The objective of this research was to study the cellulose addition effect on the geopolymerization of heated clay. The clay, composed of illite, plagioclase and kaolinite, was heated at 700°C for 2 h and mixed with cellulose (up to 10 mass%). The mixtures were NaOH-activated, and shaped samples were aged at 83°C for 30 days. The cured samples were investigated by using X-ray diffraction, Fourier-transform infrared spectroscopy and scanning electron microscopy. The influence of the cellulose addition on the mechanical/physical properties was also evaluated. The results showed that zeolite ZK-14, hydrosodalite, sodium carbonate and a geopolymer composed of poly(sialate) units were formed in all cured samples. The relative amounts of zeolite and metakaolin evolved antagonistically, whereas that of illite slightly decreased with increasing cellulose content. Metakaolin and illite were involved in the geopolymerization process. Cellulose addition led to the improvement of the flexural strength of the samples and to porosity reduction. By contrast, water absorption was increased. The positive effect of cellulose on sample performance is explained on the basis of hydrogen bonding between the functional moieties of cellulose and the active sites of sample constituents, namely zeolites, metakaolin, illite and the geopolymer. As a filler, zeolite probably contributed to sample strengthening, and the detrimental impact of Na-carbonate was insignificant. Based on the results obtained, the composites could be used as binders for brick manufacturing or as lightweight mortars.

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.

Clays and clay minerals dissolve over a broad pH range, such as during sediment diagenesis and in a variety of applications, including nuclear waste storage, landfills, and geopolymer binders in the construction industry. The solubility depends on process parameters (pH, temperature, pressure, etc.) and material properties (phase content, clay mineral composition, particle size, etc.). Pretreatments such as calcination or severe grinding change the material properties and could enhance solubility, which is called activation. The aim of the current study was to determine the solubility of three different clay minerals after calcination (metakaolinite, metamontmorillonite, and metaillite) in high molar alkaline solutions (NaOH) up to 10.79 mol/L and pH = 14.73. Furthermore, the solubility of an Al(OH)3 powder in alkaline solution (NaOH) was analyzed, as it can be used to adjust the Si:Al ratio of geopolymer precursors. The residues of the clay minerals after the alkaline treatment were investigated to disclose potential alterations in their phase contents. Based on the results of the thermal and alkaline activation, conclusions about the suitability as geopolymer precursors were made. All clay minerals showed an increase in solubility proportional to the concentration of the alkaline solution. The solubility decreased in the order metakaolinite > metamontmorillonite > metaillite. Thereby, dissolution was incomplete for all three clay minerals (<90%) after 7 days and congruent for metakaolinite and metaillite but incongruent for metamontmorillonite.

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.

As 1:1 dioctahedral clay minerals, kaolinite and halloysite have similar chemical compositions. However, halloysite often possesses a nanotubular structure and special surface reactivity compared to platy kaolinite. The objective of this current work was to determine the effect of the SiO2/Al2O3 ratio on the microstructure and properties of geopolymers derived from two kinds of kaolin: platy kaolinite and nanotubular halloysite. The chemical structures and compositions of the geopolymers obtained were characterized through X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR), whereas the microstructural analysis was performed by scanning electron microscopy (SEM), the Brunauer–Emmett–Teller (BET) method, and N2 physisorption analysis. The results indicated that calcined halloysite showed greater geopolymerization reactivity than calcined kaolinite. In addition, the mechanical properties of the clay-based geopolymers depended not only on the SiO2/Al2O3 ratio but also on the morphology of the clay. Crystalline zeolite A and geopolymer were produced after alkali-activation of kaolin with a SiO2/Al2O3 ratio of 2.5; these products possessed porous and heterogeneous microstructures having poor compressive strength. As SiO2/Al2O3 ratios increased to >2.5, geopolymers with compact microstructure and high compressive strength were produced after alkali-activation of kaolin. Notably, at a given condition, halloysite-based geopolymers exhibited greater early compressive strength, more compactness, and more homogeneous microstructure than kaolinite-based geopolymers. This can be attributed to the nanotubular microstructure of halloysite, which can release more Si and Al during alkali activation than platy kaolinite. These results indicated that the various morphologies and microstructures among clays have significant impact on the microstructure and compressive strength of geopolymers.

