Conventional superplasticizers based on polycarboxylate ether (PCE) show an intolerance to clay minerals due to intercalation of their polyethylene glycol (PEG) side chains into the interlayers of the clay mineral. An intolerance to very basic media is also known. This makes PCE an unsuitable choice as a superplasticizer for geopolymers. Bio-based superplasticizers derived from starch showed comparable effects to PCE in a cementitious system. The aim of the present study was to determine if starch superplasticizers (SSPs) could be a suitable additive for geopolymers by carrying out basic investigations with respect to slump, hardening, compressive and flexural strength, shrinkage, and porosity. Four SSPs were synthesized, differing in charge polarity and specific charge density. Two conventional PCE superplasticizers, differing in terms of molecular structure, were also included in this study. The results revealed that SSPs improved the slump of a metakaolin-based geopolymer (MK-geopolymer) mortar while the PCE investigated showed no improvement. The impact of superplasticizers on early hardening (up to 72 h) was negligible. Less linear shrinkage over the course of 56 days was seen for all samples in comparison with the reference. Compressive strengths of SSP specimens tested after 7 and 28 days of curing were comparable to the reference, while PCE led to a decline. The SSPs had a small impact on porosity with a shift to the formation of more gel pores while PCE caused an increase in porosity. Throughout this research, SSPs were identified as promising superplasticizers for MK-geopolymer mortar and concrete.

A lustrous appearance and interference-based colors make pearlescent pigments attractive for use in applications such as automotive paints, plastics, consumer electronics, and cosmetics. A combination of interference and absorption in the visible light spectrum improves significantly the hiding power as well as the color strength of pearlescent pigments while potentially extending their color range. The aim of the present study was to introduce synthetic fluorohectorites, having an appreciable diameter (~20 μm) and aspect ratio (~1000), as promising colored cores for pearlescent pigments. Fluorohectorites can adopt a variety of colors by ion-exchange reaction with cationic organic dyes of high absorption coefficient. Unlike related dye-exchanged natural montmorillonite clays, which undergo acid activation accompanied by release of dye at low pH, as is required for subsequent coating with TiO2 in an environment with low pH and elevated temperature, no leaching was observed with dye-exchanged synthetic fluorohectorites ([Na0.5]int.[Mg2.5Li0.5]oct.[Si4]tet.O10F2). Due to its significantly greater layer charge, more organic dye molecules were adsorbed per volume of the fluorohectorite than for montmorillonite. Consequently, the free volume available in the interlayer space for H3O+ diffusion was less for synthetic fluorohectorite than for montmorillonite. Acid attack via interlayer space was, therefore, retarded significantly for fluorohectorite. Acid attack from the external edges of synthetic fluorohectorites was in the range of conventionally applied mica pigment core (fluorophlogopite, ([K]int.[Mg3]oct.[AlSi3]tet.O10(F,OH)2) because of the comparable large diameter of the platelets. Montmorillonite, however, occurs with particle diameters typically <200 nm and the much increased relative contribution of edges to the total surface area also makes them more prone to acid attack and concomitant leaching. Aside from leaching stability, the confinement of organic dyes in the interlayer space restricts rotational and vibrational motions, which in turn stabilizes the dyes typically by ~100°C against thermal decomposition as compared to chloride salts of the dyes.

The present study considered the problem of halloysite nanoscroll synthesis by energy modeling of the formation of chrysotile and halloysite particles. The main aim of the study was to reveal an energy preference between scrolled and platy morphologies of the particles. Both hydrosilicates possess the ability to scroll spontaneously but relatively facile hydrothermal synthesis of the nanoscrolls is available only to the former, whereas halloysite forms mainly plates under the same conditions. This issue was investigated by a phenomenological energy model, taking into account: (1) strain energy due to the size difference between metal oxide and silica sheets; (2) surface-energy difference on the opposite sides of the layer; and (3) adhesion energy. Calculations showed that the halloysite layer had a significant scrolling potential due to the first energy component, but the surface-energy difference acted in the opposite direction and tried to unbend the layer. In contrast, these two actions were co-directional in chrysotile layers. In both cases, the formation of multi-layered plates became more energy favorable when the specific surface energy of the edges decreased. In the range 0.5–3 J/m2 for the specific surface energy, only halloysite layers showed an energy preference for platy particles over nanoscrolls, especially at small layer sizes. Certain processes, such as hydration, could reduce the corresponding specific surface energy value and, as a result, could stabilize the platy morphology of halloysite at the earliest stages of particle growth under hydrothermal conditions.

