Physical and/or chemical changes such as refinement, component dissolution, exchange/adsorption, structural evolution and recombination of phyllosilicate minerals occur continuously in a naturally weakly acidic water environment. To compare the differential dissolution of cations that occupy various sites in vermiculite, trioctahedral vermiculite was dissolved in various concentrations of oxalate for 24 h and in 0.2 M oxalate for various durations. The concentration of ions in the leaching solution and the phase, structure and morphology of the original samples and acid-leached samples were analysed. Structural analysis showed that the 001 reflections of vermiculite gradually shifted to a higher angle and eventually disappeared after the dissolution of interlayer cations caused by acid leaching. The amount and rate of dissolution of each cation in the vermiculite showed that the octahedral cation Mg2+ is more soluble than Fe2+ and Fe3+. The dissolution rates of Al3+, Mg2+ and Ca2+ were greatest in the first 4 h and then decreased gradually. Amorphous silicon dioxide and calcium oxalate were formed during acid leaching, and calcium oxalate was formed in the first 4 h. After leaching with oxalate for various periods, the cation-exchange capacity (CEC) of the samples first increased and then decreased. Micromorphology analysis showed that the acid erosion process started from the edges. The results of this work contribute to our understanding of many natural geochemical processes, and they will be useful for several applications such as soil improvement, ecological restoration and environmental protection.

Illite is a common clay mineral that is found in a wide range of geological settings. The good thermal stability and non-swelling properties of illite make it valuable in ceramic materials, paints and coatings, drilling fluids, agriculture and geological studies. To gain a deeper understanding of the physical and chemical properties of illite, in the present paper the atomic and electronic structures of a typical trans-vacant 1M Al-rich illite were constructed and calculated using density functional theory. The calculated indirect band gap of Al-rich illite was 4.99 eV. The electronic analysis revealed that the interactions in the tetrahedral sheet were more stable than those in the octahedral sheet. The substitution of Al atoms noticeably reduced the stability of the tetrahedral sheet in Al-rich illite. Other properties of Al-rich illite, including the density of states, electron population/charge, electronic charge density and bonding interaction, are also discussed and analysed in detail.

In this study, aluminium fluoride trihydrate (AlF3⋅3H2O) was used to inhibit the sintering of calcined coal-series kaolin (CCSK). In addition, the oil absorption properties of CCSK were studied. The particle-size distribution, specific surface area and porosity of the samples were investigated as a function of calcination temperature and the addition of AlF3⋅3H2O. Moreover, the ability of AlF3⋅3H2O to improve the oil absorption of CCSK was explored. The morphology, structure and phase composition of the specimens were investigated using scanning electron microscopy and X-ray diffraction. The phase transition during heating of the samples was studied using thermogravimetric analysis. The preparation with 10 wt.% AlF3⋅3H2O had the optimal sintering inhibition effect on CCSK at 1000°C. The release of SiF4 gas during heating and the formation of mullite whiskers on the particle surface caused by AlF3⋅3H2O moderated the formation of molten-phase liquid bridges between particles and inhibited sintering of the raw material powder. Furthermore, the formation of submicron mullite whiskers on the surface of the CCSK particles enhanced the oil-absorption properties of the sample significantly.