Fire resistance performance is one of the most important requirements in geological storage conditions in order to improve the resistance of storage packages to high thermal constraints (in the case of a fire for example). With the need to develop new fire-resistant materials, the aim of the present study was to develop fire-resistant geopolymer binders based on Callovo-Oxfordian (COx) argillite. Two types of kaolin with different degrees of purity were mixed with argillite in various proportions. These mixtures were calcined at 600 or 750°C. In order to assess the fire resistance of activated materials, thermal treatment at 1000°C was performed. The compressive strength and mineralogical composition of the samples were investigated before and after heat treatment. The results showed that the addition of argillite improved significantly the thermomechanical properties of kaolin-based geopolymers containing impurities, especially the mixture containing 67% argillite and calcined at 750°C. This phenomenon was not observed for the pure-kaolin geopolymer. Improvement of fire resistance was due to the formation in situ of leucite and zeolite-type phases (KAlSi2O6 and KAlSiO4) and of wollastonite (CaSiO3) at high temperature, which is linked to the Ca available in the raw materials.

Geopolymers can be transformed into zeolites under certain synthesis conditions. However, zeolite formation is not frequently reported in KOH-activated geopolymers. This study attempted to explore zeolite synthesis through geopolymerization for a curing time of 24 h using mixed NaOH/KOH alkaline solution as an activator, and then applying the geopolymer-supported zeolites to immobilize Cd(II) in paddy soil. The K2O/M2O–H2O/SiO2 and K2O/M2O–OH–/SiO2 binary zeolite crystallization phase diagrams were obtained. Zeolite A, faujasite and sodalite formed at lower K2O/M2O molar ratios (0–0.2), ferrierite formation was favoured at a K2O/M2O molar ratio of 0.2–0.4 and zeolite K-I and zeolite F-K (both K-zeolites) were observed at a K2O/M2O molar ratio of 0.6. The geopolymer-supported zeolites had micropores and mesopores and specific surface area values of 44.2–74.8 m2 g–1. The material displayed a considerable Cd(II) immobilization efficiency (55.6–58.7% at 4–6 wt.% addition of zeolite).

The aim of this study was to help drive the Tunisian construction industry towards a more sustainable approach given the existence of abundant local raw material deposits that could be exploited for the production of low-CO2 binders. Various clay sediments from the Kebili region (southern Tunisia) were characterized by chemical analysis, X-ray diffraction, thermal analysis and geotechnical tests to determine their suitability for the preparation of geopolymer binders. The clays consist of illite and kaolinite with other accessory minerals. To test the possibility of using these materials as precursors for the production of low-CO2 and low-cost geopolymers, the raw samples were calcined and activated by addition of solid sodium silicate. Compressive strength tests performed on four alkali-activated clays show that promising mechanical performance may be achieved, with mechanical strength values as high as 25 MPa after 7 days, depending on the clay composition. The mechanical strength is related to the SiO2:Al2O3 and Al2O3:(NaO2 + K2O) ratios. Careful selection of the raw materials is, therefore, an essential step in the exploitation of clay deposits to be used for the production of ecological materials such as geopolymers.

Natural zeolite (clinoptilolite)-based geopolymers were synthesized using alkali aluminate solution, including aluminate anodizing waste solution. The effect of calcination of the clinoptilolite sample at 900°C was investigated. The samples were studied by powder X-ray diffraction, thermal analysis, scanning electron microscopy and N2-specific surface area. The alkali aluminate-activated clinoptilolite geopolymers are characterized by satisfactory compressive strength (up to 37 MPa), low density and acceptable shrinkage. The clinoptilolite geopolymer obtained contains an X-ray amorphous phase and newly formed phillipsite and zeolite NaP. The presence of zeolite phases in the geopolymer agglomerate could be beneficial in products with specific qualities and properties, such as ion exchange, passive cooling, antimicrobial activity, etc.

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.

Vanadium-beard bone coal is one of important vanadium resources in China. to extract vanadium tailings from Stone coal is prduced after extracted vanadium from stone coal through the roasting, leaching and other processes. About 120-150 tons of tailings will be produced in extracting 1 ton of vanadium pentoxide. A lot of tailings that are willfully piled up have caused serious environmental pollution and wasting of resources; it is therefore necessary to realize its resource utilization. This study increases the activity of vanadium tailings by means of alkali fusion, and then uses different alkali activators to react with vanadium tailings so that geopolymer with high value added is produced. Sample of geopolymer is acquired from mixture containing vanadium tailings, alkali activators, water and a little sodium aluminate through compression-molding process under 20MPa pressure. After cured in room temperature for three days, the maximum compressive strength of the sample can reach 36.2MPa. XRD analysis indicates: quartz, the major crystal phase in vanadium tailings is decomposed and the activity of vanadium tailings is heightened. FTIR and SEM analyses show: structural change having important impact on the mechanical strength of geopolymer occurred during the process of vanadium tailings generating geopolymer.