The surface acidic properties of pillared clays (PILCs) with Al or Zr oxide pillars (prepared from a natural Portuguese smectite and a synthetic Laponite), and of a protonic NaHY zeolite, were studied by two methods: pyridine adsorption followed by infrared (IR) spectroscopy, and the catalytic transformation of 1-butene. The results of the pyridine adsorption revealed that all the pillared clays studied have mainly Lewis-type acidity, the exception being the clay pillared with Zr oxide, obtained from natural smectite, which also presents a significant number of Brönsted acid sites. The results of 1-butene transformation showed that the pillared clays exhibit catalytic properties similar to those of the protonic Y zeolite. The acid character of the solids was confirmed by the values of the cis/trans 2-butene isomers ratio. At short reaction times, product distribution showed that the main reaction is oligomerization, followed by cracking. After 15 min the products are mainly the linear isomers, cis and trans-2-butene, showing that the majority of the catalytic active sites, are already poisoned after 15 min of reaction. The particular behaviour of Laponite intercalated with Al oxide pillars is discussed. The IR spectra of the pyridine adsorbed on the fresh samples and after the catalytic assays, revealed that Lewis acid sites behave as active sites for 1-butene catalytic transformation. The consistency between the results of the two complementary techniques used for the characterization of the acidity of the solids was proved.

The Şile Region contains discontinuous, cyclic, thin coal beds and industrial clay deposits that were accumulated in lacustrine basins which received extensive volcanoclastic sediments due to transport of highly weathered calc-alkaline volcanic rocks. The Sülüklü area has the largest kaolin deposit in this region. Cyclic kaolinization depended on the degree of leaching of Si and alkalis in cyclic swamp environments and, therefore, kaolinite contents vary in each discontinuous lens-shaped clay bed and underclay within the basin. The kaolins comprise disordered kaolinite, illite, smectite, gibbsite, quartz, pyrite, anatase, K-feldspar and goethite. Depth-related changes in the distribution of clay minerals, associated with coal beds, are indicative of organic acid-mineral reactions. Kaolinite crystallization initiated at the edges of sericitic mica sheets in the form of composite kaolinite stacks. The small size (<1 µm), morphology and poor crystallinity of kaolinite crystals suggest that kaolinization post dated transportation. Primary or secondary origins of particles can be determined from the stacking sequences of kaolinite particles using high-resolution transmission electron microscopy images. Kaolinite stacks always contain a small amount of illite, but smectite is only present in the middle and upper levels. Gibbsite is a main constituent of refractory bauxitic clays locally found as discontinuous lenses and exploited from the lower level of the basin.

Genesis of kaolin deposits took place in two stages: first, there was in situ weathering of the oldest andesitic agglomerates, tuffs and ashes at the base of the lacustrine basin coupled with discharge of shallow thermal waters which were initiated by local hydrothermal alteration; second, surface weathering enhanced transportation of altered rocks from the surrounding hills into the lacustrine basin. Kaolinization took place in cyclic swamp environments, as indicated by the presence of cyclic thin- to thick-bedded coals that provided necessary humic and fulvic acids for the post-depositional alteration of altered volcanic rocks to kaolin in dysaerobic, relatively low-pH conditions in saturated groundwater zones.

Layered metal hydroxides exhibit non-uniform broadening of lines in their X-ray powder diffraction (XRPD) patterns, which cannot always be explained on the basis of crystallite size effects. In the case of hexagonal solids such as nickel hydroxide, DIFFaX simulations of the XRPD patterns show that: (1) stacking faults and turbostratic disorder at low (<30%) incidence selectively broaden the h0l reflections; (2) turbostratic disorder at high (>40%) incidence causes asymmetric broadening of the hk0 reflections and a complete extinction of the hkl reflections while leaving 00l unchanged; (3) interstratification selectively broadens the non-hk0 reflections; and (4) cation vacancies reduce the relative intensity of the 100 reflection. In contrast, a reduction in the thickness of the crystallites along the stacking direction of the layers selectively broadens the 00l reflections while a reduction in the disc diameter causes the progressive broadening and extinction of the hk0 reflections. Comparison with experimental data shows that several kinds of disorders have to be invoked to account for the observed broadening. DIFFaX simulations enable the quantification of the different kinds of disorder.

