In order to gain a deeper understanding of the rheological development of hydrating ordinary Portland cement (OPC) pastes at initial state, and to better understand their underlying processes, quantitative X-ray diffraction (XRD) analysis and rheological measurements were conducted and their results combined. The time-dependent relation between phase development and flow behavior of cement paste was investigated at two different temperatures (20 and 30 °C), over a period of two hours. Regarding the phase development during hydration, ettringite precipitation was identified as the dominant reaction in the first two hours. For both temperatures, the increasing ettringite content turned out to correlate very well with the loss of workability of the reacting cement paste. An exponential relationship between ettringite growth and flow behavior was observed that could be explained by applying the Krieger-Dougherty equation, which describes the influence of solid fraction on the viscosity of a suspension.

The rheological behavior of cement paste and the improvement of its flowability takes center stage in many research projects. An improved flowability can be achieved by the addition of superplasticizers (SP), such as polycarboxylate ethers (PCE). In order to be able to use these PCEs effectively and in a variety of ways and to make them resistant to changes in the environment, it is crucial to understand the influence of SPs on cement hydration. For that reason, the topic of this paper was the incompatibility of a specific SP and an ordinary Portland cement (OPC). The incompatible behavior was analyzed using rheological tests, such as the spread flow test and penetration test, and the behavior was compared by means of an ultrasound technique and explained by the phase content measured by in-situ X-ray diffraction (XRD) the heat evolution measured by calorimetry, and scanning electron microscope (SEM) images. We showed that the addition of the SP in a high dosage led to a prevention of the passivation of the most reactive and aluminum-containing clinker phases, aluminate and brownmillerite. This induced the aluminate reaction to take place in the initial period and led to an immediate stiffening of the cement paste and, therefore, to the complete loss of workability. The results showed that in addition to the ettringite, which began to form directly after water addition, hemicarbonate precipitated. The fast stiffening of the paste could be prevented by delayed addition of the SP or by additional gypsum. This fast stiffening was not desirable for SPs, but in other fields, for example, 3D printing, this undesirable interaction could be used to improve the properties of printable mortar.