The current position with respect to low temperature synthesis of minerals is reviewed, and attention is directed particularly to the mechanism of synthesis. Possible compositions of the hydrated aluminium ion are considered and the significance of the fact that aluminate ions are necessary to introduce tetrahedral aluminium is discussed. It is concluded that present evidence is insufficient to define the processes exactly.

Polycarboxylate superplasticizer (PCE) is sensitive to the clay present in concrete aggregates. In particular, Montmorillonite (Mnt), an impurity inevitably contained in the aggregate, can significantly influence the performance of concrete. In an effort to improve the compatibility of PCE, a zwitterionic PCE with cationic amide groups and shorter side-chain lengths was synthesized via free radical copolymerization. The optimal synthesis condition was verified via Box-Behnken design. In addition to characterizing the PCE, the performance of PCE in cement pastes with or without Na-Mnt was examined and the underlying mechanism was explored. The results show that, compared with commercially available PCE, the required dosage of PCE for cements containing Na-Mnt decreased. Unlike commercially available PCE, no intercalation occured on the newly manufactured clay-tolerant PCE within the layers of Mnt, resulting in a greater sorption thickness and improved dispersion of the cements containing Na-Mnt.

Modified sericite mica was prepared by combining the intercalation of cetyltrimethylammonium bromide (CTAB) through ion exchange and surface modification of 3-aminopropyltriethoxysilane (KH550) with the following steps: high-temperature activation of sericite mica, acid activation, sodium modification, LiNO3 treatment, the ion-exchange intercalation of the cetyltrimethylammonium cation (CTA+) and surface modification of KH550. High-temperature activation was the most critical step for the modified sericite mica, and the number of hydroxyl groups of mica under high temperature directly affected the surface modification of KH550. The effects of various activation temperatures on the surface modification of sericite mica were investigated. The structure of activated sericite mica was intact when activation temperature was 600°C or 700°C, and the surface modification of sericite mica was not affected. The structure of activated sericite mica was partially destroyed at 800°C. The optimal temperature for activating sericite mica was 700°C. The structure and morphology of modified sericite mica were characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Brunauer–Emmett–Teller (BET) analysis and loose bulk volume. The KH550 could not only chemically graft onto the surface of sericite mica, but also enter into the interlayer through electrostatic attraction after its end amino group was protonated. The interlayer spacing of modified sericite mica increased to 3.22 nm, indicating that it might be an excellent layered silicate for preparing clay–polymer nanocomposites.

This research presents the mineralogical and chemical characterization and beneficiation study of two kaolin deposits from the Borborema Pegmatite Province, Brazil. Seven samples were collected and treated in two different beneficiation routes involving magnetic separation and chemical bleaching. The fractions obtained were studied by X-ray diffraction, X-ray fluorescence spectrometry, scanning electron microscopy, particle-size analyses, electron paramagnetic resonance and determination of optical properties. The samples are composed mainly of subhedral kaolinite in the form of booklets, as well as muscovite, quartz, microcline and illite impurities. The kaolinite structural formulae indicated significant replacement of Si4+ by Al3+ in tetrahedral sites and low replacement of Fe3+ by Al3+ in the octahedral sites. The first 30 min of chemical bleaching improved significantly the optical properties of kaolin, indicating that the process is more efficient than magnetic separation.

By means of transmission electron microscopy (TEM) and the gold decoration technique, the surface microtopography of rectorite (allevardite) crystals collected from Allevard, France was investigated. On the crystal surfaces, gold decoration successfully revealed growth steps of ∼20 Å in height. Only closed polygonal steps 20 Å high occur on the 001 surface of a thick platy crystal, although spiral growth patterns were not observed. Thick platy particles were easily split into thinner plates 20 Å thick in distilled water by means of ultrasonic vibration. No step patterns were observed on the surfaces of these thin plates which correspond to the cleavage plane. The growth of this rectorite, therefore, seems to be controlled by a layer nucleation mechanism.