Over several decades, a wealth of literature has been devoted to correlations between the chemistries of phyllosilicates and their crystallographic unit-cell parameter values. The c parameter is currently used because of its relation to the layer-to-layer distance, characteristic of the various families of phyllosilicates. The b parameter is also of interest because it allows measurement of the layer lateral dimensions and inherent structural adjustments. This unit-cell distance can be extracted from X-ray diffraction traces from the (06ℓ;33ℓ) diffraction region and by attributing the main diffraction peak observed to a 060 reflection, leading to the relationship b = 6.d(060). The aim of this paper is to revisit the relationships between the b value (or equivalent) of the phyllosilicate (i.e. TO, TOT and TOTO) or hydroxide (i.e. hydroxide, oxyhydroxide and layered double hydroxide) families and the layer chemistry based on a mean ionic radius R of octahedral cations, calculated as $R = \mathop \sum \nolimits_{i = 1}^n ( {r_i.x_i} )$, where ri is the ionic radius of the octahedral cation i and xi is its molar fraction over n types of octahedral cations ($\mathop \sum \nolimits_{i = 1}^n ( {x_i} ) = 1$). The data were collected from the literature and involved both natural and synthetic samples with both dioctahedral and trioctahedral structures of the octahedral sheet. The results showed that b values can be linked strongly to R, leading to suitable linear regressions for all of the studied structures. All correlations were found to be applicable irrespective of the di- or trioctahedral nature of the octahedral sheet, and these are discussed in light of (1) the lateral dimension of the octahedral sheet and (2) the dimensional misfit between the tetrahedral and octahedral sheets. For hydroxide families, all data can be gathered on a single b vs R correlation line, and the dimensional properties of the octahedral sheet can be interpreted simply based on an oxygen–cation–oxygen mean distance. For TO structures, two general b vs R correlation trends were reported, and these were assigned to two adjustment mechanisms corresponding to distinct types of tetrahedral and octahedral distortions. For the mica TOT family, two main trends were also reported, whereas the use of the synthetic mica series allowed us to demonstrate that the obtained scattering of data was mainly driven by the presence of multiple limited solid solutions. Such chemical complexity was also noted for smectites, especially regarding the tetrahedral composition and associated variability in layer charge. This variability made it difficult to propose a general regression correlating b to R values for smectites, although the regression obtained for neutral TOT layers can apply as a first-order relation. Finally, a single general b vs R correlation was obtained for chlorites, and the observed slope of the regression was interpreted according to the role played by the isolated hydroxide sheet on the evolution of the lateral dimension of the structures.

Nine halloysite nanotubes (HNTs) have been examined using scanning electron microscopy (SEM), atomic force microscopy (AFM) and (cross-sectional) transmission electron microscopy (TEM) to evaluate details of their external and internal morphologies. The samples span morphologies within the cylindrical to prismatic-polygonal framework proposed by Hillier et al. (2016). The ‘carpet roll’ model assumed in the conceptualization of most technological applications of HNTs is shown to be far too simplistic. Both cylindrical and prismatic forms have abundant edge steps traversing their surfaces that, by analogy with plates of kaolinite, correspond to prism faces. The mean value for the diameter of the central lumen of the tubes is 12 nm. Numerous slit-like nanopores, with diameters up to 18 nm, also occur between packets of layers, particularly in prismatic forms at the junction between a central cylindrical core and outer packets of planar layers. These pores expose aluminol and siloxane surfaces, but unlike the lumen, which is assumed only to expose an aluminol surface, they do not extend along the entire length of the nanotube. Edge steps seen most clearly by AFM correspond in height to the packets of layers seen in TEM. TEM cross-sections suggest that tube growth occurs by accretion of a spiralled thickening wedge of layers evolving from cylindrical to polygonal form and reveal that planar sectors may be joined by either abrupt angular junctions or by short sections of curved layers. A more realistic model of the internal and external morphologies of HNTs is proposed to assist with understanding of the behaviour of HNTs in technological applications.

The development and application of Fe-rich palygorskite clay has been restricted significantly by its red colour and low grade. Moreover, the nano-structured properties of palygorskite and the relatively large Fe content of Fe-rich palygorskite clay have received insufficient attention. The present study involved the synthesis of Ni-based catalysts via a coprecipitation method using Fe-rich palygorskite clay as the support. The catalysts were then evaluated for their performance for catalytic steam reforming of toluene (CSRT). The experimental findings revealed that the Fe in Fe-rich palygorskite clay interacted strongly with Ni and formed Fe-Ni alloys. The catalyst with a Ni/Fe mass ratio of 14 (Ni14/FePal) calcined in air at 600°C exhibited superior performance for CSRT under the reaction temperature 700°C and S/C molar ratio of 1.0. According to the kinetics study, Ni14/FePal exhibited the lowest apparent activation energy (33.99 kJ mol−1) among the catalysts, which further confirmed the superior catalytic activity in CSRT. The characterizations of the catalysts used demonstrated that the excellent stability and resistance to coke formation of Ni14/FePal were attributable to the presence of a sufficient amount of highly dispersed Fe-Ni alloys on its surface.

