1.2. The rate peak
The transition fromaccelerating rates to decelerating rates has been
alternately explained in terms of (1) a transition fromcontrol by C–S–H
growth to control by diffusion through a thickening product layer on the
surface of cement grains [15–17]; (2) eventual reduction in the surface
area of C–S–H by bridging and filling the available space between
cement particles [15]; or (3) reduction of C–S–H surface area by the lateral
impingement of C–S–H precipitates growing along the surface of a
single grain [18]. To be plausible, both hypotheses (2) and (3) require
that C–S–H growth is the rate-controlling process both before and
after the peak hydration rate; hydration kinetics would be unaffected
by C–S–H surface area if C3S dissolution controlled the rate. Based on evidence
that the magnitude and timing of the peak rate are about the
same in pastes as they are in suspensions with high water/cement
ratio, Garrault et al. [19] concluded that (4) C3S hydration is controlled
by C–S–Hgrowth during the acceleration period butmay change to control
by C3S dissolution during the deceleration period, and then to diffusion
control at significantly later times [20].
Hypotheses (1) and (4) require a transition fromC–S–Hgrowthcontrol
to diffusion control and C3S dissolution control, respectively. Such a
transition would generally imply a change in the apparent activation
energy for the net process [21]. The most recent and accurate measurements
of activation energy for C3S hydration show no change in the
activation energy, at least for many hours after the peak rate [22]. A
near equality of the activation energies for C–S–H growth and C3S
dissolution would be a remarkable coincidence because the solids
have such different structures and compositions.
Computer modeling of changes in the 3D microstructure and chemistry
during C3S hydration offers the opportunity to quantify the influences
of the driving forces for the various processes, as well as the
individual process rates and their dependence on solution composition
in a way that is difficult, if not impossible, to do experimentally. In that
sense, the kind of computer modelingwe describe can complement experimental
observations and help gain further insight into the origins of
these hydration phenomena.
1.2. The rate peakThe transition fromaccelerating rates to decelerating rates has beenalternately explained in terms of (1) a transition fromcontrol by C–S–Hgrowth to control by diffusion through a thickening product layer on thesurface of cement grains [15–17]; (2) eventual reduction in the surfacearea of C–S–H by bridging and filling the available space betweencement particles [15]; or (3) reduction of C–S–H surface area by the lateralimpingement of C–S–H precipitates growing along the surface of asingle grain [18]. To be plausible, both hypotheses (2) and (3) requirethat C–S–H growth is the rate-controlling process both before andafter the peak hydration rate; hydration kinetics would be unaffectedby C–S–H surface area if C3S dissolution controlled the rate. Based on evidencethat the magnitude and timing of the peak rate are about thesame in pastes as they are in suspensions with high water/cementratio, Garrault et al. [19] concluded that (4) C3S hydration is controlledby C–S–Hgrowth during the acceleration period butmay change to controlby C3S dissolution during the deceleration period, and then to diffusioncontrol at significantly later times [20].Hypotheses (1) and (4) require a transition fromC–S–Hgrowthcontrolto diffusion control and C3S dissolution control, respectively. Such atransition would generally imply a change in the apparent activationenergy for the net process [21]. The most recent and accurate measurementsof activation energy for C3S hydration show no change in theactivation energy, at least for many hours after the peak rate [22]. Anear equality of the activation energies for C–S–H growth and C3Sdissolution would be a remarkable coincidence because the solidshave such different structures and compositions.Computer modeling of changes in the 3D microstructure and chemistryduring C3S hydration offers the opportunity to quantify the influencesof the driving forces for the various processes, as well as theindividual process rates and their dependence on solution compositionin a way that is difficult, if not impossible, to do experimentally. In thatsense, the kind of computer modelingwe describe can complement experimentalobservations and help gain further insight into the origins ofthese hydration phenomena.
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