Cement and Concrete Research 124 (2019) 105823

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Cement and Concrete Research

journal homepage: www.elsevier.com/locate/cemconres

Advances in understanding cement hydration mechanisms T

a,⁎ a b a
Karen Scrivener , Alexandre Ouzia , Patrick Juilland , Aslam Kunhi Mohamed
a
EPFL STI IMX LMC, MXG 230, Station 12, CH-1015 Lausanne, Switzerland
b
SIKA Technology, Zürich, Switzerland

A R T I C LE I N FO A B S T R A C T

Keywords: Progress in understanding hydration mechanisms of alite and Portland cement is reviewed. Up to the end of the
Cement induction period, dissolution rates determined by the undersaturation of the solution dominate the reaction, but,
Hydration better understanding is needed about the alite solution interface. The main heat evolution peak hydration is
Induction period dominated by the growth of outer C-S-H with a spiky or “needle” like morphology. Growth is rapid over several
Main hydration peak
hours (acceleration period) and then slows (deceleration period). At later ages the consumption of water and
Later ages
lack of water filled pores above about 10 nm, along with the consumption of anhydrous material are major
factors leading to the continual reduction in the rate of reaction. There is no evidence that diffusion becomes the
rate controlling mechanism even at this stage. The microstructure of cement differs significantly from that of
alite, largely due to the influence of alumina on C-S-H growth and distribution.

1. Introduction
This paper reviews our understanding of the kinetics and mechan-
isms of cement hydration. It follows closely from papers written for the
two previous Chemistry of Cement Conferences [1,2]. The main focus is
on the hydration of the tricalcium silicate phase, which dominates the
hydration process, especially at early ages. Nevertheless, there are im-
portant differences between alite and Portland cement, particularly in
terms of microstructural development, which are discussed.
2. Hydration of C3S/alite
The mechanisms governing the hydration of calcium silicate are
usually discussed in terms of the heat evolution curve, Fig. 1. Although
this curve has been divided into up to 7 regions, it is more straight-
forward to discuss 3 periods: I - up to the end of the induction period; II
- the main hydration peak; III - hydration after the main peak.
2.1. Period I: up to the end of the induction period
Since the last review article 4 years ago [2], no new mechanisms
have been proposed to explain the origin of the induction period. The
new literature focuses on the two main hypotheses: the protective
membrane theory and the dissolution one. Despite new experimental
data, the situation hasn't changed much with both theories having their
partisans choosing essentially to highlight their most apposite
arguments. We will try to highlight the pros and cons for each hy-
pothesis.
2.1.1. Protective membrane theory
This long-standing hypothesis is the oldest and raises the funda-
mental question: “What is the state of the solid-water interface between
the C3S surface and its surrounding pore solution?” The main argument
in support of the protective membrane theory is the indirect thermo-
dynamic consideration: to reconcile the apparent low reactivity ob-
served experimentally during the induction period with the high C3S
solubility calculated from its enthalpy of formation [3–10]. Based on
this discrepancy, several authors have proposed that a metastable C-S-H
hydrate forms which covers the reacting surface preventing extremely
fast dissolution that is otherwise expected.
The seminal paper of Gartner and Jennings [11] proposed that so-
lution data in the literature supported the existence of two types of C-S-
H – one metastable curve corresponding to solutions present during the
early hydration of C3S and one corresponding to stable C-S-H, present in
preparation of C-S-H from laboratory reagents or during later hydration
of C3S. Although, re-examination of the data in this paper [11] does not
seem to show such a clear distinction in these two categories. In a re-
cent study [12] the composition of pore solution of hydrating C3S with
water to cement ratios varying from 0:4 to 0.75 was carefully measured.
Up to 5% of hydration, all calculated activities fell on the same solu-
bility curve attributed to a metastable C-S-H with a C/S of either 1.23 or
1.44 depending if the existence of a calcium-silicate complex is

⁎
Corresponding author.
E-mail address: karen.scrivener@epfl.ch (K. Scrivener).

