On the use of the Jander equation in cement hydration modelling

The equation of Jander [W. Jander, Z. Anorg. Allg. Chem. (1927) 163: 1-30] is often used to describe the kinetics of dissolution of solid cement grains, as a component of mathematical descriptions of the broader cement hydration process. The Jander equation can be presented as kt/R2 =[1-(1-α) (1/3) ]2 where k is a constant, t is time, R is the initial radius of a solid reactant particle, and α is the fractional degree of reaction. This equation is attractive for its simplicity and apparently straightforward derivation. However, the derivation of the Jander equation involves an approximation related to neglect of particle surface curvature which means that it is strictly not correct for anything beyond a very small extent of reaction. This is well documented in the broader literature, but this information has not been effectively propagated to the field of cement science, which means that researchers are continuing to base models on this erroneous equation. It is recommended that if the assumptions of diffusion control and unchanging overall particle size which lead to the selection of the Jander equation are to be retained, it is preferable to instead use the Ginstling-Brounshtein equation [A.M. Ginstling, B.I. Brounshtein, J. Appl. Chem. USSR (1950) 23: 1327-1338], which does correctly account for particle surface curvature without significant extra mathematical complication. Otherwise, it is possible (and likely desirable) to move to more advanced descriptions of particle-fluid reactions to account for factors such as dimensional changes during reaction, and the possibility of rate controlling influences other than diffusion

Alkali-activated materials

© 2017 Elsevier Ltd.This paper, which forms part of the UNEP White Papers series on Eco-Efficient Cements, provides a brief discussion of the class of cementing materials known as 'alkali-activated binders', which are identified to have potential for utilization as a key component of a sustainable future global construction materials industry. These cements are not expected to offer a like-for-like replacement of Portland cement across its full range of applications, for reasons related to supply chain limitations, practical challenges in some modes of application, and the need for careful control of formulation and curing. However, when produced using locally-available raw materials, with well-formulated mix designs (including in particular consideration of the environmental footprint of the alkaline activator) and production under adequate levels of quality control, alkali-activated binders are potentially an important and cost-effective component of the future toolkit of sustainable construction materials

Alkali activated slag mortars provide high resistance to chloride-induced corrosion of steel

The pore solutions of alkali-activated slag cements and Portland-based cements are very different in terms of their chemical and redox characteristics, particularly due to the high alkalinity and high sulfide content of alkali-activated slag cement. Therefore, differences in corrosion mechanisms of steel elements embedded in these cements could be expected, with important implications for the durability of reinforced concrete elements. This study assesses the corrosion behavior of steel embedded in alkali-activated blast furnace slag (BFS) mortars exposed to alkaline solution, alkaline chloride-rich solution, water, and standard laboratory conditions, using electrochemical techniques. White Portland cement (WPC) mortars and blended cement mortars (WPC and BFS) were also tested for comparative purposes. The steel elements embedded in immersed alkali-activated slag mortars presented very negative redox potentials and high apparent corrosion current values; the presence of sulfide reduced the redox potential, and the oxidation of the reduced sulfur-containing species within the cement itself gave an electrochemical signal that classical electrochemical tests for reinforced concrete durability would interpret as being due to steel corrosion processes. However, the actual observed resistance to chloride-induced corrosion was very high, as measured by extraction and characterization of the steel at the end of a 9-month exposure period, whereas the steel embedded in WPC mortars was significantly damaged under the same conditions

A discussion of the papers "Impact of hydrated magnesium carbonate additives on the carbonation of reactive MgO cements" and "Enhancing the carbonation of MgO cement porous blocks through improved curing conditions", by C. Unluer & A. Al-Tabbaa

This paper is a discussion of two recent papers by Unluer & Al-Tabbaa which analysed accelerated carbonation of reactive MgO blocks. We suggest that the authors have incorrectly analysed key data, leading to overstated claims of MgO carbonation. Based on the reassignment of their X-ray diffraction data, it is proposed that little MgO carbonation occurred in the samples discussed in those papers, with CaCO3 instead forming during accelerated carbonation. We also draw attention to the thermodynamic instability of nesquehonite under ambient conditions, which calls into question the long-term stability of these binders

Electrochemical cell design and impedance spectroscopy of cement hydration

Understanding the complexity of the chemical and microstructural evolution of cement during hydration remains a controversial subject, and although numerous techniques have been used to assess this process, further insight is still needed. Alternating current impedance spectroscopy has been demonstrated to be a sensitive and powerful technique for cement characterisation in both fresh and hardened states; however, it has also shown certain experimental limitations (e.g. data interpretation, electrode, and parasitic effects) that prevent its wider acceptance. This study assesses electrochemical cell design and the impedance response during cement hydration. The results show that a significant decrease in the parasitic effects at high frequencies (caused mainly by leads and electrode effects) can be achieved through an optimal cell design and impedance measurements correction, enabling correlation of impedance measurements to particular aspects of the cement hydration process. However, due the limited solid phase microstructural development and the high conductivity of cement paste at low degrees of hydration, the parasitic effects could not be fully eliminated for fresh or early-age cement pastes

Advances in understanding alkali-activated materials

Alkali activation is a highly active and rapidly developing field of activity in the global research and development community. Commercial-scale deployment of alkali-activated cements and concretes is now proceeding rapidly in multiple nations. This paper reviews the key developments in alkali-activated materials since 2011, with a particular focus on advances in characterisation techniques and structural understanding, binder precursors and activation approaches, durability testing and design, processing, and sustainability. The scientific and engineering developments described in this paper have underpinned the on-going scale-up activities. We also identify important needs for future research and development to support the optimal and appropriate utilisation of alkali activated materials as a component of a sustainable future construction materials industry

M&S highlight : Bischoff and Perry (1991), Compressive behaviour of concrete at high strain rates

This commentary is part of our celebration of 75 years of RILEM, highlighting Materials and Structures’ most highly influential and cited publications. Highlighted paper: P.H. Bischoff & S.H. Perry (1991). Compressive behaviour of concrete at high strain rates. Materials and Structures 24(6), pp. 425–450

Quantification of the influences of aggregate shape and sampling method on the overestimation of ITZ thickness in cementitious materials

The microstructure of the interfacial transition zone (ITZ) surrounding the aggregate in a cementitious composite is quite different from that of the bulk matrix, because of its distinct physical nature including relatively high porosity and low rigidity. The thickness and volume fraction of the ITZ play a major role in determining the transport and mechanical behavior of cementitious composites. However, the ITZ thickness may be overestimated when undertaking sectional plane analysis of these composites. Analysis of Platonic particles has previously shown that the sphericity of the particle is an important parameter in determining the overestimation of the ITZ thickness, but this raises the question of whether sphericity is sufficient to uniquely characterize the influence of aggregate shape. This paper investigates the influence of particle shape on overestimation of ITZ thickness for aggregate shapes which have the same sphericity values as Platonic particles; specifically, spheroids of differing geometries. A normal line sampling algorithm, which is designed to replicate the practical experimental process used in ITZ determination, is employed to obtain the apparent ITZ thickness. The influences of particle shape, sampling method and particle size distribution are investigated in terms of the overestimation of the ITZ volume fraction, and the effective diffusivity within three-phase composites, using the differential effective medium approximation