Mineralogical characteristics influence the structure and pozzolanic reactivity of thermally and mechano-chemically activated meta-kaolinites

Increasing early age reactivity of cement replacements is a barrier to reducing the embodied carbon of blended Portland cements. Mechano-chemical activation is an emerging alternative to conventional thermal activation for clays, which can accelerate early age reactivity. Knowledge gaps on the structure and reactivity of mechano-chemically activated kaolinitic clays include the influence of Fe-bearing phases and the mineralogical characteristics of kaolinites from different sources. This study evaluated the effectiveness of mechano-chemical vs. thermal activation for an Fe-rich clay containing disordered kaolinite and 24 wt% goethite, and a low-Fe clay containing highly ordered kaolinite. In the Fe-rich clay, mechano-chemical activation simultaneously caused dehydroxylation of kaolinite to form meta-kaolinite, and dehydration of goethite to form hematite. Agglomerates of intermixed meta-kaolinite and goethite/hematite nanoparticles were shown to have similar Al and Si environments after thermal or mechano-chemical activation (as determined by STEM-EDX, 27Al and 29Si MAS nuclear magnetic resonance and electron energy loss spectroscopy). Mechano-chemical activation enhanced early age (<12 hours) reactivity for both clays. Evaluating early age reactivity by unit mass of anhydrous meta-kaolinite explains how surface-adsorbed moisture results in underperformance of mechano-chemical activation at later ageing times. External surface area alone does not predict reactivity acceleration well – edge : basal surface area of meta-kaolinite is proposed as a more relevant factor that governs early age performance of mechano-chemically activated clays. The structure–property–performance relations of mechano-chemically activated meta-kaolinites are explained through interactions of kaolinites' intrinsic mineralogical characteristics (i.e. initial particle size, aspect ratio, structural order) and extrinsic processing effects (i.e. intensive milling on structural order and physical characteristics)

Clay calcination technology: state-of-the-art review by the RILEM TC 282-CCL

The use of calcined clays as supplementary cementitious materials provides the opportunity to significantly reduce the cement industry’s carbon burden; however, use at a global scale requires a deep understanding of the extraction and processing of the clays to be used, which will uncover routes to optimise their reactivity. This will enable increased usage of calcined clays as cement replacements, further improving the sustainability of concretes produced with them. Existing technologies can be adopted to produce calcined clays at an industrial scale in many regions around the world. This paper, produced by RILEM TC 282-CCL on calcined clays as supplementary cementitious materials (working group 2), focuses on the production of calcined clays, presents an overview of clay mining, and assesses the current state of the art in clay calcination technology, covering the most relevant aspects from the clay deposit to the factory gate. The energetics and associated carbon footprint of the calcination process are also discussed, and an outlook on clay calcination is presented, discussing the technological advancements required to fulfil future global demand for this material in sustainable infrastructure development

Determining aluminium co-ordination of kaolinitic clays before and after calcination with electron energy loss spectroscopy

Developing a greater understanding of kaolinite dehydroxylation upon calcination is crucial for several industrial applications, including cements. Aluminium coordination in meta-kaolinite indicates the extent of its dehydroxylation and its potential chemical reactivity, and it is typically determined using 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. This technique however presents limitations for Fe-rich materials, given the magnetic properties of Fe ions and minerals containing Fe. In this study, the effect of calcination on Al coordination was assessed in a low-Fe clay used as a reference system, and a Fe-rich clay. Al coordination in the low-Fe clay was quantified via 27Al MAS NMR spectra deconvolution, using data collected at 9.4 T and 11.7 T. Energy dispersive X-ray spectroscopy (EDX) maps and electron energy loss spectroscopy (EELS) measurements were carried out in a scanning transmission electron microscope (STEM) on both clays. Al K-edge EEL spectra showed distinguishable 4/5-fold Al and 6-fold Al sites in both clay types. Differences in line-profile indicated a higher proportion of 4/5-fold Al in kaolinite in the Fe-rich clay compared to the low-Fe clay. Conversely, the Fe-rich clay contained a lower proportion of 4/5-fold Al in meta-kaolinite after calcination, relative to the low-Fe clay. These differences are consistent with the greater structural disorder of the meta-kaolinite identified in the Fe-rich clay by X-ray diffraction and the geological origins of both clays. Overall, this study demonstrates the potential of EELS to provide information about Al coordination for individual kaolinite and meta-kaolinite particles