In this study, the feasibility of using surfactant-modified palygorskite (PFl-1) and sepiolite (SepSp-1) for removal of anionic contaminants from water was evaluated from batch experiments. The results showed that both minerals had strong affinity for hexadecyltrimethylammonium (HDTMA), a cationic surfactant used for surface modification. The HDTMA sorption capacities were 520 and 260 mmol/kg for PFl-1 and SepSp-1, respectively. Accompanying HDTMA sorption, the sorption of counterion bromide reached 380, and 210 mmol/kg, for PFl-1 and SepSp-1, respectively, indicating that the sorbed surfactant molecules form admicelles on the minerals’ surfaces. After modification by HDTMA to sorption maxima, these clays showed strong affinity for anionic contaminants such as chromate and nitrate. The chromate sorption capacities were 42 and 34 mmol/kg for HDTMA-modified PFl-1 and SepSp-1, respectively. Desorption of counterion bromide due to sorption of chromate followed a straight-line relationship, suggesting that the sorption of chromate on surfactant-modified palygorskite and sepiolite was also due to anion exchange as with other surfactant-modified clay minerals and zeolites.

Lithiophorite is a naturally occurring phyllomanganate which has been identified in soils and ores. Studies on a synthetic version have shed light on the conditions required for the formation of lithiophorite. In this study, we successfully prepared lithiophorite under highly alkaline conditions. In addition, we found that Li+, Al3+ and hydrothermal treatment are all necessary for the formation of lithiophorite. Lithiophorite, birnessite and Li-intercalated gibbsite were examined by infrared (IR) spectroscopy. The Mn oxide sheets of lithiophorite and birnessite were found to have quite similar structural environments. On the other hand, the LiAl2(OH)6 sheets are affected more markedly by the Mn oxide sheets. After intercalation, the symmetry of the six interlayer OH groups of LiAl2(OH)6 is reduced and they are divided into two groups occupying different sites, corresponding to the IR absorption bands at 3480 and 3312 cm−1, respectively.

Clay minerals appear to change significantly under the influence of pasture development on poldered sediments in the Baie d'Authie area (Somme, France). Cores 40–90 cm deep from recent salt marsh sediments and poldered sediments developing grass pastures since 1737, 1575 and 1158 indicate that the natural mineral suite of kaolinite, mica, illite, and two disordered mixed-layered illite-smectite (I-S) phases common to the sedimentary input changes gradually but significantly in the materials. In the oldest, best-developed profile, there is a dominance of a disordered, illitic I-S in the humic upper part of the profile and a more abundant, more smectitic I-S mineral below. It appears that grass-derived humic materials tend to stabilize closed (collapsed) or illitic behavior in I-S clays. The natural evolution of the sediment (lower part of the profile) is towards a smectitic clay assemblage. Destruction of organic matter of the smectitic I-S minerals by oxidation indicates that this material can significantly modify the physical behavior of the clays keeping the structure open to polar molecules.

The Raman spectra of many kaolins are dominated by bands from ancillary anatase. Fired samples of a commercial anatase-bearing kaolin from the Jari River deposit in Brazil showed significant variations of Raman spectra as a function of the firing temperature. The spectra showed the full range of anatase bands up to a firing temperature of 900°C. From 950°C the background increased significantly, leading to an unfavorable signal/noise ratio that allowed observation of only the most intense (Eg) band at ~144 cm−1. X-ray diffraction (XRD), however, confirmed that this band, which persists up to 1200°C, results from anatase. Two factors may be responsible for the high thermal stability of anatase in this sample: its relatively large particle size of ~120 nm and possible reactions with Si and Al that become liberated during kaolinite breakdown. When evaluated with circumspection, Raman and XRD data on anatase can serve as ‘thermometers’ to elucidate the thermal history of fired anatase-bearing kaolins and other anatase-bearing clays.