In this study, stable and radioactive lead removal from aqueous solution by adsorption using bentonite, zeolite and perlite minerals obtained from various locations in Türkiye was studied in batch experiments. The adsorbents were first characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), and then the physicochemical properties were determined. The effects of various factors that influence adsorption, such as solution pH, adsorbent dosage, contact time, initial Pb2+ ion concentration, temperature and shaking rate, were studied. The adsorption of Pb2+ was modelled using the Langmuir, Freundlich and Dubinin–Radushkevich isotherms. The adsorption capacities of the minerals for Pb2+ followed the order: bentonite > zeolite > perlite, and the maximum adsorption capacities were 131.6, 36.1 and 21.5 mg g–1, respectively. The adsorption data fit well with the Langmuir isotherm. The bonding of lead ions on the adsorbents was confirmed by XRF and FTIR analyses after the adsorption process. The adsorption of Pb2+ ions on the adsorbents was spontaneous and endothermic. The adsorption process took place by cation exchange in addition to electrostatic interaction. Furthermore, radioactive 210Pb2+ adsorption on bentonite, zeolite and perlite was studied, with the analyte being analysed using a liquid scintillation counter. It was seen that in addition to Pb(II) ions, these minerals also adsorbed the radioactive decay products of 210Pb, which were 210Po and 210Bi. The removal percentages of 210Pb were 95%, 38% and 30% and those of 210Po were 75%, 60% and 74% for bentonite, zeolite and perlite, respectively.

Typical unconventional gas/liquid plays of China were studied using field-emission/focused ion beam scanning electron microscopy (SEM) for clay mineralogy and microstructural development. The SEM microstructural investigations of clay-rich shale and mudstone reservoirs provided significant information about clay mineral type, size, distribution and aggregates, which allows for interpretations regarding porosity preservation and petrophysical variability. The major clay-hosted porosity types are interparticle clay pores, intraparticle clay pores and aggregate pores. Interparticle clay pores occur in open spaces of the clay aggregates and include four subtypes: (1) elongated pores, (2) packed pores, (3) jagged pores and (4) card-house pores. Intraparticle clay pores are present within clay particles and have mostly secondary origin. These pores are diagenesis dependent and are restricted to secondary illite particles during the transformation of clay minerals from smectite to illite. Intraparticle clay pores constitute only isolated porosity and could not contribute to hydrocarbon molecule storage and migration. Aggregate pores were predominantly encountered in association with organic–clay and pyrite–clay aggregates. In places, organic–pyrite–clay aggregates can also display polymerization, but they do not contribute significantly to overall porosity and permeability. Combining SEM morphological analyses with the software ImageJ is critical in clay microstructure and porosity analyses via semi-quantitative characterization of the 3D pore surface, 2D pore profile, pore quantity, pore size, areal porosity, etc. These visual and semi-quantitative results highlight the significance of jagged pores and pyrite–clay aggregate pores in shale gas/liquid reservoirs because they may be important facilitators of gas storage and transmission.

To investigate the influence of clay mineral microstructures on mechanical properties across varying hydration levels, this study employed molecular dynamics simulations to conduct uniaxial tensile strength tests in three orthogonal directions (x, y, z) using illite, montmorillonite and kaolinite. The moisture content was varied from 0% to 10% in 1% increments and from 0% to 50% in 10% increments. The observations highlight the role of water molecules in disrupting the inherent microscopic atomic structure of clay minerals, leading to diminished stability and a decline in tensile strength. As moisture content increased, there was a pronounced increase in the layer spacing of all three clay minerals, indicative of their hydration expansion behaviour. Concurrently, discernible reductions in both the tensile strength and Young's modulus of the clay minerals were observed.