https://doi.org/10.1016/j.cemconres.2019.105823
Received 21 June 2019; Received in revised form 18 July 2019; Accepted 18 July 2019
0008-8846/ © 2019 Elsevier Ltd. All rights reserved.
K. Scrivener, et al.
I II
Fig. 1. Typical heat evolution curve of alite, broken up into 3 periods as discussed here.
considered or not.
Several studies provide evidence that some hydrates do form rapidly
upon contact with water [13–15] and these early hydrates may control
the pore solution at this stage (see also Section 2.1.4). What is ques-
tionable is the formation of a hydrate film with enough coverage to give
a diffusion barrier which so dramatically reduces the rate of C3S reac-
tion. To be effective, the hydrate layer would also need to be tightly
bound to the reactive grain. Such a membrane has never been observed
experimentally despite progress in experimental tools and methods.
Indeed, it seems very unlikely that such a continuous film of a few
nanometres could form uniformly through a dissolution precipitation
process, generally agreed to be the case for cementitious phases. The
formation of a layer continuous over the whole surface and tightly
bound to the substrate could probably only result from a topological
reaction with an incongruent dissolution as observed in the case of
certain poorly reactive glassy materials [16–22]. It has however been
shown that dissolution of C3S is congruent irrespective of the initial
saturation state of the solution [23]. The required epitaxy with the C3S
surface also seems unlikely when the different crystallographic or-
ientations exposed on grain surfaces and the radically different crystal
structures of C3S and C-S-H are considered.
Another issue regarding this approach is that it fails at explaining
the annealing experiments on C3S (thermal treatment of the anhydrous
powder [24]) which exhibit much longer induction periods without a
change in the driving force, i.e. difference in chemical potential be-
tween the surrounding pore solution and the reacting surface.
Moreover, if the rate of dissolution has to be controlled by a
membrane of metastable product, what happens after the end of the
induction period? At the end of the induction period it is considered
that stable C-S-H forms, which should cause the metastable layer to
disappear. However, the reaction rate predicted from the enthalpy of
formation is still much higher than those observed [25].
The apparent discrepancy between the low reactivity observed
during the induction period, and the high C3S solubility calculated
through the enthalpy of formation, can be the better explained by the
concept of superficial hydration of the interface introduced by Barret
[26]. This proposes that the exposed silicate species of the reacting C3S
are hydroxylated (protonation of the silicate groups) and partially de-
protonated as the pH increases over the course of hydration. Such a
vision has been supported by Pustovgar et al. [27] using 29Si{1H}
CPMAS NMR methods, which indicate Q0 silicates in close proximity to
water. Their results corroborate the ones from Rodgers et al. [28], with
a major difference in the interpretation, since the hydroxylated Q0
species found during the induction period, and previously attributed to
the protective membrane, are present prior to contact with bulk water
and show no evolution during the induction period.
2.1.2. Dissolution controlled by undersaturation
Several articles on C3S dissolution have been published over the
past few years [23,24,29–35] and summarized in [35]. It has been
shown experimentally that the rates of dissolution of pure C3S and alite
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Cement and Concrete Research 124 (2019) 105823
III
decrease non-linearly as the undersaturation of the system decreases,
i.e. as the system is moving towards equilibrium. These experiments are
all performed in conditions diluted enough to prevent the precipitation
of hydrates. Therefore, the rates obtained are not necessarily quanti-
tatively representative of dissolution rates taking place in paste where
hydrates precipitate at roughly the same time. Such rates are very
difficult to measure in real hydration conditions as it is difficult to
isolate or determine experimentally the “free” surface of C3S which is
dissolving. In real hydration conditions dissolution and precipitation of
hydrates take place simultaneously and at the same rate (since the so-
lution cannot store a significant amount of dissolved material). The
presence of hydrates on the reacting surface might well interfere with
the dissolution process.
Another difference observed, between pure dissolution experiments
and real hydrating conditions, is the surface topography. The mor-
phology of the pits observed in pure dissolution experiments is very
shallow exhibiting a lens shape whereas pits observed on C3S grains
during the course of hydration are usually very deep and irregular in
shape [23] (Fig. 2). This implies that dissolution rates obtained from
pure dissolution experiments may not be transposed directly to rates of
dissolution in hydrating conditions and some effort is still required to
explain these differences. Indeed, the surface of C3S hydrating in paste
conditions is exposed to a solution which evolves over time. This means
that it may pass through different regimes of dissolution leading to a
“history” dependent topography.
In any case dissolution experiments qualitatively show that rates of
dissolution do indeed decrease significantly as the system evolves to-
wards equilibrium. The interested readers are invited to consult [35] for
more information on this topic.
2.1.3. How to distinguish between these theories
In a set of simulation experiments, Bullard and Flatt tried to find
ways to distinguish between the passivation layer theory (i.e. protective
membrane theory) and the site deactivation hypothesis (i.e. dissolution
theory) [36]. Their results indicated that both theories can lead to si-
mulations that reproduce typical experimental features, such as the
heat evolution and the evolution of the pore solution composition.
However, when they looked at the impact of inhibition of Portlandite
precipitation on the hydration kinetics (all other things being equal),
their simulations indicated very different kinetics according to which of
the two theories was used. A strong retardation in kinetics was found in
the case of the dissolution theory whereas no retardation was observed
in the case of the protective membrane theory. This can be understood,
in the case of the dissolution theory, by the fact if CH cannot pre-
cipitate, there is no sink for calcium and hydroxide ions and the solu-
tion composition remains at a low undersaturation with respect to C3S
with a low rate of dissolution. On the other hand, the protective
membrane relies on the conversion of a metastable C-S-H to a more
stable one and in that case, the inhibition of Portlandite precipitation
would have no impact on that conversion thus there would be no re-
tardation. Bullard and Flatt suggested that identifying an additive,
K. Scrivener, et al. Cement and Concrete Research 124 (2019) 105823

Fig. 2. TEM images of OPC hydrated for (a) 12 h and (b) 24 h. From [64.

