Revealing the morphology of nano-ettringite in cement paste: A TEM study on the influence of polycarboxylate ether superplasticizers

Abstract

Ettringite forms directly after Portland cement is mixed with water. Polycarboxylate ether-type superplasticizers can stabilize nano-ettringite particles in the pore solution and modify ettringite formation. It was previously impossible to isolate the nano-ettringite from the cement pore solution at commonly used water-to-cement (w/c) ratios of 0.5 and lower. Therefore, the exact morphology of ettringite in the pore solution has not been systematically studied. This paper presents a novel method for obtaining nano-ettringite from cement paste by centrifugation with a high-density liquid. Ettringite was isolated at three different water-to-cement ratios (0.3, 0.4, and 0.5) and four dosages of a polycarboxylate ether-type superplasticizer (0.05%, 0.1%, 0.25%, and 0.4%). The size and morphology of the obtained ettringite particles were analyzed using transmission electron microscopy (TEM). The chemical composition and structure of ettringite were confirmed using electron energy loss spectroscopy, high-resolution TEM imaging, and X-ray diffraction. The ettringite particle size decreases as the superplasticizer dosage increases. As a result, the specific surface area at higher superplasticizer dosages increases from 39 m² g⁻¹ to 58 m² g⁻¹. In-situ calorimetry was used to measure the initial heat release and estimate the amount of ettringite formed. Since the initial heat did not change significantly with varying superplasticizer dosages, it suggests that the studied superplasticizer has a minor influence on the amount of ettringite at the considered concentrations. In summary, cement paste centrifugation using a high-density fluid allows the isolation of superplasticizer-stabilized nano-ettringite from cement paste. The method could be valuable for other studies dealing with the impact of ettringite morphology.