The reaction of kaolin with NaCl was followed by dynamic thermal analysis and mass spectrometry under N2, CO2, and air atmospheres and in a 10−5-torr vacuum. The weight loss was a function of the atmosphere used and, according to mass spectrometry, was due to the evolution of H2O, HCl, and very small amounts of H2. HCl was formed only after the release of 85% of the hydroxyl content of the kaolin. When the clay was pretreated with saturated salt solution, H2O and HCl evolved in more or less the same temperature range, indicating that only some of the OH groups reacted with the chloride ion. High-temperature X-ray powder diffraction patterns showed that the sodium ion reacted with the noncrystalline metakaolin to give NaAlSiO4. Chemical analysis showed that the reaction of kaolinite and sodium chloride started below 400°C. The rate of the reaction increased at higher water vapor concentration. From mass spectrometric data, the NaCl-treated kaolin appeared to adsorb CO2. Desorption at several distinct temperatures suggests that CO2 was adsorbed by different parts of the structure, i.e., holes and channels. X-ray powder diffraction and infrared absorption data indicate that the kaolinite structure persisted even after it had been heated with NaCl in a CO2 atmosphere to as high as 800°C.

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.

Kaolins and clays are important raw materials for production of supplementary cementitious materials and geopolymer precursors through thermal activation by calcination beyond dehydroxylation (DHX). Both types of clay contain different polytypes and disordered structures of kaolinite but little is known about the impact of the layer stacking of dioctahedral 1:1 layer silicates on optimum thermal activation conditions and following reactivity with alkaline solutions. The objective of the present study was to improve understanding of the impact of layer stacking in dioctahedral 1:1 layer silicates on the thermal activation by investigating the atomic structure after dehydroxylation. Heating experiments by simultaneous thermal analysis (STA) followed by characterization of the dehydroxylated materials by nuclear magnetic resonance spectroscopy (NMR) and scanning electron microscopy (SEM) together with first-principles calculations were performed. Density functional theory (DFT) was utilized for correlation of geometry-optimized structures to thermodynamic stability. The resulting volumes of unit cells were compared with data from dilatometry studies. The local structure changes were correlated with experimental results of increasing DHX temperature in the following order: disordered kaolinite, kaolinite, and dickite, whereupon dickite showed two dehydroxylation steps. Intermediate structures were found that were thermodynamically stable and partially dehydroxylated to a degree of DHX of 75% for kaolinite, 25% for disordered kaolinite, and 50% for dickite. These thermodynamically stable, partially dehydroxylated intermediates contained AlV while metakaolinite and metadickite contained only AlIV with a strongly distorted coordination shell. These results indicate strongly the necessity for characterization of the structure of dioctahedral 1:1 layer silicates in kaolins and clays as a key parameter to predict optimized calcination conditions and resulting reactivity.

Mineral chabazite has shown the unusual ability to surface template nanometal particles, especially Ag. A chabazite analog was synthesized from delaminated metakaolin. The chabazite formed retained the platy morphology of the base clay. This morphology is ideal for displaying surface-supported nanometal particles. The synthetic chabazite analog demonstrated the ability to form and support large concentrations of Ag nanoparticles, as observed in the related natural mineral. Due to greater Al content, the synthetic chabazite manifests significantly improved capacity for the formation of such Ag nanoparticles. As in the case of the mineral chabazite, surface Ag nanoparticles of high uniformity were observed in the range of 5–6 nm.

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.

