Energetically modified cement | EPFL Graph Search

Energetically modified cements (EMCs) are a class of cements made from pozzolans (e.g. fly ash, volcanic ash, pozzolana), silica sand, blast furnace slag, or Portland cement (or blends of these ingredients). The term "energetically modified" arises by virtue of the mechanochemistry process applied to the raw material, more accurately classified as "high energy ball milling" (HEBM). This causes, amongst others, a thermodynamic transformation in the material to increase its chemical reactivity. For EMCs, the HEBM process used is a unique form of specialised vibratory milling discovered in Sweden and applied only to cementitious materials, here called "EMC Activation". By improving the reactivity of pozzolans, their strength-development rate is increased. This allows for compliance with modern product-performance requirements ("technical standards") for concretes and mortars. In turn, this allows for the replacement of Portland cement in the concrete and mortar mixes. This has a number of benefits to their long-term qualities. Energetically modified cements have a wide range of uses. For example, EMCs have been used in concretes for large infrastructure projects in the United States, meeting U.S. concrete standards. The term "energetically modified cement" incorporates a simple thermodynamic descriptor to refer to a class of cements produced using a specialised highly intensive milling process first discovered in 1993 at Luleå University of Technology (LTU) in Sweden. The transformatory process is initiated entirely mechanically as opposed to heating the materials directly. The mechanisms of mechanochemical transformations are often complex and different from "traditional" thermal or photochemical mechanisms. The effects of HEBM-transformation cause a thermodynamic change that resides ultimately in a modified Gibbs Energy. The process increases the binding capacity and chemical reactivity rates of the materials transformed. Continuing academic work and research regarding "self-healing" properties of energetically modified cements is ongoing at LTU.

Effect of ZnO on the reactivity of cementitious systems

Andrea Eloisa Teixeira Pita

One of the biggest driving forces in cement research today is the mitigation of the CO2 emissions caused by its production. A potential solution to reduce the environmental impact is to replace cement with supplementary cementitious materials (SCMs). This replacement results in low strength at early ages because they are slow to react. The incorporation of minor elements has shown the potential to improve cement reactivity. A few percent of ZnO in C3S causes a signifi- cant increase in reactivity. This effect was related to the incorporation of zinc into the C-S-H struc- ture, which increases its needle length. This research investigates the effect of ZnO in more realis- tic systems such as alite, C3A-polyclinker, and C4AF-polyclinker. The positive effects observed in C3S are translated in the alite system, but differences were found in the polyclinkers, which have a prolonged induction period. This resulted due concentration of zinc in the interstitial phases and a small amount of zinc in alite phase. An amorphous phase was identified in the C3A polyclinker; it is believed to react rapidly with water, releasing Zn ions into the solution, which delays the reaction of alite. The addition of more gypsum controls the reaction of this phase, and thus the induction period is shortened.This work explores the possibilities of retaining Zn in alite to enhance the reactivity of more realis- tic cementitious systems. The cooling rate was critical, as a slow cooling rate promoted more Zn in the alite, less amorphous, and hence, an enhancement in the hydration of C3A-polyclinker doped with ZnO. The recalcination of this system did not affect the hydration of alite but increased the amount of crystalline C3A, which reacted faster. Thus, the amorphous phase was related to an aluminate phase. Moreover, a C4AF-polyclinker and a system with a lower amount of interstitial phase were investigated. The results showed a higher Zn concentration in alite but also extended induction periods. This was associated with the free ZnO and the amorphous content. Even when the hydration was delayed, the height of the alite peak increased with Zn doping, probably due to the incorporation of Zn into the C-S-H observed in pure C3S.In addition, the interaction between sulfates and zinc in the alite system doped with ZnO was in- vestigated. Severe retardation was observed, and the reason is proposed to be the formation of amorphous Zn compound. The presence of aluminum, ettringite formation, or an amorphous layer were discarded as the cause of the retardation.

EPFL2022

Effect of ZnO on the reactivity of cementitious systems

Andrea Eloisa Teixeira Pita

EPFL2022