Search Results (46)

Mining activities generate large volumes of tailings with significant environmental impact but also the potential for sustainable reuse in construction materials. This study evaluates the production of ceramic aggregates from mixtures of clay, sand, and iron ore waste subjected to thermal treatment at temperatures ranging from 600 to 1100 °C. The influence of calcination temperature on mineralogical transformations and mechanical integrity was investigated using X-ray diffraction (XRD) and the $\alpha$-Treton parameter, derived from standardized impact resistance testing. The results indicate that the formation of metakaolinite between 700 and 900 °C enhances mechanical resistance, while higher temperatures (>900 °C) lead to structural degradation, followed by partial recovery due to mullite crystallization. The $\alpha$-Treton curve exhibited clear correlation with the phase changes identified by XRD, demonstrating its applicability as a low-cost, sensitive proxy for optimizing thermal activation. A simplified methodology is proposed to optimize the thermal activation of such materials by correlating firing temperature with mineralogical evolution and mechanical integrity, contributing to the development of sustainable ceramic aggregates for pavement applications. Full article

Researchers are exploring eco-friendly alternatives to Portland cement, such as geopolymers, which require reactive aluminosilicate sources. This study evaluated the reactivity of six calcined clays (heated at 700 °C) in the presence of an alkaline solution. The calcined samples from kaolinite quarries in Kamboinsé, Kandarfa, Saaba, Sabcé, Selogo, and Tougou were subjected to chemical and mineralogical analyses. The results indicated a high aluminosilicate content (>50%), with kaolinite reaching up to 83.1%, and an amorphous fraction of up to 31.8%, a key factor influencing reactivity. Geopolymer pastes, prepared using a 12 M NaOH solution and each of these calcined clays, exhibited varying setting times: 24 h for the Saaba clay (the most reactive) compared with 48 h or even up to 7 days for the least reactive. The evaluation of the compressive strength of the geopolymer pastes revealed varying performances depending on the composition of clay. The Saaba clay showed the highest strength (14 MPa), attributed to its high kaolinite content (83.1%) and amorphous phase (31.8%), and thus reactivity. This was followed by Kamboinsé with 10.5 MPa (58.3% kaolinite; 24.3% amorphous phase), Selogo with 4.6 MPa (42.9%; 20.4%), Tougou with 1.4 MPa (44.1%; 20.4%), Kandarfa with only 0.7 MPa (31.3%; 19.2%), and Sabcé, which did not set with 0 MPa (24.1%; 13.7%). A discussion between the chemical and mineralogical compositions of the different clays and the mechanical characteristics of the synthesized pastes highlighted the importance of kaolinite content and its amorphous nature on the reactivity of the geopolymer binders. These findings highlight its potential for applications such as stabilized bricks or geopolymer concrete, offering a low-carbon alternative to traditional materials. Full article

Coal combustion generates significant volumes of ash, a technogenic by-product that poses a serious threat to regional environmental sustainability (environmental chemical contamination and air pollution). This study aims to assess the feasibility of utilizing this type of ash as a raw material component in the fabrication of refractory bricks and to investigate the fundamental properties of the resulting experimental products. Ash was incorporated into the batch composition at concentrations ranging from 10% to 40% by weight, blended with clay and water, then shaped through pressing and subjected to firing at 1000 °C and 1100 °C in an air atmosphere for 2 h. After complete cooling, the samples were subjected to compressive strength testing. Samples containing 40 wt% coal ash exhibited insufficient compressive strength and were therefore excluded from subsequent investigations. For the remaining samples, apparent density, open porosity and slag resistance were determined. The microstructural characterization was performed, and the phase composition of the samples was analyzed. The results revealed that the phase composition of the experimental samples differs significantly from that of the reference sample (ShA-grade chamotte brick in accordance with GOST 390-96, currently used as lining in metallurgical furnaces across the country), exhibiting a higher mullite content and the absence of muscovite. A small amount of kaolinite was detected in the experimental samples even after a 2-h firing process. This observation may be attributed to the effect of kaolinite crystallinity on the transformation process from kaolinite to metakaolinite. The mechanical strength of the experimental samples meets the relevant standards, while slag resistance demonstrated an improvement of approximately 15%. Open porosity was found to decrease in the experimental samples. In addition, a change in the pore size distribution was observed. Notably, the proportion of pores larger than 10,000 nm was significantly reduced. These findings confirm the feasibility of incorporating coal ash as a viable raw material component in the formulation of refractory materials. Full article