which could selectively inhibit the precipitation of portlandite while observed in hydrating conditions. Taking this anisotropy of dissolution
not affecting C3S nor C-S-H, could decisively differentiate between the into account is also be an important step in modelling approaches since
two theories. so far only isotropic dissolution is considered.
In a recent study Juilland and Gallucci [37] found that sucrose
mainly acts as an inhibitor of portlandite nucleation and growth 2.1.4. C-S-H: new insights
without having much impact on other parallel reactions involving si- Recently, synthetic C-S-H precipitation studies [42–44] have ob-
licates for pH up to 12.7, i.e. C-S-H nucleation and growth as well as served a nanoglobular morphology (Fig. 3). It may be speculated that
pure C3S dissolution. These results remain valid for pure C3S hydration this could be the metastable product conjectured to form in the first few
in paste as the measured pH did not exceed 12.8, keeping the fraction of minutes of C3S hydration reaction. Kumar et al. [42,45] synthesized
deprotonated sucrose molecules low enough to limit their calcium nanoglobular C-S-H at solution conditions with pH < 11. X-ray dif-
mediated adsorption on silicate surfaces [38]. As predicted by the dis- fraction showed that these nanoglobules are amorphous [45]. The au-
solution theory, a strong retardation was observed in this system and thors also observed that it has a Ca/Si ratio < 1.25 from 29Si DNP NMR
these experiments provide a strong argument in favour of the dissolu- studies and does not follow the ‘dreierketten’ silicate chain structure
tion theory hypothesis. that is generally found for C-S-H (Fig. 4) [42].
The work of Marchon et al. [39] on retardation induced by PCE also Schönlein et al. [43] observed similar results by mixing calcium
provides indirect evidence for the dissolution theory. In their work pure nitrate and sodium silicate in a syringe that were filtered and collected
dissolution experiments showed a strong impact of the PCE on the after a few minutes. The authors illustrated the metastable nature of the
measured rate of dissolution for undersaturation conditions enabling nanoglobular C-S-H which transformed into nanofoils when it is filtered
the calcium mediated adsorption of these molecules (2 orders of mag- after about 15–30 min of reaction. Here, the pH is not controlled during
nitude lower in the most pronounced case). This reduction in dissolu-
tion rate allowed the retardation behaviour seen in annealing experi-
ments to be exactly reproduced with a defined dosage of a PCE [40].
Pourchez et al. also proposed that PCE would impact the dissolution
process of C3S and Nicoleau came to a similar conclusion for latexes
[41].
In light of these findings, the idea that reaction is limited by a
protective membrane as a diffusion barrier should be set aside. The
hypothesis of the dissolution theory as a mechanism responsible for the
induction period as proposed originally [24] remains valid. Never-
theless, more work is needed to characterise the solution composition
and the early hydrate formation, particularly a better understanding of
the reacting alite surface is needed, i.e. hydroxylated state, etch pit
formation, step retreat, kink site formation and crystallographic defects.
Indeed, TEM images during the main hydration peak (Fig. 2), reveal
a strong anisotropy in the front of dissolution on reacting alite grains.
These features clearly highlight the importance of crystallographic or-
ientation. This has been quantitatively assessed by Robin et al. [34]
showing that strong differences in rate of dissolution are found for a
same degree of undersaturation. Furthermore, the evolution of the rate
of dissolution as a function of the undersaturation did not follow a
single trend. This means that the relative contribution of each plane of
different crystallographic orientation to the overall rate of dissolution
can vary as a function of the undersaturation. An important next step
would be to establish whether the fastest dissolving crystallographic
orientation analysed in pure dissolution experiments are the same as Fig. 3. Globular C-S-H structure from [42].

