Kaolinite can be used for many applications, including the underground storage of gases. Density functional theory was employed to investigate the adsorption of hydrogen molecules on the kaolinite (001) surface. The coverage dependence of the adsorption sites and energetics was studied systematically for a wide range of coverage, Θ (from 1/16 to 1 monolayer). The three-fold hollow site is the most stable, followed by the bridge, top-z and top sites. The adsorption energy of H2 decreased with increasing coverage, thus indicating the lower stability of surface adsorption due to the repulsion of neighbouring H2 molecules. The coverage has obvious effects on hydrogen adsorption. Other properties of the H2/kaolinite (001) system, including the lattice relaxation and changes of electronic density of states, were also studied and are discussed in detail.

The use of natural clays for the removal of dyes from wastewater, an important part of environmental remediation, is desirable due, not least, to their low cost. Palygorskite (PAL), a rigid-structure clay, is a good candidate for use in the elimination of industrial effluents, based on its exceptional adsorptive properties. Recently, a new palygorskite deposit has been discovered in Cuba and its use in the adsorption of dyes has not yet been explored in detail. In the present study, the use of unmodified natural Cuban palygorskite as a host for dyes was evaluated. Congo red (CR) and methylene blue (MB) were the anionic and cationic dyes tested, respectively, because of their wide use and toxicity to the environment. Several physical-chemical parameters were studied in order to establish the best experimental conditions under which to achieve the greatest dye load per gram of clay. Natural mixtures with different percentages of montmorillonite were also tested to evaluate their effect on the adsorption of the dyes. The results indicated that at pH values of ~7–9 and an initial dye concentration of 0.1 mg mL–1, the process was efficient. X-ray diffraction (XRD) analysis proved the surface adsorption of both dyes on the clays. The main interactions involved in the clay-dye system were electrostatic forces and H-bonds. Adsorption of CR seemed to be controlled fundamentally by the palygorskite phase. Such results support the use of this natural clay as an efficient host for the removal of MB and CR from wastewater.

In order to improve the dispersibility of halloysite nanotubes (HNTs) in polytetrafluoroethylene (PTFE), the modification of HNT surfaces was studied with three types of modifiers (polymethyl methacrylate [PMMA], sodium dodecyl sulfate [SDS] and carboxylic acid). The modified HNTs were characterized by Fourier-transform infrared (FTIR) spectrometry, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and contact angle measurements. The HNTs were used to reinforce the mechanical properties of PTFE. The mechanical results indicated that the tensile strength of the modified HNT-filled PTFE nanocomposites (F-HNT/PTFE) improved to an acceptable degree and Young's modulus increased significantly. The tribological results showed that the wear rate of F-HNT/PTFE decreased by 21–82 and 9–40 times compared to pure PTFE and the pristine F-HNT/PTFE, respectively.

A halloysite clay from Nador (NE Morocco) was studied to evaluate its suitability in the ceramics industry. A cross-section involving all the Messinian facies was performed in the Melilla Neogene basin, at the foot of the Gourougou volcano, to establish the origin of the halloysite and estimate its reserves. White layers of halloysite and red clays rich in smectite occurring in contact with basal-reef limestone were characterized by mineralogical (XRD, IR), textural (SEM) and physico-chemical analyses (grain-size, Atterberg limits, DTA/TG, XRF and specific surface area). Ceramic properties were evaluated for halloysite fired from 500 to 1100°C to evaluate technical processing for ceramic production.

The halloysite clay consists of fine particles with a high plasticity and a large specific surface area. The XRD investigation revealed the presence of 7 Å non-hydrated halloysite along with gibbsite, alunite, K-feldspar and traces of smectite and illite.

The presence of halloysite was confirmed from the characteristic IR bands at 3695 and 3618 cm−1 and the predominance of tubular crystals observed in the SEM. The chemical analysis revealed high contents linked to the presence of Al-rich phases (gibbsite and alunite). DTA/TG and XRD results of fired clay samples proved the dehydroxylation of halloysite and a rearrangement of metakaolinite to form mullite and spinel at 975°C.