Artificially modified adsorbing materials mainly aim to remedy the disadvantages of natural materials as much as possible. Using clay materials such as rectorite, sodium bentonite and metakaolinite (solid waste material) as base materials, hydrothermally modified and unmodified materials were compared. CM-HT and CM (adsorbing materials) were prepared and used to adsorb and purify wastewater containing malachite green (MG) dye, and the two materials were characterized through methods such as BET, FT-IR, SEM and XRD. Results: (1) The optimal conditions for hydrothermal modification of CM-HT were a temperature of 150 °C, a time of 2 h, and a liquid/solid ratio 1:20. (2) Hydrothermal modification greatly increased the adsorptive effect. The measured maximum adsorption capacity of CM-HT for MG reached 290.45 mg/g (56.92% higher than that of CM). The theoretical maximum capacity was 625.15 mg/g (186.15% higher than that of CM). (3) Because Al-OH and Si-O-Al groups were reserved in unmodified clay mineral adsorbing materials with good adsorbing activity, after hydrothermal modification, the crystal structure of the clay became loosened along the direction of the c axis, and the interlayer space increased to partially exchange interlayer metal cations connected to the bottom oxygen, giving CM-HT higher electronegativity and creating more crystal defects and chemically active adsorbing sites for high-performance adsorption. (4) Chemical adsorption was the primary way by which CM-HT adsorbed cationic dye, while physical adsorption caused by developed pore canal was secondary. The adsorption reaction occurred spontaneously. Full article

In the present work, the development of geopolymeric materials with Na or K based on industrial kaolin samples, with variable kaolinite content and alkaline silicates, is studied. XRF, XRD, FTIR and SEM-EDS have been used as characterization techniques. Three ceramic kaolin samples, two from Algeria and one from Charente (France), have been considered. In particular, chemical and mineralogical characterization revealed elements distinct of Si and Al, and the content of pure kaolinite and secondary minerals. Metakaolinite was obtained by grinding and sieving raw kaolin at 80 μm and then by thermal activation at 750 °C for 1 h. This metakaolinite has been used as a base raw material to obtain geopolymers, using for this purpose different formulations of alkaline silicates with NaOH or KOH and variable Si/K molar ratios. The formation of geopolymeric materials by hydroxylation and polycondensation characterized with different Si/Al molar ratios, depending on the original metakaolinite content, has been demonstrated. Sodium carbonates have been detected by XRD and FTIR, and confirmed by SEM-EDS, in two of these geopolymer materials being products of NaOH carbonation. Full article

In this study, the structure and phase transition of kaolin lithium clay at different calcination temperatures were studied and discussed; subsequently, the effects of Li leaching with sulfuric acid under various factors were investigated in detail. The experimental results indicated that an optimal Li leaching rate of 81.1% could be achieved when kaolin lithium clay was calcined at 600 °C for 1 h, followed by leaching with 15.0% sulfuric acid at 80 °C for 2 h. The TG-DSC, XRD, and SEM analyses showed that the layered structure of the clay was not destroyed during the leaching and calcination processes. During the process of calcination, kaolinite was converted to metakaolinite via dehydroxylation. During the process of leaching, the Al on the surface of the metakaolinite was dissolved by sulfuric acid, resulting in the destruction of the Al-O structure; then, Li⁺ was exchanged for H⁺ to the surface of the mineral and entered the solution under the action of diffusion. The leaching kinetics showed that the leaching process was controlled by a diffusion model, and the activation energy (E_a) was 41.3 kJ/mol. The rapid extraction of Li from calcined kaolin lithium clay with sulfuric acid leaching offers a high-efficiency, low-energy-consumption strategy for the utilization of new lithium resources. Full article