3
K. Scrivener, et al.
Fig. 4. Typical foil like morphology of C-S-H grown in solution [42].
their synthesis and not reported, so cannot be compared with the ex-
periments of Kumar et al. [42] where the morphology is a function of
the pH which in-turn determines the relative abundance of the different
species in solution.
Krautwurst et al. [44] also observed such morphology which they
called spheroids, which crystallized at later ages (> 600 min, in their
solution conditions) to form ordered layers within these globules.
However their final product is a crystalline C-S-H and such a high de-
gree of crystallinity is generally not found in the real system.
It could be supposed that during the initial minutes of dissolution,
nanoglobules are formed as a metastable phase as the pH builds up.
When the pH is above 12, then the nanofoils of C-S-H form as illustrated
by Kumar et al. [45]. Nonetheless, is seems very unlikely that such a
globular product (if present on the surface) would significantly inhibit
dissolution.
Apart from this anomoulous globular structure, C-S-H synthesized
from solution is always reported to have a foil like structure as shown in
Fig. 4. This foil morphology reflects the underlying layer structure of
the C-S-H which experiments and atomistic modelling show is a heavily
defective tobermorite structure [42,46,47]. C-S-H growing on grains of
alite, cement or filler may occasionally have a fairly foil-like appear-
ance, but more usually the foils seem to merge together to give the
typical spiky or “needle” morphology seen in Fig. 5. Despite the ap-
pearance of quasi one-dimensional growth of these needles, they are
still based on the layer structure of defective tobermorite.
2.2. Period II: the main hydration peak
In discussing the mechanisms governing the main peak it is im-
portant to stress that just being able to fit this curve does not validate
the model used to generate the curve. This point is underlined by the
fact that Costoya's [48] PSD experiment has been fitted by at least five
completely contradictory models [49–53]. As a consequence, hydration
models must be, in addition, assessed according to their physical,
chemical and microstructural soundness.
In the past, the two most popular hypotheses used to explain the
heat evolution peak were the diffusion layer and impingement hy-
potheses. As discussed below, neither of these hypotheses can explain
the experimental evidence. Two more recent hypotheses, confined
growth and dissolution limitation hypotheses, are then introduced and
critically discussed. Finally, we describe the C-S-H growth hypothesis
proposed by Bazzoni [54] and already presented in 2014 [2], which has
now received quantitative support thanks to the needle model [50].
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Cement and Concrete Research 124 (2019) 105823
Fig. 5. Alite grain with C-S-H “needles” growing on surface around the time of
the main heat evolution peak. Within the red circles, the surface of the alite.
From [58]. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
2.2.1. The diffusion layer theory
The diffusion layer theory postulates that as C-S-H precipitates on
the surface of the cement grains, it forms a thickening layer that ulti-
mately becomes thick enough to act as a diffusion barrier. Many models
before 2000 rely on this hypothesis, in particular HYMOSTRUC [55].
Even if many textbooks refer to this hypothesis as plausible, the evi-
dence built up against it over the last decade is overwhelming.
The arguments against the diffusion theory were already detailed in
the previous ICCC articles [1,2]:
1. Existence of gaps (as in Fig. 2)
If the outer C-S-H shell acted as a diffusion barrier, then the con-
centration of species and supersaturation within the gap would be
higher, so that precipitation should happen inside it rather than outside
the shell at the end of the “needles”. Yet precipitation carries on at the
ends of the needles, not in the gap, up to the end of the first day, which
is well after the peak.
2. No change in activation energy
If there was a transition of mechanism at the peak time, then the
activation energy of the first mechanism, during the acceleration, and
the second mechanism, during the deceleration, would likely be dif-
ferent. However, the activation energy, after 4 h, has been measured to
be constant not only throughout the whole peak but up to a few days
[56], indicating no change of mechanism during the first few days.
3. Unrealistic and changing values to fit the data of Costoya
Ten years ago, Bishnoi modelled the diffusion hypothesis through
his then newly developed platform μic (pronounced “mike”) [57] and
showed that the C-S-H diffusion coefficient had to be varied over one
order of magnitude to fit tricalcium silicate powders having different
fineness [52]. Such a variation of the diffusion parameters appears ad
hoc and required only to save the hypothesis given that no variation of
any C-S-H properties (which are forming from solution) has ever been
measured to depend on the powder fineness.
To these we add a fourth, which is that a continuous layer is not
formed at the time of the peak as illustrated in Fig. 5. This figure
shows a representative alite grain close to the main hydration peak, at
this stage quite significant parts of the grain surface (circled) are visible
between the needle like growths. With this level of porosity, the
K. Scrivener, et al.
Fig. 6. Schematic illustration of Avrami type nucleation and growth. [52]. The rate of growth is proportional to the surface area, so initially increases. When the solid
phases start to impinge the free surface for growth decreases and so is the rate.
transport of species through the layer could not be slowed down en-
ough.
Once inner product starts to form, which occurs from about one day,
thick rims of product eventually form around the reacting grains as in
Fig. 17. It is an open question as to whether these layers act as diffusion
barriers, this will be discussed later (Section 2.3.4).
2.2.2. Nucleation and growth with impingement
This theory proposes that the progressive impingement of C-S-H