The effect of mechanical activation on the ion-exchange selectivity of natural zeolites from Russia, namely clinoptilolite-bearing tuffs and chabazites, was studied. The structural modifications and thermal properties were investigated, and the specific surface area and porosity of mechanically activated zeolites were determined. At activation doses of up to 1.0 kJ g–1 the main processes are the breakdown of the zeolite particles and pore structure changes. At greater activation doses amorphization takes place. It was shown that during the initial stage of activation in most cases the clinoptilolite selectivity for Sr2+ increased slightly and then decreased; the selectivity for Cu2+ increased 100 times; and the selectivity of chabazite-1 for Sr2+ increased 300 times.

Basal X-ray peaks from normal and ethylene glycol-saturated tarasovite have been measured to 0.0.36 and 0.0.38, respectively; the mean basal spacings were 43·73 ± 0·44 and 46·05 ± 0·33 Å, with CV values of 1·31 and 0·97. The spacings indicate a near approach to a 3 : 1 illite-smectite but the CV values indicate a greater variability than is normally consistent with the allocation of a special name. Comparison of the observed spacings with those for illite showed that the more deviant values were always adjacent to positions of illite reflections. A modified Mering treatment of diffraction by mixed-layer sequences was used to estimate the proportion of illite layers; the average result was 79·9 ± 2·0%. The mineral is considered to have 3 : 1 illite-smectite units with randomly added illite layers, bringing the ratio from 75% for the ideally ordered sequence to near 80%.

Despite the high-grade diagenesis experienced by the Skoorsteenberg Formation mudstones, Tanqua Karoo basin, South Africa, geochemical data have been interpreted to reveal primary mineralogy and so help understand provenance evolution. The geochemical signatures show systematic variations related to stratigraphy. The main changes in mudstones from the lower to the upper part of the section include: (1) an increase in the feldspar content of the primary sediment and a decrease in the content of Al-rich clay (probably dioctahedral smectite); (2) a decrease in the degree of chemical weathering of the sediment, representing a change to a dryer and/or cooler climate; (3) an increase in TiO2/Al2O3 representing increasing mafic sources; (4) an increase in CaO/(K2O+CaO) also possibly representing increasing mafic sources. Mass flux and differential diagenesis are unlikely to be responsible for the depth-related changes since the rocks have undergone the same degree of high-grade diagenesis and the mudstones are interrupted by other lithologies, so disturbing any sort of diffusion gradient. These variations could plausibly be the result of one or more of differential weathering, evolving provenance characteristics or variable hydrodynamic fractionation of the sediment. The ratio of Zr/Y, a possible indicator of hydrodynamic fractionation, increases only slightly and irregularly up-section. There is no relationship between the silica content, representative of the quartz-silt content of the sediment, and TiO2/Al2O3 showing that the amount of quartz, and so the degree of hydrodynamic fractionation, has not controlled mudstone geochemistry. The stratigraphic increase in feldspar content, the decrease in Al-rich clay content and increase of both TiO2/Al2O3 and CaO/(K2O+CaO) must be due to a combination of marginally evolving provenance characteristics (more mafic and felsic rocks exposed to weathering with time) and changes in the degree of rock weathering (less chemical weathering with time).

A mixed-layer illite-smectite, illite-rich calcareous mudstone intruded by a basaltic dyke at the Perthus Pass (southern Massif Central, France) allows us to study the transformation of clays subjected to a brief thermal gradient. X-ray diffraction, scanning electron microscopy, electron microprobe and atomic absorption spectroscopy analyses were performed on samples at variable distances from the mudstone-dyke contacts.

A roughly similar evolution is seen on both sides of the dyke: quartz, calcite, kaolinite and illite disappear; Ca-silicates, albite and saponite-beidellite form, late meteoric halloysite crystallizes in open fractures.

Chemical and mineralogical transformations are related to heat diffusion from the dyke. Theoretical calculations highlight the influence of the dyke orientation. The mineralogical reactions observed in rocks are similar to those observed in experimental conditions. The formation of new swelling phases with a high retention capacity linked to a short duration, large-temperature increase, should constitute a positive process for Repository Performance Assessment.

