Infrared analyses of clay mineral samples are usually performed by transmission techniques. While transmission measurements are easy and inexpensive, the sample preparation plays a critical role in the quality of the data. Alternatively, attenuated total reflection (ATR) provides a powerful and often simpler analysis method. However, the ATR spectra reveal significant differences when compared to transmission spectra sometimes leading to confusion in the interpretations. Indeed, optical effects play a prominent role in the ATR spectral profile and their identification is mandatory for obtaining quantitative information regarding molecular/particle orientation or film thickness. The objective of the present study was to perform exact spectral simulations of montmorillonite films by making use of optical theory, including the determination of the anisotropic optical constants from the experimental reflectance spectra by Kramers-Kronig (KK) transformation. This methodology was used: (1) to choose the appropriate optical conditions for advanced and reliable characterization of clay minerals; (2) to extract quantitative information such as the estimation of the film thickness; and (3) to discriminate optical phenomena (optical interferences) from chemical/structural features of the sample.

Despite the numerous studies on geomaterials in Tunisia, quite a few clay varieties are not yet well defined. In fact no detailed geological, mineralogical, or geochemical characterizations of Tunisian palygorskite deposits have been carried out to date. The purpose of the present work was to study the continental Eocene clay deposit at the southern end of the Tunisian North axis, between Jebel Rheouis and Jebel Boudinar, to determine its potential as a clay reserve. Nine samples were collected from the Cherahil formation representing the lower, middle, and upper levels. The analytical results obtained using several techniques (chemical analysis, X-ray diffraction, specific surface area measurements, Fourier-Transform infrared spectroscopy, scanning electron microscopy) revealed that palygorskite is the dominant clay mineral. Dolomite and quartz are present as associated minerals. Chemical analysis of sample AR9 showed a smaller potassium content compared to other samples. Sample AR9 consists essentially of dolomite associated with palygorskite and quartz. Other samples (AR5, AR6, and AR7) collected from the same Cherahil formation contained palygorskite as the main phyllosilicate mineral (80%). The important reserve of palygorskite was found in the middle of the Cherahil formation. Dolomite and quartz associated with palygorskite reduced the length and crystallinity of the fibrous clay morphology. Analysis by scanning electron microscopy proved that the crystallinity of palygorskite was less in the lower and upper parts of the Cherahil formation. The central palygorskite deposit may be of interest for pharmaceutical (adsorbent drug) and other applications. The two other levels of Cherahil formation are mineralogically heterogeneous and considered economically less important than the middle level, which is rich in palygorskite.

The present study provides an example of the accurate identification of polytypes of trioctahedral 1:1 layered silicates from single-crystal X-ray diffraction data collected with the aid of a four-circle diffractometer equipped with an area detector. Single crystals of the mineral cronstedtite from the Nagybörzsöny gold ore deposit, northern Hungary, were studied. The chemical composition of some crystals was determined by electron probe microanalysis (EPMA). The precession-like images of the reciprocal space (RS) sections created by the diffractometer software and presented in the study were used to determine the OD (ordered-disordered) subfamilies (Bailey’s groups A, B, C, D) and particular polytypes. With one exception, all crystals studied belong to subfamily A. The rare polytype 1M, a = 5.51, b = 9.54, c = 7.33 Å, β = 104.5°, space group Cm is relatively abundant in this occurrence. Another polytype 3T, a = 5.51, c = 21.32 Å, space group P31 was also found. Both polytypes occur separately or in mixed, mostly 1M dominant crystals. Some 1M polytype crystals are twinned by order 3 reticular merohedry with a 120° rotation along the chex axis as the twin operation. A rare 1M+3T mixed crystal with 1M part twinned also contains a small amount of subfamily C. A possible presence of the most common 1T polytype of this subfamily cannot be confirmed because of overlap of the characteristic reflections with those of 3T. Several completely disordered crystals produced diffuse streaks instead of discrete characteristic reflections on the RS sections. The EPMA revealed Fe, Si, traces of Mg, Al, S, and Cl. One black crystal originally considered to be cronstedtite was identified as (111) twinned sphalerite. Some crystals of cronstedtite are covered partially by a honey-brown crust or small crystals of siderite.