The Moroccan halloysite might be suitable for refractory ceramic applications. However, addition of quartz sand might be necessary to avoid crack development during firing and to reduce the plasticity of raw halloysite and minimize shrinkage during sintering.

The increase of the absorption efficiency of boron (B) by plants is essential for increasing crop productivity. The intercalation of B in MgAl layered double hydroxides (LDHs) is an alternative to evaluating how these materials can provide B to plants. In this work, a MgAl LDH intercalated with borate ions (Mg2Al-B-LDH) was synthesized by the constant pH coprecipitation method, and the material produced was evaluated as a matrix for storage and as a source of B for plants. The Mg2Al-B-LDH was characterized by XRD, ATR-FTIR, TGA-DTA, specific surface area, pore size and volume, and SEM. A bioassay was performed to verify the supply of B to plants from the two sources in the forms of H3BO3 and of Mg2Al-B-LDH to sunflower plants grown in pots. The LDH basal spacing value of 12.0 Å is characteristic of intercalation of tetraborate octahydrate ions [B4O5(OH)42−]·8H2O between the layers. There was an increase in the dry matter (DM) and B content of the plants relative to those treatments where no B was added. The lack of statistical difference for plant yield between the two sources of B suggests a lack of stability of the Mg2Al-B-LDH structure under the acidic condition of the soil.

The use of clays as industrial catalysts requires optimization of modification methods during their preparation. The objective of this paper was to improve the traditional method of bentonite impregnation using ultrasound. For this purpose, three series of samples with Fe3+/clay molar ratios of 0.6–11 mmol/g were prepared, which differed in terms of preparation procedure. The first batch of samples was subjected to the conventional method of impregnation, where total synthesis of catalysts took 4 h. The other two series of samples were prepared with impregnation improved by ultrasound: preparation of Fe-polycation (5 min) and then its incorporation with a clay suspension for 5 and 10 min. The effect of clay preparation method on the catalyst stability and efficiency in a heterogeneous Fenton process was studied on aqueous solutions of synthetic Reactive Blue 4 dye. The catalysts prepared by the conventional method and the improved ultrasound method achieved high efficacy (91–97%, respectively), but their stability was different in the Fenton process. The catalysts prepared using ultrasound for 10 min exhibited greatest stability in the Fenton process. The catalysts synthesized with different Fe loadings displayed an increase in specific surface area and mesoporosity. Samples prepared by the improved impregnation method are comparable in terms of their characteristics with their counterparts prepared by the conventional method. It is thus possible to reduce the time taken by traditional catalyst synthesis by using optimized exposure time to ultrasonic waves.

The aim of this research was to determine the temperature of kaolin calcination in order to obtain an intermediate product (metakaolin) for the synthesis of geopolymers with potential application as self-supporting zeolitic membranes. The products obtained were analysed with X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The structural analysis of the metakaolins obtained suggested that the optimal temperature for the proposed application is 700°C. After alkali activation of metakaolin, it is possible to obtain zeolite A and hydroxysodalite. The factors analysed, determining the type and quantity of crystalline phases, were activation temperature and concentration of sodium hydroxide solution (activator). The largest amounts of zeolites were obtained by alkali activation with 9 mol/dm3 NaOH solution at 70°C.

The present study examined the microstructure and mechanical properties of ceramic composites based on a kaolin from Djebel Debbagh, northeast Algeria, composed mainly of kaolinite and halloysite with the addition of various amounts of BaCO3. The composites were prepared by high-energy ball milling and sintered at 1100°C and 1200°C for 3 h. The samples sintered at 1200°C without BaCO3 were composed mainly of mullite, which disappeared with increasing BaCO3 content. X-ray diffraction investigation showed the presence of hexacelsian (BaAl2SiO6 and BaAl2Si2O8), which disappeared at BaCO3 contents >50 wt.% in favour of barium aluminium and barium silicate phases. At 40 wt.% BaCO3 content, the porosity of the composites decreased from 0.7% to 0.1% and the microhardness increased from 7 to 8 GPa, respectively, at 1100°C and 1200°C due to the amorphous phase.

