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The thermal analysis of zinc oxide-contaminated Portland cement blended with thiocyanates and determination of their effect on hydration and properties

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Abstract

The contamination of cement binders with zinc represents a significant problem due to the negative effects on cement hydration. Zinc compounds cause a drastic increase in setting time due to prolonging the induction period. The currently accepted mechanism behind this effect is the formation of Ca(Zn(OH)3)2·2 H2O hydrates on the surface of cement grains that deplete Ca2+ ions from the pore solution and creates a diffusion barrier. Hydration accelerators are commonly employed in the concrete industry to counter long setting time caused by low temperature and contamination by heavy metals. These compounds influence both hydration kinetics and composition of hydration products. The influence of various compounds on the mechanism of cement hydration can be studied using calorimetric methods such as isoperibolic and isothermal calorimetry. The hydration of the material was stopped, and the properties of hydrated cement pastes were studied using differential thermal analysis, X-ray diffraction and scanning electron microscopy. Some setting accelerators have been found to significantly decrease setting time of zinc-contaminated cement. Out of the most used compounds in commercial accelerators, the efficiency of thiocyanates is yet to be determined. The results show that thiocyanates induce a visible change in hydration mechanism of cement to various degrees depending on concentration and on the presence of the specific cation. Alkali thiocyanates drastically retard the hydration of zinc-contaminated OPC. With further retarded hydration of cement, the mechanical properties were negatively impacted. Calcium thiocyanate on the other hand effectively accelerates setting and positively impacts compressive strength at low doses. Main difference between the influence of alkali and calcium thiocyanates on setting is the change in ettringite content. Alkali salt promotes AFm phases at the expense of ettringite content while calcium salt promotes formation of ettringite at early stages of cement hydration.

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Funding

This outcome has been achieved with the financial support by the project: GA19-16646S “The elimination of the negative impact of zinc in Portland cement by accelerating concrete admixtures”, with financial support from the Czech Science Foundation.

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  1. Faculty of Chemistry, Institute of Material Chemistry, Brno University of Technology, Purkyňova 118, Brno, Czech Republic

    Lukas Matejka, Pavel Siler, Radoslav Novotny, Jiri Svec, Jiri Masilko, Jan Koplik & Frantisek Soukal

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  1. Lukas Matejka
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  2. Pavel Siler
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  3. Radoslav Novotny
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  7. Frantisek Soukal
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LM contributed to original draft preparation, investigation and formal analysis. PS contributed to conceptualization and editing. JS, JM, RN and JK contributed to investigation, data curation, formal analysis and methodology. FS contributed to project administration and supervision.

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Matejka, L., Siler, P., Novotny, R. et al. The thermal analysis of zinc oxide-contaminated Portland cement blended with thiocyanates and determination of their effect on hydration and properties. J Therm Anal Calorim 148, 1321–1349 (2023). https://doi.org/10.1007/s10973-022-11666-0

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