Bisphenol A (BPA), an endocrine disrupting compound, is of concern because of its wide presence throughout the environment and its harmful effects. The present study aimed to prepare an eco-friendly, low-cost, and efficient adsorbent for removal of BPA from wastewater. A natural Tunisian clay was used as a raw material. First, the clay was purified and then modified with hexadecyltrimethylammonium bromide (HDTMA) using microwave heating. The optimal conditions for clay modification were as follows: activation ratio = 0.3:(g/g), solid/liquid ratio = 5%, and microwave heating condition (2:min, 100:W). The purified and modified clays, abbreviated as HP and HMH, respectively, were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and nitrogen adsorption/desorption analysis (BET). Adsorption tests were conducted in a batch reactor process under various conditions. The tests showed that the BET specific surface area of HMH is considerably smaller than that of HP, whereas the basal spacing increased from 14.99 to 22.07 Å after modification, indicating the success of HP organophilization. The adsorption of BPA onto HMH was not affected by the pH of solution between 2 and 10 and only slightly by temperature variation from 23 to 50°C, but was affected significantly by the initial concentration of BPA, contact time, and organo-clay dose. At equilibrium, the data obtained were fitted to Langmuir and Freundlich models. The best fit was obtained by the Langmuir model with a maximum monolayer adsorption capacity of 217.39 mg/g at 23°C. The thermodynamic study suggested that the removal of BPA by HMH was spontaneous (ΔG < 0), exothermic (ΔH < 0), and favorable. The present study demonstrated that HMH synthesized from an abundant and cheap natural clay could be used successfully as a low-cost adsorbent for the removal of BPA from wastewater.

Loess is a collapsible soil; when it collapses, it can cause significant damage to structures built on it. Improvement in the stability and strength performance of loess is necessary to meet engineering needs. In the present study, the effects on the physical-chemical and rheological characteristics of Ghardaïa loess of adding bentonite and lime (southern Algeria) were examined. Rheological characterization of suspensions was implemented to assess the mechanical sensitivity of the bonds and the structural inter-particle resistance to both the chemical effect and mechanical impact. By analyzing the viscosity results and the evolution of the rheological parameters, the improvements needed in terms of the resistance characteristics of the loess-bentonite and loess-lime mixtures were evaluated and confirmed. The loess physical sensitivity was examined through grain-size distribution and plasticity properties. The pH and electrical conductivity of the mixtures were also used to explore structural modifications. Physical test results showed that introduction of the additives changed the loess texture and improved the plasticity of mixtures. Chemical examination (via change in pH and electrical conductivity) revealed the structural changes in the mixtures studied. Rheological test results showed that increasing concentrations of bentonite and lime improves the mechanical strength and increased the yield stress, consistency, and viscosity of the suspensions. The creation of cement interactions between mixture particles explained the increase in those parameters. Hydration, agglomeration, and inter-particle flocculation induced by the additives promoted these interactions. The experimental results led to the conclusion that bentonite and lime may represent an effective means to improve the performance in terms of preventing loess collapse and to increase its resistance to mechanical impact. The results presented in the present study may provide a geotechnical and rheological working database for the control and treatment of loess collapse and landslides in the region under study. Technical data related to loess may, therefore, be beneficial in terms of civil engineering, public works, hydraulics, and the manufacture of construction materials.

Soil–alkali interaction leads to abnormal soil behavior due to significant changes in mineralogy and morphology. The effect of alkali on the swelling behavior of natural clays has been explored in recent years, but the swelling behavior of alkali-transformed clay minerals is still unclear. The objective of the current study was to investigate the effect of alkali concentration on swelling characteristics of natural and alkali-transformed kaolinitic clays. The study was complemented further with micro-level investigations. Red earth and kaolin, which are regarded as non-swelling kaolinitic clays, were utilized. The results showed that alkalis induced greater swelling in natural clays than in alkali-transformed clays. The results revealed further that alkali-transformed clays exhibited decreases in swelling when exposed to increased alkali concentrations. Moreover, the degree of transformation played an important role in the swelling behavior of alkali-transformed kaolinitic clays when inundated with water and with various alkali concentrations. These variations may be attributed to the different extents of mineralogical and microstructural changes caused by alkali treatment.

The stability, dispersion, and rheological properties of clay suspensions are important in the process of drilling. Organic clays were obtained traditionally by cation exchange, which is thermally unstable due to weak electrostatic interaction between the cationic surfactant and clay minerals. The purpose of the present study was to yield a stable and well dispersed organic bentonite (OBent) as a rheological additive for oil-based drilling mud. The co-modified method was used to modify bentonite by a cationic surfactant (cetyltrimethoxyammonium bromide: CTAB) and a silane coupling agent (hexadecyltrimethoxysilane: HDTMS). Firstly, the basal spacing of bentonite was enlarged by intercalation of CTAB, and the thermal stability of bentonite was improved by covalent bonds of HDTMS onto the bentonite platelets. The as-prepared OBent was characterized by infrared analysis, X-ray diffraction analysis, thermogravimetric analysis, and scanning electron microscopy. The hydrophobicity, solubility, viscosity, and tribological performance of the OBent were also recorded. The test results showed that the hydrophobicity of the co-modified bentonite was improved significantly, and was greater than that of bentonite modified with single surfactant CTAB or HDTMS. The bentonite modified by the surfactant together with the silane coupling agent had stable rheology and a lower coefficient of friction than the single surfactant-modified bentonite because more HDTMS entered into the interlayer spaces and formed chemical bonds at the inner surface of platelets.