K-Ar isotopic dating has been applied to alkali-rich nanometer-sized illite separates of bentonites since the late 1990s. In the present study, K-Ar and Rb-Sr isotopic analyses were based on mineralogical determinations and morphological observations of similarly nm-sized separates (<0.02, 0.02–0.05, and 0.05–0.1 μm) depleted in alkalis and recovered from Santonian (85.8–83.5 Ma) bentonites of the Campos Basin located offshore the southeastern Atlantic coast (Rio de Janeiro State, Brazil). On the basis of XRD analyses and geochemical/mineralogical simulations, the size fractions consist essentially of the smectite-rich end-member of the smectite-to-illite trend with no more than 9% authigenic illite layers. High K-Ar values from 42.6 ± 3.2 to 70.2 ± 2.1 Ma confirm the occurrence of detrital illite in one sample at least, the age data being meaningless. A second group of K-Ar values ranges from 15.5 ± 10.7 to 41.3 ± 10.8 Ma, while the smallest (<0.02 and 0.02–0.05 μm) fractions with <0.42% K2O lack detectable radiogenic 40Ar and yield analytically 0 Ma ages. Two samples including that with the detrital illite were leached with dilute acid and the Rb-Sr method was applied to the untreated, leachate, and residual fractions of the different separates. The combined isotopic data suggest that illitization started at ~44 ± 4 Ma when the bentonites were subjected to a temperature of ~60°C. The leachable Sr yielded 87Sr/86Sr ratios of 0.7106–0.7108, which is greater than those of seawater either during deposition or recently, and of the initial ashes. They do not correspond to the chemical signature of pore fluids, but more likely to removals from fragile edges of the illite-smectite layers probably impacted by the rough initial chemical treatment applied to empty the smectite interlayers. Illitization was either a side effect of a major contemporaneous smectitization or an independent process that occurred later, in the progressively buried bentonite beds. Of variable duration, it was probably dependent on burial-induced temperature increase in the bentonites, which monitored the fixation of K in the smectite layering with or without a changing fluid chemistry. On the basis of the combined K-Ar and Rb-Sr isotopic data, illitization lasted either until ~15 Ma or even 0 Ma for some of the finest size fractions.

Because they are so widespread, the use of saponites is significant in many industries. The modification of saponite-rich clay minerals is known to improve their existing characteristics and may provide new functional properties. The objective of the present paper was to characterize the effects of adding nanosized graphene-like molybdenum (Mo) and tungsten (W) sulfides on the textural and surface characteristics of composites based on native saponite and saponite pre-modified with nanoscale magnetite. The textural characteristics were investigated by the nitrogen adsorption-desorption method and scanning electron microscopy. The total acidity, Hammett Brönsted centers, and Quasi-Equilibrium Thermo Desorption (QE-TD) Lewis centers were characteristics used to probe the acid-base properties of the modified composites. In all cases, modification proved to have a significant effect on both the surface and textural properties of the clay matrix. Modification of the native saponite by graphene-like Mo and W sulfides resulted in a decrease in the specific surface area, except a slight increase in the surface area of the magnetite-containing saponite was observed. Analysis of the acid-base characteristics of native and magnetite-modified saponite (MMS) indicated the ability of modified MoS2 and WS2 additives to alter the acid-base state of the surface. The addition of graphene-like Mo and W sulfides increased the total acidity of native and MMS, with MoS2 modification being more promising because, in almost all the samples, saponite composite materials increased the number of both Brönsted and Lewis active centers compared with WS2, which was determined by the corresponding methods. The acid-base characteristics of the saponite-containing samples, which were studied in an aqueous medium by various methods, are in good correlation with each other, and are consistent with the sorption activity of cationic and anionic dyes.