hydrates from neighbouring grains lead to the transition from accel-
eration to deceleration. The rate of reaction is assumed proportional to
the surface of the growing hydrates. As hydrates impinge against each
other the surface in contact with water decreases and so does the rate.
This idea originated in the context of metal melts and was modelled by
Avrami [59]: Fig. 6 [52] illustrates this theory.
Modifications of this basic idea have been made to account for the
fact that the hydrates nucleate on the surface of the cement grains,
rather than homogeneously in space: so-called Boundary Nucleation
and Growth (BNG) [60]. BNG models were further refined to consider a
C-S-H densification mechanism [52] or anisotropic growth [49].
Many studies have tried to fit Avrami or BNG type models to kinetic
data, but different parameters emerge for each data set and there is a
lack of consideration as to whether the fitting parameters have any
physical meaning. For example, the fits to the Costoya data [48] by
Scherer et al. [49] require the growth rate of C-S-H to vary by a factor of
2.5 with the particle size of the cement and give thicknesses for the C-S-
H layer at the peak > 2 times higher than the thicknesses observed
experimentally.
However, the most conclusive evidence against the impingement
theory is the very weak effect of water to cement ratio on the main
hydration peak. The main hydration peak barely evolves from water to
cement ratio 0.4 to 0.8 as pointed out by Kirby and Biernacki in [61]. If
impingement was to explain the transition from acceleration to decel-
eration then the interparticle distance, which is directly linked to the
water-to-cement ratio, should influence it; yet this not the case. More
dramatic are the experiments of Garrault et al. [62] in dilute suspen-
sion, with water-to-cement ratio of 50, where the interparticle distance
is then in the order of tens of microns, well beyond any C-S-H thickness
measured at any time, and where a main hydration peak is still ob-
served at the same time and same height.
2.2.3. The confined-growth hypothesis and related models
Following the criticism of deceleration due to impingement, several
authors proposed that growth of C-S-H was restricted to happen no
more than one micron far from the grain surface in agreement with SEM
observations [51,53,63]. Although these models are closer to SEM ob-
servations, the imposition of the distance limit for hydrate formation is
completely arbitrary. However, in a sense it anticipates the limitation
on the length of the growth of the C-S-H needles, which is discussed
later. These models also suffer from other shortcomings. Biernaki and
Xie [63] elaborated a model based on a single grain size and Honorio
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Cement and Concrete Research 124 (2019) 105823
et al. [53] extended this to the full particle size distribution. However,
both predict 2 μm grains to release more heat at 24 h than any other
grains, but such small grains have already vanished by the peak time.
The model of Masoero et al. [51] also extended the model of Biernaki
and Xie, with a different treatment of the boundary for C-S-H growth:
when tested on Costoya's PSD experiment this predicts C-S-H thick-
nesses of 1 μm, which is more than twice the upper bound measured by
Costoya: (100–400 nm).
2.2.4. Another view: dissolution theory and the coalescence of etch pits
As discussed earlier, dissolution controlled by the undersaturation
of the solution, is the dominant mechanism during up to the end of the
induction period. Nicoleau and Nonat [33] proposed that this me-
chanism continues to determine the rate of reaction throughout the
main heat evolution peak. To summarise their views, the increasing rate
of reaction during the acceleration period is due to the opening of etch
pits which causes an increase in the alite contact surface area. Because
the flux of dissolution is proportional to the surface area of the dissol-
ving substance (here alite), etch pit opening results in higher exposed
alite surface and thus heat flow. At some point, the surface decreases,
for example by etch pits coalescence, which leads to the transition to
the deceleration period.
The main argument that dissolution is controlling the reaction rate,
is that the undersaturation of the C3S continually decreases throughout
the main heat evolution peak, but this is not a definitive argument for a
rate controlling step. If dissolution was rate controlling, the rate of
reaction would continually decrease (no deceleration period) and the
observed decrease can only be explained by a decrease in the surface
area. Etch pits have been observed during the whole hydration peak
[25,62], but there is no disappearance of the etch pits in the decel-
eration period. This is clear in Fig. 2, where the roughness of the re-
acting grain at 12 h (near the peak) is qualitatively the same as at 24 h
(at the end of the peak). Given the very different rates between the peak
and 24 h the roughness of the grains would need to decrease dramati-
cally (to around 10–15% of the roughness at the peak), if the change in
rate comes only from the amount of alite surface dissolving. Even at
28 days, Fig. 17, the grains show a high roughness, with a crystal-
lographic orientation. As discussed in Section 2.3.4 the impact of water
to cement ratio on the later kinetics also contradicts the argument that
dissolution is the sole rate controlling step.
2.2.5. C-S-H growth: the needle model
The work of Bazzoni [54] indicated that during the acceleration
period, clusters of C-S-H (needles) progressively nucleate on the cement
grains and grow rapidly to a certain length. The deceleration period
corresponds to a drastic slowing down of the growth rate of the C-S-H,
which at this point covers most of the surface of the grain (Fig. 7).
A key element in the development of this new hypothesis is the
impact of small amounts of zinc doping in alite [65]. This experiment
was repeated by Li [66] and the key results are shown in Fig. 8. The rate
of heat evolution shows that zinc doping has quite different effects on
K. Scrivener, et al.
Fig. 7. Evolution of the needle length with time for an alite paste at w/c = 0.7.