The nature and morphology of Al(OH)3 polymorphs obtained by precipitating Al and tartrate at pH 12.0 and at a tartrate/Al molar ratio (R) of 0.1 were studied by X-ray diffraction, transmission electron microscopy and electron diffraction. Co-crystallization of unusually long (up to 18 µm) ‘stick-shaped’ gibbsite with platy particles of both nordstrandite, mainly, and bayerite was observed. Face-to-face associations of plates nucleated perpendicularly on the gibbsite surfaces parallel to the c axis produced peculiar elongated ‘brush’ -shaped particles. In a strongly alkaline environment the inhibiting effect of tartrate on Al(OH)3 polymorph formation is reduced and production of co-crystallized phases with structural crystallographic similarities can be observed.

The aim of this paper was to define the nature and the relative chronology of the diagenetic clay bearing assemblages within sandstones of the Middle Proterozoic Kombolgie formation (Northern Territory, Australia). The detrital minerals of these rocks comprise quartz, accessory zircon, tourmaline, rutile and rare phengitic white micas. Diagenetic features consist of pore-sealing secondary quartz overgrowths, strong compaction shown by interlocked structures and stylolith joints, local hematization and the occurrence of two distinct clay parageneses. Blocky crystals of dickite constitute the earlier diagenetic clays. Their FTIR spectra and their DTA curves, with a sharp dehydroxylation endothermic peak near 680°C, are characteristic of the well-ordered dickite already encountered in many deeply-buried sandstones. Quartz overgrowth may be contemporaneous with the crystallization of dickite. Illite occurred during a subsequent stage as grain coatings and as pseudomorphs of dickite in the residual pores of the sandstones. Illite seems to be contemporaneous with the major deformation features associated with compaction phenomena at the maximal burial conditions experienced by the sandstone formation. These illites are essentially of 2M1 polytype. They display pseudohexagonal platy crystals with average diameters ranging from 2 to 10 µm. Their chemical composition is Al-rich (Ca0.01Na0.02K1.72) ()(Si6.27IVAl1.73)O20(OH)4. These Proterozoic rocks provide a natural reference for the illite end-member occurring as a replacement of kaolin subgroup minerals during burial diagenesis of sandstones The textural properties of the Kombolgie sandstones (absence of fracture network, low porosity, well-developed macroscopic stylolith joints…) and the crystal structure of both the diagenetic dickite and illite would tend to indicate that the Kombolgie sandstones were buried at a depth exceeding 5 km.

Vermiculites and phlogopites can be exfoliated by chemical and thermal treatment methods to obtain chemically inert, adsorbent, fire-resistant, low-density materials with excellent thermal and acoustic insulation properties. The water content of the clay generally determines the extent of exfoliation and the presence of interstratification is claimed to increase the rate of exfoliation. Considering the strong interaction between water and microwaves, the effect of microwave power on exfoliation characteristics of vermiculites and phlogopites after treatment with water and hydrogen peroxide solution were studied at 600, 950 and 1300 W for microwave exposure times of 10, 20, 30, 60, 120 and 300 s. It was observed that the water molecules in the interlayers of the individual flakes were driven off quickly by microwave treatment causing layer separation in the samples. The vermiculite sample showed 2.8 and 5.6 times, respectively, the exfoliation ratio of the phlogopite samples, in accord with their water contents.

Natural soils change by long-term pedogenetic mechanisms, but tillage effects can also strongly affect the evolution of soils, mainly their physicochemical properties. The present paper describes the impact of fertilizers and amendments on soil mineralogy in experimental plots, without plant interaction.

The soils of the 42 plots experiment at the INRA experimental station in Versailles (France) have been managed with fertilizers without plant growth since 1929. Strong changes in pH were observed and cation exchange capacities doubled between low and high pH (from 3.6 to 8.2). Strong acidification caused more evolution in the clay particle distribution without selective action on the clay composition.

