Microcapsules are successfully used in various applications such as self-healing, drug delivery and military camouflage. The shells of the microcapsules based on the traditional surfactant-stabilized emulsion template method are often single organic materials. The surfactants generally have insufficient stability against demulsification during preparation of the microcapsules. In the present study, kaolinite was used as an emulsifier for stabilizing Pickering emulsions and subsequently as an enhancer for forming microcapsules. Kaolinite-armoured polyurea microcapsules were fabricated based on the interfacial polymerization of isophorone diisocyanate at the oil–water interfaces of kaolinite-stabilized Pickering emulsions. The prepared microcapsules with core–shell structure were spherical and exhibited good dispersibility in anhydrous ethanol. The shell thickness (~0.5–1.0 μm) and diameter (~20.0–160.0 μm) of kaolinite-armoured polyurea microcapsules may be tailored by varying the dosages of isophorone diisocyanate and kaolinite and the emulsifying speed of the high-shear homogenizer. Hence, the encapsulation and release performance of microcapsules may be controlled. The kaolinite particles were embedded and armoured in a polyurea matrix. The formed kaolinite-embedded and -armoured polyurea structures might prolong the release of the encapsulated lipophilic Sudan Red (III) from 20 to 45 h. The microcapsules have controllable encapsulation and release characteristics for lipophilic compounds and are cost effective, making them suitable pesticides.

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.

An extensive X-ray diffraction investigation of Keuper Marl samples from the English Midlands shows the existence of both chloritic and interlayered chloritic clays.

Chemical experiments show that the interlayer component of the chloritic phase can be removed. This suggests that the ‘chloritic materials of unusual type’, known since the early 1950s to exist in the Keuper Marl, represent chlorite-montmorillonite intergrades.

The mineralogy of any sample identified by an X-ray investigator, is influenced by the completeness of the chlorite interlayer. Since the amount of interlayer material is variable any ‘absolute’ differentiation between species is difficult.

Melt blending using a twin-screw extruder was used to prepare composites of polypropylene (PP)/organic rectorite (PR). The organic rectorite (OREC) was modified with dodecyl benzyl dimethyl ammonium bromide (1227). Wide-angle X-ray diffraction (WAXD) and transmission electron microscopy were used to investigate the dispersion of OREC in the composites. The d spacings of OREC in PR composites was greater than in OREC itself. The dispersion of OREC particles in the PP polymer matrix was fine and uniform when the clay content was small (2 wt.%). The rheology was characterized using a capillary rheometer. The processing behaviour of the PR system improved as the amount of OREC added increased. Non-isothermal crystallization kinetics were analysed using differential scanning calorimetry. It was shown that the addition of OREC had a heterogeneous nucleation effect on PP, and can accelerate the crystallization. However, only when fine dispersion was achieved, and at lower rates of temperature decrease, was the crystallinity greater. Wide-angle X-ray diffraction and polarized light microscopy were used to observe the crystalline form and crystallite size. The PP in the PR composites exhibited an a-monoclinic crystal form, as in pure PP, and in both cases a spherulite structure was observed. However, the smaller spherulite size in the PR systems indicated that addition of OREC can reduce the crystal size significantly, which might improve the ‘toughness’ of the PP. The mechanical properties (tensile and impact strength) improved when the amount of OREC added was appropriate. Dynamic mechanical analysis showed that the storage modulus (E′) and loss modulus (E″) of the nanocomposites were somewhat greater than those of pure PP when an appropriate amount of OREC was added. Finally, thermogravimetric analysis showed that the PR systems exhibited a greater thermal stability than was seen with pure PP.

Cationic binuclear oxo- and carboxylate bridged Fe(III) complexes of N-alkyl-N,Nbis(2-pyridylmethyl)amines are introduced into the interlayer region of smectites by cation exchange reactions. The reaction can be divided into three steps. After a predominant loading of external surfaces, cation exchange sites at internal surfaces react, accompanied by considerable stmctaral expansion. Both reaction stages belong to the steep section of the exchange isotherms. At a certain loading, which depends on the complex substituents and the layer charge of the smectite, the isotherms become flat. With bulky shaped complex cations and highly charged smectites, exchange is not quantitative; vermiculite-type minerals show a very small complex uptake. For this behaviour, both thermodynamic and kinetic reasons must be considered. From these results the number of cation exchange positions at external surfaces of smectite crystals may be estimated.

Spötl et al. (1996) have re-examined studies published by us on clay materials of sandstones in the Paris Basin. They refute the XRD characterization, K-Ar dating and formation temperature of one of the interstratified illite-smectite phases identified and have provided an alternative explanation of the published results. However, the authors ignored some basic data provided in the publications under discussion, and they have not been able to explain readily why some of the data were discarded. Furthermore, part of their disagreement is unsubstantiated. We maintain that, on the basis of coherency and consistency of all the data obtained, as well as on independent published results, the most satisfactory interpretation for the thermal evolution of the Paris Basin is the one that we suggested in our publications.

A dioctahedral bentonite was treated hydrothermally with KCI solutions (0.025-1 M) at different temperatures (60-200°C) and times (1-360 days) to evaluate its use as a barrier for radioactive waste disposal. Equations relating adsorbed K on smectite with initial and equilibrium K concentrations in solution, temperature and time have been obtained. These equations are useful for modelling the influence and behaviour of these variables and contribute to the performance assessment calculations for radioactive waste repositories. Likewise, the thermodynamic parameters of the K adsorption process have been calculated. Other relationships, including silica in solution and pH, are also shown.

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.

The low-frequency conductivity of aqueous kaolinite suspensions has been measured as a function of volume fraction and concentration of KCl, K2SO4 and BaCl2, respectively. These measurements were interpreted with a theoretical model accounting for surface conductivity and particle shape. For the first time, an internally consistent data set was established by measuring all parameters necessary to solve the relevant equations. The simultaneous availability of surface conductivity, surface charge density and diffuse layer charge density permitted the estimation of counterion mobilities in the stagnant layer and a consistency check for the evaluation procedure of the conductivity experiments. In agreement with current literature results, monovalent counterions were found to have a Stern layer mobility similar to their bulk mobility, whereas the mobility of divalent counterions in this layer is reduced by a factor of ∼2.

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.

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.

The rheological and filtration properties of a Tunisian clay are presented and compared with those of Wyoming bentonite. The study was part of an evauation of Tunisian mining resources in general, and of the bentonitic deposits in particular. Qualitatively, the two clays exhibit the same rheological and filtration behaviour but quantitatively the properties of purified Wyoming bentonite are distinctly better at the same concentration. The difference can be related to the mineralogical structure and the presence of 13% illite in the Tunisian clay. Standard tests show that the rheological behaviour of the purified Tunisian clay is close to that of the raw Wyoming bentonite and conform to the American Petroluem Institute (A.P.I.) standards for medium-depth drilling formulations.

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.

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.

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.

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.

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).

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%.