From [54].
the period 1 (up to the end of the induction period) and period II (main
heat evolution peak). The end of the induction period is delayed, pos-
sibly due to an impact of zinc on the alite dissolution, but also by the
inhibition of the nucleation of C-S-H, seen in the micrographs at 1 h. In
contrast, the main heat evolution peak is greatly enhanced, with an
increase in the cumulative heat at one day of around 65%. The en-
hancement of the main heat evolution peak corresponds to much longer
C-S-H needles in the case of the zinc doping, seen in the micrographs.
A new model was developed by Ouzia [50] to validate the hy-
pothesis that the reaction kinetics during the main heat evolution peak
are dominated by C-S-H growth. The model takes all its input para-
meters from experimental measurements and has no free fitting para-
meters. The use of an analytical, rather than numerical approach means
that calculations can be made rapidly and that both realistic grain
shapes (form factor and surface roughness) and realistic particle size
distributions can be accounted for. The disadvantage is that the mi-
crostructure is not simulated so impingements cannot be explicitly
calculated.
The model simulates the growth of C-S-H as cylinders (called nee-
dles) perpendicular to the surface of the cement grain (Fig. 9) and
computes the volume of C-S-H by summing the individual needles vo-
lumes over all grains. The volume of alite, water and C-S-H are com-
puted from the alite hydration reaction:
η1 Valite + η2 VH → η3 VCSH + η4 VCH
Finally, the heat of this reaction is computed and compared with the
experiments. The required input parameters are the nucleation and
growth rates of C-S-H with time, estimated from SEM and TEM images
and the PSD, form and roughness of the anhydrous grains, from laser
granulometry and SEM images,
The model was tested on 20 sets of experimental data (14 in [50]
and 6 more in [58]), covering ranges of particle sizes and alite doping
experiments. Experiments, which is a wider set of experiments than any
other alite hydration model yet published. Moreover, by contrast with
all previous models, the parameters were measured and thus con-
strained within experimental confidence intervals. Across the range of
experiments, the average error on the heat flow and DoH were re-
spectively of 16.2% and 10.1%. The model was able to capture varia-
tions of the peak height by a factor of 30. It was particularly interesting
6
Cement and Concrete Research 124 (2019) 105823
that for undoped alite or C3S very similar parameters for the C-S-H
nucleation rates, growth rates and needle length at the end of the fast
grow period could be used to simulate the kinetics of several different
preparations of alite or C3S.
The needle model quantitatively shows that the peak coincides with
the time at which most of the needles have nucleated and are in their
fast growth regime. The progressive coverage of the grain surface AND
the slowdown of the needle growth together account for the transition.
From a mechanistic point of view, the main hydration peak should
therefore be seen as a single episode, the separation into acceleration
and deceleration period is arbitrary and a heritage of Kondo and Ueda
[67] who were the first to qualitatively describe the calorimetry curve
of alite hydration in 1968. The model shows there is no qualitative and
sudden change of mechanism, only a progressive one which starts at the
onset of the acceleration and ends at about one day. This is why in
Fig. 1, we proposed to group the whole main peak in a single hydration
stage.
2.2.6. Key insights from the needle model
• Impact of dissolution of small grains
Experiments of fractionated powders [68] and other observations
[69] indicate that grains below about 5–7 μm are totally consumed by
the time of the peak. This led to the postulation that the disappearance
of these small grains may be a contributing factor to the deceleration
period [70]. The needle model [50] shows that the dissolution of the
small grains actually does not change the overall shape of the peak and
does not alone cause the transition from acceleration to deceleration.
Nevertheless, it does sharpen and shift it to the left whenever the PSD
incorporates a large fraction of grains below 10 μm. The experiments of
Bergold et al. [71] illustrate this effect: they studied very fine alite
powders and observed a shift of several hours of the peak time.
• Kinetics of the acceleration period are a linear function of
surface area
Whenever the dissolution of the small grain is negligible, the DoH
and heat flow, HF, were shown to be linear, not just monotonic, with the
needle length and initial specific surface of the powder:
η1
DoH (t ) = Δr H ∗ ∗ Malite ∗ Sspe ∗ l24h ∗ f (kn , s, tc , t )
η3
η1 df (kn , s, tc , t )
HF (t ) = Δr H ∗ ∗ Malite ∗ Sspe ∗ l24h ∗
η3 dt
where ΔrH is the enthalpy of reaction, η1 and η3 are the volumetric
stoichiometric coefficients of the alite hydration equation, Malite the
volumetric mass of alite, Sspe the initial specific surface of the powder,
l24h the needle length at 24 h, kn the nucleation rate, s the needle base
surface (needles are assumed to be cylinders) and tc the characteristic
needle growth rate, and f is the bell-shape curve defined by the un-
derlying algorithm (see [50] for details).
As a consequence, when calorimetry curves are replotted per unit of
initial specific surface, they show an interesting trend: Fig. 10. Coarse
enough powders exactly align on the same curve whereas powders
which incorporate a large fraction of grains below 10 μm are sharpened
and shifted left, though their acceleration periods still align. This re-
presentation per unit of surface also illustrates the influence of the
dissolution of the small grains on the main hydration peak. These re-
sults are consistent with experimental observations [687273].
• The influence of Zn on nucleation and growth
The needle model shows that the difference in needle length is
sufficient to quantitatively account for the impact of zinc doping on the
K. Scrivener, et al. Cement and Concrete Research 124 (2019) 105823