While the clay content varied only slightly, the organic matter content changed considerably, decreasing with non-organic treatment and increasing in the plot with manure treatment. The major clay minerals in the experimental plots are two disordered illite-smectite mixed-layer minerals, with minor amounts of illite/mica and kaolinite. Most treatments effected only minor changes in clay mineralogy. However the illite (non-expandable mineral) content increased in plots with K addition either as KCl treatment or in manure amendments by increasing the illite content and the illite (non-expandable layer) content of the I-S minerals. Manure changed the I-S mineral to a greater extent.

This paper describes an improved simple, sample-mounting method for random powder X-ray diffraction (XRD), namely the razor tamped surface (RTS) method, which prepares a powder mount by tamping the loose powder with the sharp edge of a razor blade. Four kaolinites and a quartz powder were used to evaluate the RTS method by quantifying the degree of orientation in the sample mounts using orientation indices. Comparisons between the RTS and other published simple methods, consisting of front loading, back loading and side loading, indicate that the RTS method produces minimum packing density and minimum preferred orientation in the powder mounts of all five samples. The quartz powder used in this study does exhibit a tendency to preferred orientation. The mechanism by which the RTS method reduces preferred orientation is examined by comparing the width of the sharp blade edge with the size of clay particles. The advantages and disadvantages of the RTS method are also discussed.

Several micas containing different octahedral and interlayer cations were synthesized at different temperatures under conventional- and microwave-hydrothermal conditions and these phases were characterized by powder X-ray diffraction, solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. A Zn K-mica with Zn in the octahedral sheets and K in the interlayers was synthesized in the temperature range 150–200°C and a novel Zn Rb-mica with Zn in the octahedral sheets and Rb in the interlayers was synthesized at 200°C. The synthesis of either Mg, Co or Ni K-micas, however, was found to be difficult or impossible at these low temperatures. Solid-state 29Si MAS-NMR revealed that the Al in the tetrahedral sites is disordered with several nearest-neighbor Si environments. In general, microwave-assisted hydrothermal conditions led to better crystallization of the Zn K-micas compared with the conventional method.

The chemical and structural properties of Mg smectites in the Vicálvaro sepiolite deposit have been studied in detail. The characterization was performed on different size-fractions of selected smectitic samples (5−2 µm; 2−1 µm; 1−0.5 µm; <0.5 µm and <0.1 µm). The chemical compositions of individual particles (5−1 µm) and of bulk undifferentiated fine fractions (1−<0.1 µm) were determined by energy dispersive spectroscopy-scanning electron microscopy and interpreted with the aid of X-ray diffraction (XRD) and infrared spectroscopy (IR) methods. The XRD and IR data demonstrate that all of the Mg smectite materials studied are mainly composed of a complex mixture of stevensite, saponite and mica-type minerals. Although the presence or absence of saponite cannot be confirmed absolutely, stevensite is a significant component of these Mg smectites. This is proven by the calculated layer charge reduction after the Hofmann-Klemen effect. The results are in close agreement with the suggested mechanism of topotactic overgrowth of stevensite on pre-existing phyllosilicate templates. This characterizes clay diagenesis in saline-lake systems.

The effects of ultrasound treatment on the mean particle size, crystal structure, crystallite dimensions and specific surface area of natural muscovite and biotite samples have been investigated. Sonication of macroscopic flakes of muscovite and biotite produced a drastic particle-size reduction. The conditions for the preparation of micron and submicron-sized muscovite and biotite particles of narrow particle-size distribution by sonochemistry are described. The effect of sonication on particle-size reduction is more significant for muscovite than for biotite. Thus, for long sonication times (100 h), submicron and micron particles are predominant in muscovite and biotite, respectively. The resulting materials are crystalline, as assayed by X-ray diffraction, only broadening of the diffraction lines due to size-reduction was observed. Nuclear magnetic resonance studies revealed that the coordination of Al and Si was not modified by the treatment. Chemical analysis showed that the composition of the sample was not affected by the sonication except for a small contamination by Ti from the tip cup of the sonication instrument.