Suitability of excavated London Clay as a supplementary cementitious material: Mineralogy and Reactivity

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Unlocking the potential of UK clays for the production of low-carbon cements

This study evaluated the potential of different UK clays to be activated with the purpose of using them as supplementary cementitious materials (SCMs). A comprehensive field survey was carried out by the British Geological Survey, collecting more than 41 different clay samples from different locations. The clay samples were subjected to laboratory-based characterization, analysing their chemical and mineralogical composition through X-ray fluorescence spectroscopy (XRFS), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The majority of clays contained <40 wt.% kaolinite; the total clay content ranged widely from 10 – 82 wt.%, and carbonate minerals were frequently present, up to 20 wt.%. Clays were classified into four groups based on their mineralogical composition; from the two groups with mineralogical attributes deemed most suitable for calcination, 11 selected clays were then calcined at 800°C and their chemical reactivity was determined using the calorimetry method of the R3 test. Results revealed that after thermal activation, UK clays yielded R3 values ranging from 200 to 500 J/g SCM, classifying them as SCMs with moderate reactivity. Although clays with higher kaolinite content typically exhibited superior reactivity, the results indicated that additional factors, such as total clay content, need to be considered for predicting reactivity, particularly for mixed clays

Use of sawdust Eucalyptus sp. in the preparation of activated carbons Utilização de serragem de Eucalyptus sp. na preparação de carvões ativados

Wood sawdust is a solid residue, generated in the timber industry, which is of no profitable use and can cause serious environmental problems if disposed inadequately. The aim of this study was to use the eucalyptus sawdust in the preparation of activated carbons AC) and test them as adsorbents of methylene blue (MB) and phenol, representative pollutants from aqueous effluents of various industries. The eucalyptus sawdust was characterized by instrumental analysis such as elementary analysis (CHNS-O), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The activated carbons were prepared by physical activation with carbon dioxide AC_CO2, (10º C min-1, 850º C, 1h) and by chemical activation with potassium carbonate AC_K2CO3 (10º C min-1, 850º C, 3h). The AC_CO2 and AC_K2CO3 were characterized by CHN-O, TGA, FTIR, N2 adsorption/desorption (BET) to evaluate the specific surface area and SEM. The resulting activated carbons were tested for their ability to adsorb MB and phenol in water. The activated carbons produced in this work were predominantly microporous and showed specific surface area of about 535 m² g-1. The AC_K2CO3 was more effective in the adsorption of MB (81 mg g-1) and phenol (330 mg g-1) than AC_CO2 (32 mg g-1 and 172 mg g-1, respectively, for MB and phenol).<br>A serragem é um resíduo sólido, gerado na indústria madeireira, que não tem uso rentável e pode causar sérios problemas ambientais quando disposta inadequadamente. Neste estudo, objetivou-se utilizar a serragem de eucalipto na preparação de carvões ativados (AC) e testá-los como adsorventes do corante azul de metileno (MB) e fenol; moléculas que representam poluentes de efluentes industriais. A serragem de eucalipto foi caracterizada por análises instrumentais, tais como: análise elementar (CHNS-O), análise termogravimétrica (TGA), espectroscopia na região do infravermelho (FTIR) e microscopia eletrônica de varredura (SEM). Os carvões ativados foram preparados por ativação física com dióxido de carbono AC_CO2, (10º Cmin-1, 850ºC, 1h) e pela ativação química com carbonato de potássio- AC_K2CO3 (10º Cmin-1, 850º C, 3h). O AC_CO2 e AC_K2CO3 foram caracterizados por CHN-O, TGA, FTIR, adsorção/dessorção de N2 (área BET) para avaliar a área superficial específica e SEM. Os carvões ativados resultantes foram testados quanto à capacidade de adsorver MB e fenol na água. Os carvões produzidos apresentaram características de material microporoso, apresentando área superficial média de cerca de 535 m²g-1. O AC_K2CO3 foi mais eficiente na adsorção do MB (81mgg-1) e fenol (330mgg-1) que o AC_CO2 (32mg g-1 e 172 mg g-1, respectivamente, para MB e fenol)