Organo-kenyaites were prepared from a cetyltrimethylammonium hydroxide (C16TMAOH) solution and solid sodium kenyaite (Na2Si22O45.10H2O) mixture. The effect of the initial cetyltrimethylammonium solution on the structure of the intercalated materials was investigated by CHN analyses, X-ray diffraction (XRD), thermogravimetric analysis, SEM, and 29Si and 13C solid NMR techniques. For C16TMAOH concentration 0.25 mM, the Na+ cations were fully exchanged. Initial C16TMAOH concentrations higher than 0.25 mM had little effect on the intercalated amount of C16TMA+ cations. The organic cations content reached a plateau of 0.66 mmol/g. The arrangement model of C16TMA+ cations corresponded to a tilt of the organic cations to the silicate layers with an angle of 42° as deduced by XRD studies. The C16TMA+ cations exhibited mainly trans-configuration of the methyl chains, as was shown by solid 13C NMR. The thermal stability of the organo-silicates was studied using in situ FTIR and in situ XRD in the range 25–450°C. The C16TMA-kenyaites were stable at temperatures below 200°C. They collapsed at higher temperatures due to the decomposition of the intercalated surfactants. These organo-kenyaites were used to remove the acidic dye molecule, eosin. The removal tests were performed at varying conditions of initial dye concentrations, organic content in the organo-kenyaites and heating temperatures. In general, the organic modification improved the removal capacity of the Na-kenyaite from 2 mg of eosin/g to 60 mg of eosin/g, and this capacity was related to the organic contents and the calcination temperatures of the organo-kenyaites.

The recent discovery of a Roman ceramics manufacturing workshop at Montelabate (Perugia, Italy), in use from the first century BC until the late-fourth to fifth centuries AD, offers a unique opportunity to study the technical processes for producing Roman amphorae. Ancient and modern clays were sampled and analysed; they do not differ significantly, supporting the hypothesis of the exploitation of the rich local clay source that allowed a continuity of production. Characterization of the clays was performed using geotechnical methods (Atterberg limits and size distribution) and by thermogravimetric and differential thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray diffraction and X-ray fluorescence analyses. The material was suitable for pottery making with the addition of calcite and quartz sand temper. Production waste and discarded materials as well as good-quality products were also analysed with the same methodology. It is therefore possible to reconstruct the ancient technology by defining the recipe for the production of the amphorae and their firing temperature on the basis of the decomposition of clay materials and the presence of newly formed minerals.

Earthquake-induced rock shear through a bentonite-filled deposition hole in a repository for spent nuclear fuel is an important scenario for the safety analysis because it may cause substantial damage to the canister hosting the spent fuel. Appropriate tools to investigate the effects on the buffer and the canister are required.

The study described here explored the laboratory tests conducted to develop a material model of the bentonite buffer to be used in the simulations, the material models that these tests have provided and finite element (FE) simulations of three scale tests of a rock shear for comparison between modelled and measured results. The results were used for validation of the material models and the calculation technique that was used for modelling different rock-shear cases.

The laboratory study consisted of swelling-pressure tests and tests to determine shear strength and stress-strain properties. The material model is elastic-plastic with a nonlinear stress-strain relation which depends on the density of the bentonite buffer and is a function of the strain rate. The three scale tests were modelled using the Abaqus finite element code. Good agreement between modelled and measured results was observed, in spite of the complexity of the models and the difficulties associated with measuring stresses and strains under the very fast shear.

The modelling results thus validate the modelling of the SR-Site. The modelling technique, the element mesh and the material models used in these analyses are well fitted and useful for this type of modelling.