The present work aims to prospect and study the plastic and superplastic clay deposits in the state of São Paulo, Brazil, as a source of raw materials for the ceramic tile industry and especially for the production of porcelain stoneware tiles. To achieve the proposed objectives, a geological study was carried out through the mapping and identification of the present lithologies, lithogeochemical characterization using X-ray diffraction, inductively coupled plasma optical emission spectrometry, cation-exchange capacity and organic carbon and characterization of the ceramic technological properties, including granulometric analysis by sedigraph and Brunauer–Emmett–Teller specific surface area. According to their geological characteristics, the studied deposits were classified into two types: a detrital sedimentary deposit, restricted to Quaternary alluvial sediments and Neogenic Tertiary formations and composed of silt-sandy clay and plastic, kaolinitic, refractory and silico-aluminous facies; and an alterite type, found in Permo-Carboniferous rocks of the Paraná Basin, composed of laminated/massive weathering siltstones, with the highly plastic, fluxing clay minerals illite, kaolinite and smectites. Among the targets studied in these deposits, argillaceous facies with plastic and superplastic characteristics were identified, which affect their applicability in compositions for producing porcelain stoneware tiles and stoneware.

The synthesis of nano-silica is gaining the attention of researchers due to its numerous applications in various fields such as medicine, the food industry, catalysis, agriculture and construction, amongst others, because of its unique physicochemical features. However, achieving its facile synthesis and finding inexpensive source material that is locally available requires further exploration for its large-scale production. This paper reports the synthesis and characterization of nano-silica from locally available laterite clay using the sol-gel method. The product was analysed using X-ray florescence, X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. It was observed that the product was spherical, agglomerated and amorphous in nature. The obtained nano-silica was found to have 97% and 95% purity for sodium hydroxide and potassium hydroxide, respectively. The synthesized nano-silica is expected to play pivotal role as a pozzolanic activator in the construction industry.

Dodecyl dimethyl benzyl ammonium (DDBA) is a novel cation surfactant used to modify clay minerals. DDBA-intercalated montmorillonite is formed by the ion exchange between DDBA cations in the solution and cations in the montmorillonite interlayers. By using molecular dynamics simulations, we investigated the basal spacings, interlayer structures and dynamics of DDBA-montmorillonites. The results showed that the calculated basal spacings agreed well with experimental values and that the layering behaviours of DDBA had been revealed. The ammonium groups of DDBA ions preferred staying close to the centre of Si–O six-member rings. The benzyl group and lauryl group were oriented in parallel in the monolayer state, whereas they were tilted in other states. DDBA ions have very low mobility in the interlayer region, indicating that the negatively charged montmorillonite surfaces can effectively fix this positively charged surfactant. The microscopic structures and dynamics obtained in the present study provide atomic-scale insights into the properties of DDBA-intercalated clay minerals.

This study reports a leaching process along with a novel physical pretreatment technique to remove iron impurities from kaolin using oxalic acid. A detailed examination of the physical properties of the minerals confirmed that almost none of the leaching-resistant iron oxides, specifically hematite, was completely interlocked with the clay minerals. Accordingly, a pre-agitating technique followed by high-pressure washing of the sample on a 600 μm sieve were applied. In this method, by discarding up to 20% of the raw material, >54% of the total iron content of the raw kaolin was removed, and the iron content was reduced from 9.75% in the initial sample to <6.00% in the passing fraction. Application of this pretreatment method rendered the leaching process successful at 97°C using 0.3 M oxalic acid solutions for 1 h under atmospheric pressure. Compared to the leaching of the raw material without pretreatment, which consumed at least 0.5 M oxalic acid over a minimum period of 2 h, the method used was very cost-effective and favourable, reducing the iron content of the product to <1% and producing high-quality kaolin.