Copper slag is an industrial residue with a large unutilized fraction. This study presents the development of alkali-activated composites from a copper slag named Koranel^®. The effects of metakaolinite, ordinary Portland cement (OPC) and surfactants were investigated. The reactivity of Koranel with potassium silicate solutions with molar ratio R = SiO₂/K₂O varying from 1 to 2.75, with 0.25 intervals, was investigated using isothermal calorimetry. The reactivity was relatively low at 20 °C; the reaction started after a few hours with a low silica modulus, to several weeks with the highest silica modulus. The substitution of Koranel by OPC (5 wt.%) or by metakaolinite (10–20 wt.%), both led to higher reaction heat and rate; meanwhile, the addition of 2 wt.% polyethylene glycol/2-methyl 2,4 pentanediol delayed the reaction time in the system containing metakaolinite. Raising the curing temperature from 20 °C to 80 °C shortened the setting time of the low reactive systems, from several days to almost instantaneous, opening perspectives for their application in the production of prepreg composite materials. The use of carbon fabric as reinforcement in the alkali-activated matrix led to composite materials with flexural strength reaching 88 MPa and elastic modulus of about 19 GPa—interesting for engineering applications such as high-strength lightweight panels. Full article

The possibility of using microsilica in the production of mullite–silica refractories was assessed. The chemical and mineralogical compositions of the raw materials, refractory Arkalyk clay and microsilica, were studied. It has been found that primary mullite and quartz formation occurs due to dehydration of kaolinite with the formation of intermediate metakaolinite. The introduction of alumina and microsilica into the charge composition promotes the formation of secondary mullite due to the interaction of aluminum oxide and highly dispersed chemically active microsilica. Free silica in compositions undergoes polymorphic transformations with the formation of cristobalite and tridymite. Mullite–silica refractories with an open porosity of 21%, a compressive strength of 42 MPa, and a thermal deformation temperature under the load of 0.2 MPa–1350 °C were obtained. Full article

Coal gangue (CG) and coal gasification coarse slag (CGCS) possess both hazardous and resourceful attributes. The present study employed co-roasting followed by H₂SO₄ leaching to extract Al and Fe from CG and CGCS. The activation behavior and phase transformation mechanism during the co-roasting process were investigated through TG, XRD, FTIR, and XPS characterization analysis as well as Gibbs free energy calculation. The results demonstrate that the leaching rate of total iron (TFe) reached 79.93%, and Al³⁺ achieved 43.78% under the optimized experimental conditions (co-roasting process: CG/CGCS mass ratio of 8/2, 600 °C, 1 h; H₂SO₄ leaching process: 30 wt% H₂SO₄, 90 °C, 5 h, liquid to solid ratio of 5:1 mL/g). Co-roasting induced the conversion of inert kaolinite to active metakaolinite, subsequently leading to the formation of sillimanite (Al₂SiO₅) and hercynite (FeAl₂O₄). The iron phases underwent a selective transformation in the following sequence: hematite (Fe₂O₃) → magnetite (Fe₃O₄) → wustite (FeO) → ferrosilite (FeSiO₃), hercynite (FeAl₂O₄), and fayalite (Fe₂SiO₄). Furthermore, we found that acid solution and leached residue both have broad application prospects. This study highlights the significant potential of co-roasting CG and CGCS for high-value utilization. Full article

Geopolymers offer a potential alternative to ordinary Portland cement owing to their performance in mechanical and thermal properties, as well as environmental benefits stemming from a reduced carbon footprint. This paper endeavors to build upon prior atomistic computational work delving deeper into the intricate relationship between pH levels and the resulting material’s properties, including pore size distribution, geopolymer nucleate cluster dimensions, total system energy, and monomer poly-condensation behavior. Coarse-grained Monte Carlo (CGMC) simulation inputs include tetrahedral geometry and binding energy parameters derived from DFT simulations for aluminate and silicate monomers. Elevated pH values may can alter reactivity and phase stability, or, in the structural concrete application, may passivate the embedded steel reinforcement. Thus, we examine the effects of pH values set at 11, 12, and 13 (based on silicate speciation chemistry), investigating their respective contributions to the nucleation of geopolymers. To simulate a larger system to obtain representative results, we propose the numerical implementation of an Octree cell. Finally, we further digitize the resulting expanded structure to ascertain pore size distribution, facilitating a comparative analysis. The novelty of this study is underscored by its expansion in both system size, more accurate monomer representation, and pH range when compared to previous CGMC simulation approaches. The results unveil a discernible correlation between the number of clusters and pores under specific pH levels. This links geopolymerization mechanisms under varying pH conditions to the resulting chemical properties and final structural state. Full article