Clay-swelling inhibitors are often used to prevent the hydration of clay minerals, which can reduce the risk of wellbore instability and reservoir damage. The molecular behaviour of clay-swelling inhibitors at the montmorillonite–water interface is crucial for revealing their inhibition mechanisms and for evaluating and designing inhibitor molecules. N1,N1'-(ethane-1,2-diyl)bis(N1-(2-aminoethyl)ethane-1,2-diamine) (NETS), a low-molecular-weight clay-swelling inhibitor, is used widely to prevent clay swelling. Herein, the adsorption mechanism of NETS on the surface of montmorillonite (Mnt) was investigated using molecular dynamics (MD) simulations. In particular, the effects of molecular conformation and temperature on adsorption ability were investigated. The results show that the adsorption ability of NETS on the Mnt surface was affected significantly by the molecular conformation. Specifically, the dihedral angle of NETS adsorbed on the surface of Mnt decreases by ~20° and tends to adsorb on the surface of Mnt in a plane state. In addition, the adsorption stability of NETS on the Mnt surface decreased with increasing temperature, as was found using MD simulations. Detailed analysis shows that increasing temperature can lead to more frequent conformational changes, which weaken the interaction between NETS and Mnt, thus reducing adsorption stability. These molecular insights into the interaction mechanism between NETS and Mnt are beneficial for the evaluation of inhibitory effects and for the selection and molecular design of new clay-swelling inhibitors for use in drilling fluids.

In many countries, compacted bentonite is a candidate engineering barrier material for safe disposal of high-level radioactive waste. The Swedish Nuclear Fuel and Waste Management Company (SKB) set up an in situ experiment (the ABM project) to compare the stability of different bentonites under the conditions of exposure to an iron source and to elevated temperature (up to 130°C) at the Äspö Hard Rock Laboratory, Sweden. Results for the Japanese bentonite (Kunigel V1) are summarized in the present study.

Mineralogical investigation using X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) suggested no transformation of smectite or neoformed clay phases. However, a distinct change in exchangeable cations of smectite was indicated (i.e. from Na type to Fe type and/or Ca type) in the bentonite in the vicinity of the steel heater.

Measurements of hydraulic conductivity and swelling properties suggest that no significant changes occurred in the bentonite even in the vicinity of the steel heater. This is attributed to the limited portion of the bentonite affected by the iron–bentonite interactions and the incomplete ion-exchange reactions. The methylene blue cation exchange capacity and the determination of the exchangeable cations showed that the lateral distribution for these parameters was constant. However, the total exchangeable cation population has changed significantly compared to the initial sample.

In polymer composites, montmorillonite nanosheets are crucial as fire retardants, reinforcers, anti-corrosives, detoxifying agents and ultraviolet-protection agents. However, the quality of montmorillonite nanosheets can be improved by optimizing the raw bentonite purification process in which undesirable phases are removed. Optimization of Iranian calcium bentonite purification for nanomontmorillonite synthesis considering various parameters based on various physical approaches to dispersion and ultrasonication was investigated; the calcium bentonite purification was performed using sodium hexametaphosphate followed by either sedimentation or centrifugation, and the nanomontmorillonite synthesis was performed using ultrasonic treatment. The effects of suspension concentration, milling type, pH and centrifugation duration and speed on the separation of various impure phases were evaluated qualitatively and optimized. The raw and purified bentonite and the synthesized nanomontmorillonite were characterized using X-ray powder diffraction, X-ray fluorescence spectroscopy, Fourier-transform infrared spectroscopy and scanning electron microscopy. The cation-exchange capacity was also measured in the raw and purified samples. Optimal experimental conditions in the dispersed samples were achieved at a 2.5 wt.% concentration of bentonite suspension and planetary milling at pH 7. While the ultrasonic treatment was more effective than the dispersion approach for cristobalite elimination, a smaller lateral size of the montmorillonite sheets, optimized at 0.5 wt.% concentration of the suspension, was achieved. The increased cation-exchange capacity after the purification improved the exfoliation and delamination of montmorillonite nanosheets in the presence of cetyltrimethylammonium bromide as the surfactant. The interplanar spacing of (001) planes of 15 Å in raw bentonite shifted to 21 Å and 19 Å in purified and non-purified samples, respectively, after synthesis.