This study examines the leaching of aluminium from calcined kaolin (metakaolin) with citric, oxalic and lactic acid and binary combinations of these organic acids. The investigated parameters were the pulp density, acid concentration, pH, agitation speed, temperature and contact time. The kinetics of aluminium dissolution from metakaolin in binary organic acid mixtures were determined and scanning electron microscopy examination and energy-dispersive spectrometry mapping of Si and Al of untreated kaolin and residual solids were also carried out. Aluminium dissolution increased with temperature, time, acid concentration, pulp density and acidity. At maximum dissolution, citric–oxalic (1:4 w/w) and lactic–oxalic (1:4 w/w) mixtures dissolved 77% and 78% aluminium, respectively, from metakaolin in 11 h. The activation energy ranged from 57.8 to 74.6 kJ/mol. The most effective parameter in the dissolution of aluminium was the temperature, indicating that the reaction was not diffusion-controlled. It was concluded on the basis of the activation energy values and the sensitivity of the reaction to temperature that the dissolution was under chemical-reaction control.

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 effect of heating, to temperatures between 400 and 1200ºC, on the dehydroxylation of kaolin and the pozzolanic activity of the resulting amorphous material were determined by a variety of analytical techniques. Mixtures of concrete containing variable amounts of kaolin calcined at 700ºC were analysed and the results compared with those for concrete samples containing two different types of imported metakaolin. As shown in this work, Colombian kaolin can be used effectively as a raw material to obtain a highly active product (metakaolin). The optimum heating temperature for the kaolin is between 700 and 800ºC.

Lime-based mortars with admixtures of metakaolin (10, 20 and 30 wt.%) and fine sepiolite (5 wt.%) were prepared with the aim of facilitating their use as repair mortars in low-humidity conditions. The mechanical properties and the dynamic modulus of elasticity were studied after 28, 90 and 180 days of curing. With an increasing amount of metakaolin in lime mortars, improved mechanical strength was observed mainly after 90 days. Addition of fine sepiolite, due to its adsorption properties for storing water for later supply to the mortar system and its microfibrous morphology, led to an improvement of compressive and flexural strength of blended air lime/air lime-metakaolin mortars, espec ially at later ages of curing. Incorporation of fine sepiolite into air lime-metakaolin mortars resulted in comprehensive densification of the core of the mortars. Air lime mortar containing 5 wt.% of fine sepiolite and 20 wt.% of metakaolin appears to be an optimal admixture.

Turkey has a long tradition (starting with prehistoric civilizations) and experience in exploring for raw clay materials and processing them into ceramic products. Many of these products, such as tiles and sanitary ware, are manufactured for domestic and export markets. Kaolin is one of the raw materials of major importance for the ceramic and paper industry, as well as for a number of auxiliary applications. There is ongoing interest in applying kaolin in the construction industry as a raw material in the production of white cement clinker and as an artificial pozzolanic additive for concrete (in the form of metakaolin). This report presents results related to search, assessment and evaluation of available resources for advanced cement and concrete additives.

Metakaolins formed by total dehydroxylation of kaolinite, dickite and nacrite were hydrothermally treated at 240°C, for 2, 21 or 182 days, at initial pH = 5– 6 or 1. Kaolinite was the only mineral of the kaolin subgroup crystallized in these treatments. Kaolinite is less ordered for pH = 4– 6 than for pH = 1. This can be attributed to the influence of specific chemical, morphological, and/or crystalline properties of the metakaolins. Two different processes of kaolinite formation and crystal growth must be involved depending on the pH and metakaolin. The first process implies the dissolution of the metakaolin and crystallization of thin prismatic or dendritic kaolinite particles which curl, probably due to surface tension. The second process implies the rapid formation of small pseudohexagonal kaolinite particles which would aggregate and coalesce to form bigger particles.

Alkaline activation involves a reaction between aluminium silicates and compounds with alkalis or alkaline-earth elements in a caustic environment and under certain thermal and pressure conditions. It has been used in the production of non-structural building materials and in so-called ‘green’ concrete, as products display high mechanical strength, low chemical reactivity and high resistance to fire. Green concrete could be an eco-efficient alternative to concrete made using ordinary Portland cement (OPC), reducing CO2 emissions substantially. The main goal of this work is to test common clays, glass cullet and other industrial wastes as an alternative to the commonly used binders (metakaolin or fly ash) in geopolymers. Optimized formulations show interesting mechanical strength (approaching 20 MPa) after just 48 h of curing. The addition of F-sand as aggregate minimizes the shrinkage upon curing and the amount of activator required, and increases the density/degree of compaction of the bodies, thus improving their mechanical resistance within certain limits. Curing in ambient conditions also has a beneficial affect on the mechanical strength.