Fig. 8. Impact of zinc doping (3%) on hydration kinetics and microstructure of C-S-H. From the heat evolution curve the end of the induction period is delayed, while
the main hydration peak is dramatically enhanced. The large difference in the height of the main peak corresponds to a drastic change in the morphology of the C-S-H
needles, which are much longer and more clustered in the case of the zinc doped alite. Taken from [66].

reaction kinetics, Fig. 11. three phenomena together: dissolution, transport and precipitation. As
discussed earlier, one aspect, which needs to be understood better, is
how the reacting alite surface evolves and how the dissolution is af-
2.2.7. Next challenges
fected, by the deposition of hydrates on the surface and by the presence
To understand the mechanisms behind the observed nucleation and
of ions in the vicinity of the surface.
growth rates is clearly one of the next challenges. So far, most models
As a step in this direction Bellmann and Scherer [74] measured
take these parameters as input parameters but do not endeavour to
growth rates of C-S-H as a function of the solution concentration. In
explain them in terms of more fundamental mechanisms. Why is there a
Naber et al. [25] they used this date to calculate the expected rate of
burst of nucleation that lasts about 4 h, not 1 h, not 10 h? Why do
reaction from the measured pore solution evolution. The good agree-
needles initially grow fast and then slow down? Why does zinc promote
ment with the experimental rates, adds further support to the argument
the C-S-H growth?
that C-S-H formation strongly influences the hydration kinetics during
Because the driving force for precipitation is the supersaturation,
the main heat evolution peak.
and because the supersaturation is dictated by the balance between the
Another important contribution has been the modelling of C-S-H
dissolution and precipitation, future models should try to couple these

