiolite alteration to smectite under mild hydrothermal conditions were investigated by solid-state 27Al and 29Si magic-angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopy, X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). Palygorskite altered to smectite in the presence of NaOH at 150°C. 27Al MAS-NMR spectroscopy showed that the Al coordination changed from chiefly octahedral in palygorskite to chiefly tetrahedral in the smectite product. 29Si MAS-NMR spectroscopy showed that the nearest neighbor environment of Si also changed when palygorskite altered to smectite. The XRD data showed that the synthetic smectite is trioctahedral in nature with tetrahedral charge. The TEM results revealed that the needle-like morphology of palygorskite was preserved in the product smectite. The MAS-NMR results in conjunction with the above XRD and TEM studies suggest that the mechanism of palygorskite alteration was a dissolution and recrystallization process rather than a solid-state reorganization to form 2:1 layer silicate units from the preexisting chain structure. Sepiolite altered to smectite in the presence of 2 N salt solutions at 300°C. The trioctahedral nature of the product smectite as detected by XRD and the foil-like morphology of product smectite as shown by TEM suggest that the mechanism of sepiolite transformation to smectite was also a dissolution and recrystallization process. The tetrahedral Al coordination detected by 27Al MAS-NMR in the smectite altered from sepiolite corroborated the XRD and TEM results.

Volatiles formed on heating clay minerals contain a variety of cations and anions and are highly reactive. Gas chromatograph-mass spectrometer analysis of long-chain n-alkanes exposed to such volatiles showed that some decomposition occurred even <250°C. Reactions with anions donated by the volatiles led to compounds containing atoms other than C and H, e.g., Cl. The products obtained from n-alkanes heated in a stream of clay volatiles to 500°C resembled those produced by corresponding alkane-clay mixtures heated to 250°C. At higher temperatures contact between the alkanes and montmorillonite or halloysite led to changes in the assemblages formed, whereas kaolinite or sepiolite had no effect. Thus, the first reactions that occurred when clays were heated with n-alkanes were apparently induced by the volatiles; at higher temperatures catalysis due to direct contact came into play with some of the clay minerals.

The structure of sepiolite from a piston core obtained on Ninetyeast Ridge in the Indian Ocean was modified by exposure to ethylene glycol vapor. With ethylene glycol, the sepiolite Oil X-ray powder diffraction peak expanded from 12.4 to 12.8 Å, and the 130 peak contracted from 4.53 to about 4.45 Å. The cell modification is consistent with concomitant expansion along the c-axis and contraction along the b-axis. This structural distortion is not permanent, however, inasmuch as the sepiolite returned to its original state 6 to 12 hr after it was removed from the ethylene glycol-saturated atmosphere.

Three methods were investigated to separate palygorskite from mixtures of clay minerals in soils and sediments. The methods were based on the hydrophobic properties of a dodecylammonium-smectite complex and used the <0.2-μm fractions of reference palygorskites that contained smectite and sepiolite impurities. Palygorskite was separated from dodecylammonium-clay complexes by: (1) selective dispersion of palygorskite in H2O; (2) selective extraction of palygorskite by a water:decanol phase separation; and (3) selective extraction of palygorskite by a water: nitrobenzene phase separation. Whereas all three methods resulted in palygorskite separation, selective dispersion was the simplest and employed the more desirable reagents. Small amounts of relatively pure palygorskite in the <0.2-μm fractions were concentrated from palygorskite-containing clays from Texas, Saudi Arabia, and Libya as shown by X-ray powder diffraction and transmission electron microscopy data. A sepiolite impurity in the Georgia palygorskite was concentrated with the palygorskite. Hydrolysis of the dodecylammonium-smectite complex was suggested by the decrease in d-spacing of some samples after the extensive washing necessary for dispersion. An appreciable amount of the fibrous mineral was intimately associated with layer silicates and could not be separated.

The catalytic activity of sepiolite from Amboseli, Tanzania, for the dehydration and dehydrogenation of ethanol at 150°–300°C has been studied using a flow reactor. Both reactions occur, but the catalyst activity decreases with use. The products include water, carbon dioxide, ethene, ethanal (acetaldehyde), diethyl ether, but-1,3-diene, but-2-enal (crotonaldehyde), and an unidentified aromatic compound. The proportions change with temperature, the dehydrogenation reaction being favored at the higher temperatures. The BET surface areas of the sepiolite are 316 m2/g (nitrogen adsorption at — 197°C) and 212 m2/g (ethanol vapor adsorption at 25°C, assuming a molecular cross-sectional area of 24.6 Å2), indicating a possible greater penetration of pores and channels by nitrogen compared with ethanol vapor under these conditions. The pore-size distribution reveals that approximately 55% of the surface area measured by nitrogen adsorption is contributed by micropores.

To eliminate mercury vapor from gas streams, three major methods are used: condensation, absorption, and adsorption. This work deals with adsorption, using elemental sulfur as an active phase supported on sepiolite and palygorskite fibrous clays. Sulfur loads of 5–30% were deposited by catalytic oxidation of hydrogen sulfide at temperatures of <200°C, the clays acting first as a catalyst of the reaction and then as a carrier of the obtained sulfur. The ability of the sulfurized clay adsorbents to retain mercury was studied at 45°C and 1 mm Hg pressure. The high values found, about 4 g Hg/g S supported on clays, compared with 1.69 g Hg/g S on activated carbon under the same conditions are related to a more appropriate pore size distribution, with more of the pore widths >6 nm for the sulfurized silicates. Also, the allotropic state of the deposited sulfur, where Sπ (octo-catena) is better than Sλ (octo-cycle), may also be a contributing factor.