The present work deals with the hydrothermal synthesis of Na zeolites (Na-A, Na-X and Na-P) and hydroxysodalite using kaolinite calcined at 650°C as starting material. The focus was on definition of the most favourable conditions for the synthesis of zeolite Na-A and Na-X from metakaolin in order to economize on both energy (i.e. synthesis temperatures) and reaction time and to enlarge the field of pure and isolated synthesized phases. Metakaolin was mixed with calculated amounts of NaOH solution and sodium silicate and five sets of experiments were carried out at ambient pressure and 68±0.1°C varying the SiO2/Al2O3 ratio from 2.2 to 7. Optimal conditions for crystallization of Na-A zeolite from kaolinite were reached with a SiO2/Al2O3 ratio of 2.2 plus 4 M NaOH without adding sodium silicate; transformation into hydroxysodalite develops after ∼8 h. For SiO2/Al2O3 ratios between 4 and 7, crystallization of the separate Na-X zeolite phase could be achieved and transformation into Na-P and hydroxysodalite occurred after 382 h and 190 h, respectively. For SiO2/Al2O3 ratios between 5 and 6, transformation of metakaolin into Na-X plus Na-A, hydroxysodalite and Na-P occurred, and the field within which Na-A and Na-X zeolite exists overlapped that of the other zeolites.

The products of synthesis were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR) and thermal analyses (TG-DTG-DTA).

Obtaining pure Na-A and Na-X zeolite from kaolinite treated at low metakaolinitization temperature (650°C) and low hydrothermal synthesis temperature (68°C) represents a considerable economic advantage in terms of both energy and time.

This paper describes a study of the hydraulic reactions between metakaolin (MK) and air lime using electrochemical impedance spectroscopy (EIS) and nuclear magnetic resonance spectroscopy (NMR). Tests were carried out at 20, 25 and 30°C on lime-MK pastes with 10:1 w/w ratio. Tests over 28 days allowed identification of relevant changes in the EIS signals and characterization of pastes using thermal analysis (TGA/DSC), scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP) and uni-axial compressive tests. Tests over shorter periods of time (up to 42 h) allowed more detailed studies of the hydraulic phases formed at the very beginning of the reactions.

Results of thermal analyses demonstrate formation of hydraulic compounds such as CSH, C4AH13 and C3ASH6 and show their evolution over time. MIP analysis demonstrates changes in pore size distribution related to the formation and trasformation of hydraulic phases. Variations of impedance response with time are shown to be associated with reaction kinetics. Changes in the NMR signal within the first 42 h of reaction are shown to be associated with the dissolution of calcium hydroxide in the pore solution. Overall, this paper demonstrates the importance of NMR in the study of hydraulic reactions in lime based materials and the ability of EIS to detect the formation of hydraulic compounds and the end of the calcium hydroxide dissolution process.

The kinetics of dissolution of Amazonian metakaolin in hydrochloric acid (HCl) was studied using the ‘Shrinking Core Model’ for spherical and ‘flat plate’ particles of constant size. The Amazonian kaolin was calcined at 700°C for 2 h. The calcined samples (metakaolins) were leached in an HCl solution with 5% excess at 70, 80 and 95 ± 3°C for 3 h. Samples were collected every 15 min and subjected to Al analysis by the EDTA titrimetric method. Experimental data showed that the spherical morphology produced a better fit with respect to the regression coefficients. The activation energy of the reaction was 90.6 kJ/mol. The chemical process is a first-order leaching reaction. The results of the present study are consistent with those from previous research on this topic, which used HCl with an excess of >90%.