Tosudite, a regularly interstratified chlorite-smectite, crystallizes as an alteration mineral of several preexisting Al-bearing silicates (feldspars, kaolin minerals, chlorites) present in arkosic sandstones hosted in uranium deposits in Niger. X-ray diffraction patterns show a sharp superstructure at 29–29.6 Å for an air-dried state and a peak at 30.8–31.6 Å following ethylene glycol solvation. The 060 reflection at 1.507–1.509 Å indicates an overall dioctahedral character, and the very low coefficient of variation of the d00l reflections for the solvated mineral (0.03–0.13) permits validation of the regular interstratification justifying its identification as tosudite. Microprobe analysis allowed specification of the component layers of this mixed-layer mineral. The chlorite is a di-trioctahedral type analogous to sudoite (Si3Al4Mg2(OH)8), and the smectite component is a low-charge montmorillonite type Tosudite is characterized by large Al2O3 and MgO contents and small Fe content; its composition corresponds approximately to the formula where octahedral occupancy is ∼7. Scanning electron microscope (SEM) observations show that tosudite is closely associated with some uranium minerals: tosudite crystallization occurred during a late alteration event which post-dates burial diagenesis and during which uranium was remobilized by Mg-rich oxidizing fluids.

When moist clay bodies are heated on one side it is often observed that moisture moves towards the cooler side. This phenomenon has been studied using clay-water mixtures of initially uniform moisture content packed into sealed, vertical tubes, along which a constant temperature gradient is maintained, the tubes having a reservoir of water at constant temperature at their lower, cool ends. Figure 1 shows the moisture distributions obtained after various times in columns of a commercial kaolin (Supreme Kaolin) which contained initially 16-18 per cent. moisture. A “stepped” type of distribution results from the movement of the moisture, the step moving down the column with increasing time.

La determinación del orden o desorden en la dirección perpendicular a las láminas en una nontronita anhidra ha sido efectuada a partir de las reflexiones 001 y 003 y de una parte de la difusión a pequeños ángulos. Mediante la comparación de diagramas experimentales y curvas calculadas a partir de modelos, se pretende poner en evidencia si el sistema es ordenado o desordenado y en el segundo caso la manera de establecer un modelo que traduzca el desorden del sistema. Se llega a la conclusión de que la nontronita potásica anhidra es un sistema desordenado en la dirección perpendicular a las láminas en el que aparecen espaciados correspondientes a varias distancias discretas afectadas por proporciones determinadas.

This study is located on the bentonite outcrop of ‘El Toril’ (Cabo de Gata, Almeria, Spain), where acid solutions have resulted in an alteration front that has caused physical, chemical and mineralogical changes in the bentonite material. The main objective is to assess these changes and to draw a model of evolution of this front in the outcrop. The most important chemical and mineralogical changes observed consist mainly of the loss of mass in the bentonite, the formation of kaolinite, the precipitation of jarosite and alunite from leachates and important changes in the rare earth element distribution pattern. No sulphurs have been identified in the pyroclastic rock at the top of the outcrop, but the presence of dissolution marks and the high concentrations of As, Pb and V in the rock overlying the bentonite point towards the existence, in principle, of these sulphurs and suggest that meteoric alteration is mainly responsible for the genesis of the outcrop.

In 1947, based on field observations and some chemical data, the Leping white earth was first recognized as a sepiolite clay of marine origin and of early Permian age. Later investigations in the 1960s using DTA, XRD and EM confirmed this identification (Zhang Renjun, 1984). Recently, in the ‘Science Spring’, new sepiolite clay deposits have been found in south China and it has become apparent that sedimentary sepiolite in this region is closely connected with the marls of the Lower Permian system.

Ceramic tile production by the wet route requires clay suspensions with a high solid content and low viscosity. In this work the deflocculation of clays in aqueous suspensions was investigated by varying the type of clay and additive. Three kaolinitic and two illitic clays were characterized and dispersed with deflocculants based on lithium, sodium and potassium silicates and polyacrylates. The clays were characterized by chemical and mineralogical analyses, particle size distribution, zeta potential, organic carbon content, cation exchange capacity (CEC) and specific surface area (BET). Deflocculation curves were determined by measuring the viscosity for 50 wt.% clay slips. The results indicate that additive consumption is closely related to CEC and BET, which correspond respectively to the chemical and physical characteristics of the clay mineral's surface. Moreover, viscosity values at the deflocculation point are closely related to BET.