The Upper Pliocene sediments near Lebrija in southern Spain contain commercial deposits of palygorskite and sepiolite. These sediments of continental origin consist chiefly of carbonate, marl, and clay resting on marine Pliocene quartzose sand. The lowest unit, the “Marly-Calcareous Bed,” consists of sepiolite-rich marl associated with concretions and irregular layers of chert, <0.5 m thick, and local diatomite layers, as well as limestone, sandy limestone, marl, and clayey sandstones. This unit has a maximum thickness of 30 m and contains three clay-mineral suites as follows: (1) bottom—sepiolite ± palygorskite; (2) center—sepiolite and palygorskite ± illite; (3) top—palygorskite and illite, ± sepiolite and smectite. Sepiolite decreases and palygorskite and illite increase toward the top, reflecting the composition of detrital material supplied to the basin. Beds 0.5–1 m thick locally and containing 50 to 60% sepiolite have been called “Tierra del Vino” (wine earth) because the material formerly was used to clarify and purify wine. The sepiolite-rich beds are as much as 15 m thick in the eastern part of the area. The upper unit is called the “Palygorskite Bed” because certain layers, 0.3 to 3 m thick, contain 35 to 75% palygorskite. The palygorskite-rich layers are interbedded with limestone and marl, and the entire unit is 15 m thick. The total resource of palygorskite is estimated at about 9 million tonnes.

The sediments are believed to have been deposited in a brackish, lacustrine environment. Originally, tectonic stability and an arid climate favored the formation of sepiolite at about pH 8. Later, after significant weathering of the source rocks, detrital illite was transformed to palygorskite in the Mg- and Si-rich waters. Here, palygorskite was also precipitated directly.

The methylation of the fibrous clays, sepiolite and palygorskite, should be facilitated by their large content of surface silanol groups and the low acidity and inaccessibility of coordinated water molecules. Infrared spectroscopy showed that the reaction of diazomethane with these clays resulted in the methylation of their silanol surface groups. The grafting of CH3 groups on the surfaces of these clays produced a decrease in the surface area due primarily to the lowering of the microporosity.

Modifications of the external surface area and the two types of microporosity of sepiolite (structural microporosity and inter-fiber porosity) were examined as a function of the temperature of a vacuum thermal treatment to 500°C. The methods used included: reciprocal thermal analysis, N2 and Ar low-temperature adsorption microcalorimetry, gas adsorption volumetry (for N2, Ar, and Kr at 77 K and CO2 at 273 and 293 K), water-vapor adsorption gravimetry, and immersion microcalorimetry into liquid water at 303 K. If the sample was not heated >100°C, only 20% of the structural microporosity was available to N2, whereas 52% was available to CO2 at 293 K. In both experiments, the channels filled at very low relative pressures. At >350°C, the structure transformed to anhydrous sepiolite, which showed no structural microporosity. The inter-fiber microporosity decreased from 0.031 to 0.025 cm3g (as seen with N2), and the external specific surface area decreased from 120 to 48 m2/g. The water adsorption isotherms showed a lower and lower affinity of the external surface of fibers for water as the temperature of thermal treatment increased. The thickness of the bound water on the external surface was estimated to be ≤ 3.5 monolayers, i.e., less than 10 Å.

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.

The instability of palygorskite and sepiolite under soil conditions was investigated to determine if these fibrous minerals transform directly to smectite under laboratory conditions. The treatment of 100 mg (0.12 mmole) of palygorskite with 1 mmole of NaOH solution (17 ml) at 150°C for 24 hr yielded a smectite. Analcime and smectite were formed when ≥ 3 mmole of NaOH was used. The addition of ≤ 6 mmole NaOH to sepiolite destroyed it gradually. On addition of ≥ 8 mmole NaOH, sepiolite altered to an X-ray amorphous material. In the presence of Al and Si, however, it transformed to smectite and analcime. Transmission electron microscopy, cation-exchange capacity, and X-ray powder diffraction studies of the products suggest that alteration wa. (1) via solution, o. (2) by a structural reorganization wherein the basic 2:1 silicate structural units were unchanged.

In vitro studies of the destruction (lysis) of bovine red blood cells (erythrocytes) by some silicate minerals showed the reaction to be complete in less than 1 hr and very destructive to the cell membrane. The activity as lysing agents was found to be in the order smectites > silica > palygorskite ≃ sepiolite > chrysotile > kaolinite. Different compositions (Fe, Al, Mg, Li, vacancy) of the octahedral sheet of the smectite and fibrous clay minerals did not appreciably alter their hemolytic activity. The most active particle size range for kaolinite and montmorillonite was 0.2-2 μm. Structural folding of palygorskite reduced lysis suggesting that edge surfaces and silanol groups are important in this process. Aluminum oxides and hydroxides caused no lysis, and coatings of positively charged aluminum-hydroxy polymers on montmorillonite, silica, palygorskite, and kaolinite significantly reduced lysis.