Ion-exchange modeling is one of the most widely used methods to predict ion adsorption data on clay minerals. The model parameters (e.g. number of adsorption sites and the cation adsorption capacity of each site) are optimized normally by curve fitting experimental data, which does not definitively identify the local environment of the adsorption sites. A new approach for constructing an ion-exchange model was pursued, whereby some of the parameters needed were obtained independently, resulting in fewer parameters being based on data-curve fitting. Specifically, a reversed modeling approach was taken in which the number of types of sites used by the model was based on a previous first-principles Density Functional Theory study, and the relative distribution of these sites was based on the clay’s chemical composition. To simplify the ion-exchange reactions involved, montmorillonite was Na-saturated to produce a well-controlled Na-montmorillonite (NaMnt) adsorbent. Ion adsorption data on NaMnt were collected from batch experiments over a wide range of pH, Cs+ concentrations, and in the presence of coexisting cations. Ion-exchange models were developed and optimized to predict these cation adsorption data on NaMnt. The maximum amount of adsorption of monovalent cations on NaMnt was obtained from the plateau of the adsorption envelope data at high pH. The remaining equilibrium constants (pK) were optimized by curve fitting the edges of the adsorption envelope data. The resultant three-site ion-exchange model was able to predict the retention of Li+, Na+, K+, and Cs+ very well as a function of pH. The model was then tested on adsorption envelopes of various combinations of these cations, and on Cs+ adsorption isotherms at three different pH values. The pK values were constant for all assays. The interlayer spacing of NaMnt was also analyzed to investigate its relation with cation adsorption strength. An X-ray diffraction study of the samples showed that the measured d001 values for these cations were consistent with their adsorption pK values. The Cs+ cation showed a strong ability to collapse the interlayer region of montmorillonite. In the presence of multiple competing cations, the broadening and presence of multiple d001 XRD peaks suggested that the cations in the interlayers may be segregated.

Alkaline solutions have significant effects on the mineral composition and on the microstructure of bentonite; in relevant geoenvironmental engineering applications, therefore, the properties of bentonite buffer materials must be taken into consideration in the presence of alkaline solutions. The objective of the present study was to determine the effect of alkaline conditions on the swelling of bentonite mixed with sand. Bentonite-sand mixtures were soaked in a NaOH solution and allowed to react over prescribed periods of 6, 12, and 24 months. Swelling deformation tests were conducted on the alkali-treated bentonite-sand mixtures; the swelling of the mixtures decreased significantly with increased reaction time. The fractal ec-σ relationship (ec is void ratio of bentonite, σ is vertical stress) was employed to express the swelling characteristics of the alkali-treated mixtures, wherein the swelling coefficient decreased as the bentonite content was reduced. Dissolution traces over the clay surfaces degraded the microstructural phase, thereby slightly increasing the fractal dimension. At higher dosages of bentonite, the swelling of bentonite-sand mixtures always followed a similar ec-σ relationship as that found for bentonite alone. On the contrary, in the mixtures with a small bentonite content that surpassed the designated threshold pressure, the void ratio of clay in the mixtures deviated from the ec-σ curve due to the appearance of the sand skeleton. The bentonite content for a particular bentonite-sand mixture at which deviation from the ec-σ curve began was ~50%. This deviation was almost negligible at 50% initial bentonite content in the bentonite-sand mixtures; after treatment with NaOH solution, however, a pronounced deviation in the ec-σ curve was observed which was caused mainly by the decrease in the bentonite percentage. Finally, the vertical pressure threshold was also estimated using the ec-σ relation for bentonite-sand mixtures with small bentonite contents over a range of various alkaline solution reaction times.

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.

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.

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.