The conversion of CO2 into carbon feedstock via CO2 hydrogenation to methane requires a stable catalyst for reaction at high temperatures. Zeolite NaY (abbreviated hereafter as NaY) synthesized from naturally occurring kaolin provides a stable support for Ni nanoparticles. Kaolin can be further dealuminated using sulfuric acid to reduce the Si/Al ratio, but the presence of the remaining sulfur is detrimental to the formation of NaY. The objective of the present study was to synthesize NaY from dealuminated metakaolin, using a method that minimizes the detrimental effects of sulfur, and to investigate the effect of its activity on CO2 methanation. Kaolin from Bangka Belitung, Indonesia, was calcined at 720°C for 4 h to form metakaolin (M) and subsequently treated with sulfuric acid to form dealuminated metakaolin (DM). Excess sulfur was removed by washing with deionized water at 80°C. Zeolite NaY was then synthesized from the M and DM via a hydrothermal method; the relationship between morphology, structural properties, and the catalytic activity of NaY was determined for CO2 methanation at 200–500°C. The presence of excess sulfur following dealumination of metakaolin produced NaY with small surface area and porosity. After Ni impregnation, the synthesized NaY exhibited significant catalytic activity and stability for the reaction at 250–500°C. Analysis by scanning electron microscopy and high-resolution transmission electron microscopy showed the formation of well-defined octahedral structures and large surface areas of ~500 m2/g when NaY was synthesized using DM. Catalytic activity indicated significant conversion of CO2 (67%) and CH4 selectivity (94%) of Ni/NaY from DM in contrast to only 47% of CO2 conversion with 77% of CH4 selectivity for Ni/NaY synthesized from M. Dealuminated metakaolin also produced robust NaY, which indicated no deactivation at 500°C. The combination of well-defined crystallite structures, large surface area, and small Al contents in NaY synthesized from DM helped in CO2 conversion and CH4 selectivity for the reaction at 200–500°C.

The formation conditions and stability fields of Fe-serpentines are still poorly understood in both terrestrial (natural or anthropic) and extraterrestrial environments. Knowledge of the effects of physical-chemical parameters on compositional and structural features of Fe-serpentines is lacking, and only a few thermodynamic parameters of these minerals are available in the literature. To fill these gaps, the synthesis of these minerals, while controlling all the physicochemical experimental parameters, was undertaken. Two hydrothermal syntheses were carried out at 90°C to investigate the effect of two different starting mineralogical mixtures on the nature of Fe-serpentines. The run products were identified by several analytical techniques (powder X-ray diffraction, transmission, and scanning electron microscopy). Berthierine crystals were synthesized from a starting mixture of kaolinite and metal iron. The berthierines synthesized show different morphologies and iron contents (~3–38 at.%). From a starting mineralogical mixture composed of quartz and metal iron, cronstedtite crystallizes. Most of the crystals are 1M polytypes. Magnetite is always associated with both berthierine and cronstedtite. Lepidocrocite was observed only in the experiment with kaolinite. These experimental results demonstrated that Fe enrichment in serpentines depends on the silicate precursor (kaolinite or quartz) of the starting mixture. The results are also in agreement with the geochemical equilibrium predicted by thermodynamic modeling, i.e. the formation of berthierine and cronstedtite in association with magnetite at the expense of metal iron and silicates.

Geopolymers have the potential to function as an environmentally friendly substitute for ordinary Portland cement, with up to 80% less CO2 emission during production. The effect is best utilized for geopolymers prepared with amorphous silica instead of waterglass (Na2xSiyO2y+x) to adjust the Si:Al ratio. The reactivity of the precursors with the alkaline activator affects the final mineralogical properties of the binder. The purpose of the present study was to investigate the amount of different phases formed during geopolymerization and to understand the quantitative evolution of carbonation during geopolymer synthesis by determining the solubility of metakaolinite and amorphous SiO2 in NaOH at various concentrations. The solubility was studied by ICP-OES measurements. X-ray diffraction was used for qualitative and quantitative phase analysis of the geopolymers. The solubility of the precursors increased with calcination temperature of metakaolinite, reaction time for amorphous SiO2, and at higher NaOH concentrations. Partial dissolution resulted in free Na+, which is a source for the formation of carbonates in the geopolymers. Thermonatrite occurred prior to trona formation in all samples.