Melted rocks (clinkers and paralavas) of the Mongolian combustion metamorphic (CM) complexes were formed during modern and ancient (since the Quaternary) wild-fires of brown coal layers in the sedimentary strata of the Early Cretaceous Dzunbain Formation. According to XRD, Raman spectroscopy, and SEM-EDS data, cordierite, sekaninaite, indialite, ferroindialite, silica polymorphs, mullite, Fe-mullite, anhydrous Al-Fe-Mg silicate spinel (presumably new mineral), and other phases were identified. It has been established that isomorphic impurity of potassium in the cordierite-group minerals does not correlate with their crystal structure (hexagonal or orthorhombic). Indialite and ferroindialite retained their hexagonal structure in some fragments of the CM rocks, possibly due to the very fast cooling of local zones of sedimentary strata and the quenching of high-temperature K-rich peraluminous melt. Clinkers, tridymite–sekaninaite, and cristobalite–fayalite ferroan paralavas were produced by partial melting of Fe-enriched pelitic rocks (mudstone, siltstone, and silty sandstone) in a wide temperature range. The formation of mullite, Fe-mullite, and Al-Fe-Mg silicate spinel in clinkers developed from dehydration–dehydroxylation and incongruent partial melting of Fe-enriched pelitic matter (Al-Mg-Fe-rich phyllosilicates, ‘meta-kaolinite’, and ‘meta-illite’). Large-scale crystallization of these minerals in the K-rich peraluminous melts occurred, presumably, in the range of T > 850–900 °C. The subsurface combustion of coal layers heated the overburden pelitic rocks from sedimentary strata to T > 1050 °C (judging by the formation of cordierite-group minerals) or locally till the melting point of detrital quartz grains at T > 1300 °C and, possibly, till the stability field of stable β-cristobalite at T > 1470 °C. Ferroan paralavas were formed during the rapid crystallization of Fe-rich silicate melts under various redox conditions. From the analysis of the liquidus surface in the Al₂O₃–FeO–Fe₂O₃–SiO₂ major-oxide system, it follows that the least high-temperature (<1250 °C) and the most oxidizing conditions occurred during the crystallization of mineral assemblages in the most-enriched iron silicate melts parental for cristobalite–fayalite paralava. Full article

Today’s sustainable development policy in Europe, which is driven by concerns about the greenhouse effect and environmental protection, mandates a reduction in CO₂ emissions into the atmosphere. The cement industry and steel mills that produce reinforcing bars are among the largest and most emissions-intensive sectors emitting CO₂ into the atmosphere. This article analyzes the possibility of achieving significant reductions in CO₂ emissions by using basalt bars (BFRP) and glass bars (GFRP) in concrete structures, and—in the case of concrete—by using cement with the addition of metakaolinite and zeolite. There is a lack of literature reports on whether modifying concrete with the additions of metakaolinite and zeolite as substitutes for part of the cement affects the adhesion of FRP bars to concrete. It can be assumed, however, that improving the microstructure of concrete also improves the contact zone between the bar and the concrete. The aim of this research is to fill the aforementioned gap in the literature data by determining how the presence of metakaolinite and zeolite affects the adhesion of reinforcing bars to concrete and testing selected properties of hardened concrete. The test samples were prepared following the appropriate beam test procedure. The obtained results made it possible to perform a comparative analysis of reference samples and those with metakaolinite and zeolite additions. The research showed that introducing active pozzolanic additives in the form of metakaolinite and zeolite into concrete improved adhesion stress values by approximately 20% for glass GFRP bars and 15% for basalt BFRP bars, especially in the destruction phase. Full article