Kaolin and diatomite are abundant and widely available geological materials that may immobilize or stabilize functional chemical species on their surfaces for various applications. Acid-treated kaolin and diatomite were intercalated with photocatalyst Ag-TiO2 nanoparticles using the sol–gel technique to prepare nanocomposite ceramic materials. The nanocomposites were sintered between 900°C and 1000°C to induce thermal reactions and to enhance nanoparticle–substrate attachment. Chemical and thermal characterizations of the acid-treated materials and intercalated nanocomposites were performed with energy-dispersive X-ray (EDX) analysis and differential scanning calorimetry (DSC), respectively. The Brunauer–Emmett–Teller (BET)-specific surface area and scanning electron microscopy (SEM) were employed for physical and microstructural characterization of the nanocomposites, respectively. Morphological studies revealed a uniform distribution of Ag-TiO2 nanocrystallites in pores and on mineral particle surfaces. The BET analysis showed remarkable surface and grain modification by sintering. Decreases in the BET-specific surface area were observed for the sintered ceramic nanocomposite, Ag-TiO2-kaolin (20.244 to 5.446 m2/g) and Ag-TiO2-diatomite (19.582 to 10.148 m2/g).

This paper describes a detailed petrographic and isotopic study of hypabyssal sheets of quartz-syenite that represent the ultimate differentiation product of the oceanite alkaline magmatic reservoir of the Piton des Neiges stratovolcano (Réunion Island). Clay minerals of the corrensite to chlorite series crystallized during the late-magmatic activity, with quartz, carbonates and accessory minerals from juvenile fluids filling the primary porosity of the quartz-syenite. It is proposed that a double chemical transfer occurred at the end of the crystallization process: degassing of the exsolved CO2-rich and SiO2-rich fluid from the magmatic chamber through the porous quartz-syenite and diffusion of Al, Fe and Mg from the intruded basalts affected by the juvenile fluids towards the primary porosity of the quartz-syenite, feeding the crystallization of late-magmatic clays in the residual primary pores after quartz and carbonate deposition. This process may be generalized to alkaline plutonism, as well as to the primitive crusts of terrestrial planets, and may be the first source of clays in early planets.

Five clay deposits in Foumban, west Cameroon, were studied for their morphological, mineralogical and geochemical properties to determine their suitability for ceramics. The clays were examined with X-ray diffraction, X-ray fluorescence, thermal gravimetric analysis and Fourier-transform infrared spectroscopy. Field studies showed that a homogeneous clayey layer occurs at the upper part of the laterite cover of the interfluves, while the valleys are occupied by a clayey heterogeneous hydromorphic material. The clays are composed of kaolinite, illite, smectite and chlorite, associated with quartz, K-feldspars, plagioclase, goethite, traces of rutile and hematite. Geochemical analyses of these samples show a relatively large amount of SiO2 (45–71%), Al2O3 (14–31%) and relatively little Fe2O3 (up to 11%), suggesting weathering of mainly granitic and rhyolitic parent rocks. The majority of these clays may be used in the production of structural ceramics such as bricks (refractory or not) and tiles. The relatively high proportion of the alkalis (K2O + Na2O; 6–8%) in some samples from Marom and Njindare areas might be responsible for the low firing temperatures. The abundance of smectite limits the application of some Koutaba and Marom clays for structural ceramics, while the high Fe2O3 contents (>8%) in some Bangourain clays indicate that some pre-treatment might be necessary prior to use.

A novel method to perform small-scale laboratory experiments that reproduce concrete–bentonite and concrete–groundwater interactions has been developed. Such interfaces will prevail in engineered barrier systems used for isolation of nuclear waste. With the goal of optimizing the experimental method, this work has analysed the geochemical interaction of distilled water, low-pH cement mortar and FEBEX-bentonite for 75 days. Limited but evident reactivity between the materials was observed, mainly decalcification in cement mortar, carbonation at the interface with bentonite and Mg enrichment in bentonite. These results are consistent with the state-of-the-art literature and were used to validate this small-scale pilot laboratory experiment to establish the basis for further studies comparing the behaviour of different buffer and cement materials.