Halloysite and kaolinite are dioctahedral TO phyllosilicates that drive the interest of scientists for formulating environmentally friendly materials, and consequently in the field of ceramics. The main scope of this study was the understanding of the texture evolution upon the dehydroxylation reaction and the influence of the presence of halloysite. In situ synchrotron (002) and (111) poles figures were recorded on the DiffAbs beamline at SOLEIL Synchrotron, from room temperature to 1000 °C, on kaolinite and/or halloysite-rich samples shaped by tape casting. Commercial kaolins and halloysite provided by Imerys company were used. The samples were labeled KRG100, KCS100, H100, KRG50H50 and KRG59H50 in relation with the wt. % of kaolin (KRG, KCS) or halloysite (H) clays. In samples KCS100 and KRG100, a strong texture was observed until in situ annealing at 700 °C, with respect to the c-axis of kaolinite. On the contrary, the texture with respect to the c-axis of halloysite for the sample H100 was weak whatever the temperature was. Moreover, this weak texture disappeared before the complete dehydroxylation of halloysite. This is due to the opening of some halloysite tubes. When considering the samples KRG50H50 and KCS50H50, a significant texture was observed with the c-axis preferentially oriented perpendicular to the sample surface. The presence of kaolinite platelets predominated onto the alignment of halloysites tubes. Furthermore, it was noted that the halloysite influenced the (002) diffracted intensity into the temperature range 20 °C to 400 °C. Above 400 °C, the behavior obtained for the (002) reflection in samples KRG50H50 and KCS50H50 was similar to the behavior noticed for pure kaolins KRG100 and KCS100, respectively. The dehydroxylation temperature range appeared to be relevant with combined effect of kaolinite and halloysite transformations arising from KRG100 or KCS100 and H100 samples. Therefore, the onset point of dehydroxylation is 550 °C ± 25 °C for KRG100, KCS100, KRG50H50 and KCS50H50. For the pure halloysite H100 sample, the dehydroxylation starts at the lower temperature 475 °C. It was also noted that during the dehydroxylation of kaolinite, the characteristic portion of ring related to the diffracted intensity of the (111) reflection located at χ = 45° tended to disappear above 550 °C and led to the formation of a new transitory phase with a (111) reflection with perpendicular alignment to the c-axis. Indeed, an epitaxial relationship with the (111) kaolinite reflection could be assumed. Further X-ray scattering experiments allowed highlighting the effective offset temperature of the dehydroxylation, which was identified as close to 720 °C. The metakaolinite achieved structural transformation to another transitory phase at 1000 °C. Full article

In this study, the research aim is to enhance the activity index of activated coal gangue and study its activation mechanism. The activation process of coal gangue was optimized through orthogonal tests, and the Back-Propagation (BP) neural network model was improved using a genetic algorithm. With the effects of grinding duration, calcination temperature, and calcination duration, the morphological changes and phase transformation processes of coal gangue were studied at the micro and meso levels to clarify the activation mechanism. The results indicated that the effect of calcination temperature on the strength activity index of coal gangue was most significant, followed by grinding duration and calcination duration. The potential activity of coal gangue can be effectively stimulated through mechanical and thermal activation, and the content of potential active minerals in coal gangue powders was also increased. The activation process of coal gangue for the optimal scheme was obtained as grinding at 76 min first and thermal treatment at 54 min at 749 °C. As the thermal activation under 950 °C, some unstable external hydroxyls, and internal hydroxyls in kaolinite from coal gangue were removed, the Al^Ⅵ-O octahedron was destroyed, and kaolinite was transformed into spatially disordered metakaolinite with very high activity. Full article

The global demand for energy and industrial growth has generated an exponential use of fossil fuels in recent years. It is well known that carbon dioxide (CO₂) is mainly produced, but not only from fuels, which has a negative impact on the environment, such as the increasing emission of greenhouse gases. Thus, thinking about reducing this problem, this study analyzes microwave irradiation as an alternative to conventional heating to optimize zeolite A synthesis conditions for CO₂ capture. Synthesis reaction parameters such as different temperatures (60–150 °C) and different time durations (1–6 h) were evaluated. The CO₂ adsorption capacity was evaluated by CO₂ adsorption–desorption isotherms at 25 °C and atmospheric pressure. The results showed that the synthesis of zeolite A by microwave irradiation was successfully obtained from natural kaolinite (via metakaolinization), reducing both temperature and time. Adsorption isotherms show that the most promising adsorbent for CO₂ capture is a zeolite synthesized at 100 °C for 4 h, which reached an adsorption capacity of 2.2 mmol/g. Full article