In an automated installation powered by direct current (DC), the boiling curves and heat-transfer-coefficient (HTC) dependencies on the superheat values (ΔT) under free convection conditions for the water nanodispersions of clay minerals – illite, montmorillonite, palygorskite and genetic mixtures of the latter two – were obtained. The effects of some factors on pool boiling heat transfer were also studied.

A significant influence of the shape and anisotropy of nanoparticles (NPs) on the heat-transfer parameters of nanofluids (NFs) was detected. A significant critical heat flux (CHF) enhancement (up to 200–300%) at boiling of the nanofluids studied was established, which is due to nanoparticle deposition on the heater surface during nanofluid boiling. The structure of the nanomaterials deposited is important in the enhancement of heat transfer at boiling of nanofluids and in avoiding boiling crises.

The present study showed the effectiveness of clay-mineral nanofluids for extra emergency cooling of overheated surfaces of powerful equipment in the event of the sudden onset of a boiling crisis.

Despite many reviews and original articles, the actual crystal structure of tubular halloysites remains unclear. Analysis of the structural features of defect-free kaolinite, refined by Bish & von Dreele (1989), shows that the ordered 1Tc kaolinite structure can be described equally well by the orthogonal layer cell {a0, b0, γ0} (γ0 = 90°) or by two enantiomorphic oblique layer cells {a1, b1, γ1} and {a2, b2, γ2}, related to each other by a mirror plane. To simulate diffraction effects for tubular halloysite, the parameters and atomic coordinates of the orthogonal layer unit cell and the layer-displacement vectors t1 and t2 responsible for formation of the kaolinite enantiomorphs were deduced by transformation of the parameters of the defect-free kaolinite refined by Bish & von Dreele (1989). Modelling X-ray diffraction patterns show that the samples consist of either single, two or three phases, with the number and their structural features depending on the morphology of the particles. Samples formed of prismatic particles consist of halloysite-like structure (HLS), kaolinite-like structure (KLS) and halloysite cylindrical structure (HCS) phases occurring in various proportions. Samples of proper cylindrical tubes consist of a single HCS phase, whilst samples formed by particles having morphologies intermediate between proper cylindrical and well-developed prismatic forms consist of the KLS and HCS phases. The KLS phase is comparable to low-ordered platy kaolinite with identical unit-cell parameters, layer-displacement vectors and arbitrary stacking faults, except that the layer displacements are not random as in kaolinite, but are distributed at R = 1 such that t1 and t2 displacements have a strong tendency to be segregated. Structural parameters describing the HLS and KLS phases are identical, but in the HLS phase there is a strong tendency to the regular alternation of the t1 and t2 displacements, and the HLS phases do not contain arbitrary stacking faults. A characteristic feature of the three-phase prismatic samples is that the stacking of the layers along the c* axis is periodic and the layer thicknesses are similar to those of platy kaolinite. In contrast, in the KLS phase formed in samples with particles of intermediate morphologies, the hydrated 10 and 7.25 Å layers are interstratified. The relationship between the structural and morphological features of the coexisting phases suggests a sequence of phase formation from the centre to the surface of halloysite tubes that progresses from the HCS to the HLS via the KLS phase. The results of this study demonstrate that all kaolinite and halloysite (7 Å) varieties are built by the same fundamental structural units.

Three clayey materials named MY3, KK and KG originating from the Foumban region (west Cameroon) were analysed to determine their granulometry, plasticity, major-element chemistry and mineralogy. Dilatometric and ceramic behaviour were also investigated. Clays were shaped by uniaxial pressing in a steel mould. Shaped samples were heated at 1300, 1400 and 1500°C. The end products were characterized in terms of their density, porosity and compressive strength. Raw materials differ in terms of their mineralogical composition, grain-size distribution, Al2O3 content and the nature and abundance of impurities inducing specific thermal behaviour during dilatometric analysis and sintering tests. The final material properties may be related to the main features of the raw materials used.