7
K. Scrivener, et al.
Fig. 9. Schematic illustration of the needle model algorithm. At time step 1 a
first generation of needle nucleates (in red). At step 2, a second generation
(blue) of needles nucleates while the first one grow fast. Gradually the surface is
covered and the needles grow slower and slower. The peak time corresponds to
the time where most of the generations have nucleated and needles are still in
their fast growth regime. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
precipitation from solution concentrations by Andalabi et al. [75]. The
past two decades of research on mineral nucleation and growth has
revealed a more diverse picture of these phenomena as demonstrated in
the recent textbook of Van Driessche, 2017 [76]. Common minerals
such as calcium carbonate, calcium sulfate, iron oxides, silica and
alumina have been shown to follow the non-classical nucleation theory.
New concepts have been brought forward like nucleation pathway,
clusters, liquid/amorphous precursors, crystalline intermediates, nu-
clei/crystallites aggregation etc., to describe the complex nucleation
and growth pathways of these minerals. The old “classical pathway”
thus appears to be just one among other pathways, and not necessarily
the most energetically favorable.
The paper of Andalabi et al. [75] suggests C-S-H precipitation em-
braces two overlapping phenomena: primary nucleation and growth,
secondary nucleation and growth. The primary nucleation and growth
generate crystallites of the order of 3 to 6 nm, the secondary nucleation
generate crystallites in the vicinity of already formed ones. The model
parameters - interfacial tension, cohesion energy, growth rate constant,
kinetic order of growth and aspect ratio – are fitted to the evolution of
calcium concentrations with time measured during synthetic C-S-H
precipitation. The values obtained show good agreement with those
obtained experimentally by other researchers. In particular, the C-S-H
particles are found to about 3–6 nm thick and about 100 nm wide
sheets, which matches very well TEM observations of synthetic C-S-H
[42,45]. This method provides a promising approach to look at the
impact of different parameters – such a solution composition and par-
ticularly other ions (sulfate, alumina, zinc, etc.).
In this section, it has been argued that the growth of outer C-S-H as
needles is the dominant influence on the hydration during the main
heat evolution peak. Towards the end of this period the formation of
“inner” product starts, in the regions originally occupied by the anhy-
drous grains. This inner product has an isotropic morphology, quite
different from that of the outer product, which appears granular in TEM
images. The start of the formation of inner product could be related to
the change in growth rate of the outer C-S-H. Initially the rate of growth
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Cement and Concrete Research 124 (2019) 105823
of the C-S-H with the “needle” morphology if much faster so this
dominates. As the rate of growth of the needles slows down, the rate of
formation of the inner product becomes comparable so both form at a
similar rate. However more work is needed in this area.
2.3. Period III: later ages
As discussed in the previous ICCC papers [1,2], there are still very
few studies which have investigated the kinetics and mechanisms
governing the later hydration period, after the main hydration peak.
The space filling hypothesis was raised as a leading mechanism at later
ages [2]. The fact that hydration is ultimately limited by the space was
made clear in the seminal work of Powers [77,78] and is a fundamental
assumption in the famous Power's model, where anhydrous cement
remains unreacted below a w/c of 0.38. If this was not the case then
cement pastes with a water to cement ratio below about 0.38 would
eventually expand significantly when stored in water, which is known
not to occur.
However, the work of Berodier indicated that “lack of space” starts
to impact the hydration kinetics after only a few days [79]. Whereas the
influence of w/c on the hydration for the first day is negligible, its
impact on the later ages is dramatic: 0.6 w/c PC pastes exhibit 15%
more DoH at 28 days than 0.4 w/c ones. The impact of water to cement
ratio on later kinetics is clearly illustrated for alite hydration in Fig. 12.
There are two (non-exclusive) ways in which the lack of space can
limit hydration, considering that hydrates precipitate from solution and
so can only grow in water filled spaces. Either the volume of water
available for precipitation is depleted or the remaining water filled
pores are smaller a critical pore size for precipitation.
2.3.1. Space filling limitation by lack of water
The space available for precipitation is space occupied by water, so
the original water to cement ratio controls the space available for
precipitation. Recently, Ouzia [58] showed quantitatively that the vo-
lume opened by the gap, which forms between the hydrate shell and the
reacting grain has a very important impact on the water filling of spaces
in sealed samples. Because the water flows from the external space (the
space outside of the C-S-H shells) to the gaps, the water in the external
space may be exhausted and precipitation stopped there.
Fig. 13 illustrates this effect on a 10 μm grain at w/c = 0.32 (the
volume of water is then exactly identical to the volume of alite). When
the gap is 1 μm, the grain has lost 50% of its mass so that half of the
initial water has flowed in. To this must then be subtracted the amount
of water that reacted with alite to form the hydrates. This computation,
shows there is no more water in the external space, which implies that
the outer hydrates cannot grow anymore.
This leads to a rule of thumb for space filling:
DoHexternal − space − filled = 1.6 w/c
Whenever the DoH is equal or superior to 1.6 w/c, there is no more
external water available and precipitation then stops in the external
Fig. 10. Simulated calorimetry curve computed for
different log-normal PSD whose mode varied from
0.7 μm to 91.6 μm. On the right, the curves have
been normalized by surface area and show the im-
pact of the small grain dissolution: it is negligible for
PSD coarser than 11.5 μm (all curves exactly align)
but for the finer PSD, it gradually decreases and
shifts the peak left. The fact that all curves align
during the acceleration period show that alite sur-
faces chemically react in the same manner in-
dependently of the PSD: the surfaces of small grains
is not more, or less, reactive than the surface of big
grains, from [50].
K. Scrivener, et al.
Fig. 11. Comparison of experimental results of Bazzoni et al. [65] for coarse (left) and fine (right) alite with and without zinc, with simulations from needle model
[50]. Left plot: coarse powder, right one: fine powder.
space.
This equation was corroborated at 20 °C and 40 °C as Fig. 12 shows:
a clear inflection point is seen on the 0.32 w/c systems cross
1.6 ∗ 0.32 = 52% of DoH.
2.3.2. Space filling limitation by a limiting critical pore size
In addition, more evidence has emerged indicating the importance
of the lack of water filled pores greater than a limiting critical pore size
[8081]. The role of pore size on crystal growth can be understood from
the schematic shown in Fig. 14. This shows a crystal which has grown
to fill the central (large) pore and can only continue to grow into to
smaller pores of radius rc. To do this the crystal must increase its cur-
vature, which requires a higher concentration of ions in a solution in
equilibrium with it.
If the system is completely saturated the Ionic activity product (K)
of the solution at equilibrium with a crystal of radius r is given by the
Freundlich equation [82]:
RT K ⎞ 2y
∙ln ⎜⎛ ⎟ =
Vm K sp rc
⎝ ⎠
where: R is the gas constant, T is temperature, Vm is the molar volume
of the crystal, γ the interfacial energy of the crystal, rc the radius of the
crystal-liquid interface, K the ion activity product of the solution and
Ksp the equilibrium ion activity product of a flat crystal surface.
This phenomenon of the limitation of water filled pores for crystal
growth is most obvious in the case of the formation of carboaluminate
phases (hemi (Hc) and mono carboaluminate (Mc)) in ternary blends of
Portland cement, calcined clay and limestone (LC3), Fig. 15 (left) [80].
As the calcined kaolinite content of the calcined clay component in-
creases the amount of Hc and Mc pass through a maximum and then
decreases. The time at which the Hc and Mc stop forming, corresponds
to the time where the pore entry size (by MIP) is refined to below about
10 nm. The Fig. 15 (right) shows a calculation for the ion activity
product of the solution in equilibrium with a crystals of monocarbo
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Cement and Concrete Research 124 (2019) 105823
aluminate of different curvatures using the equation above compared to
the measured pore solution [83]. This indicates that the pore solution
can only sustain growth in pores above about 10 nm in size.
Of course, the calculation in the example above oversimplifies the
real situation. The equation above only applies when all pores are water
filled. In reality almost all cementitious materials are only partially
saturated, because voids are formed after setting due to chemical
shrinkage. The existence of menisci causes under-pressure in the pore
solution, which will affect the equilibrium. Furthermore, the energy of
crystals is usually anisotropic. Nevertheless, the close agreement be-
tween the lack of water filled pores above a certain size observed ex-
perimentally and the calculation is remarkable. More work is needed to
better understand the mechanisms acting here and the balance between
growth, which appears to stop at the certain point, without producing
expansion and the closely related phenomenon where a continued state
of supersaturation in the solution leads to the exertion of crystallisation
pressure and macroscopic expansion, such as in the case of sulfate at-
tack (internal and external) [85-88] and periclase hydration.
2.3.3. The predominant role of outer C-S-H in the later ages
Returning to the kinetics of alite hydration, the needle model as
presented in [50] was later expanded to the later age kinetics in [58]. In
this extension the filling of space and impingements between hydrates
was dealt with by a statistical treatment. To support this development
of the model, the growth of outer C-S-H needles after the main peak was
quantified on SEM images of polished surfaces. Although the rate of
growth slows down dramatically, it was seen that they grow as much
from 1 to 28 days as during the first day. As a consequence, the volume
of outer C-S-H produced in the later ages is not negligible. The com-
putations show, that on average there is in total twice as much outer C-
S-H as inner C-S-H. This may sound surprising when one considers the
appearance of SEM polished sections (e.g. Fig. 17) but the following
argument may help: by 24 h, typical pastes have reached 50% of DoH.
This hydration results in almost all outer C-S-H. There is a further 30%
of DoH up to 28 days, the product of which are about equally
Fig. 12. Hydration kinetics for alite at 20 °C (left)
and 40 °C (right) at different water to cement ratios
and for different alite finenesses. The continuous and
dashed lines are superimposed up to a given DoH
beyond which they abruptly separate because of the
space filling. The horizontal dashed lines indicate the
rule of thumb prediction for external space filling:
80% line corresponds to the w/c = 0.5, the 51.2% to
the w/c = 0.32 and the 41.6% to the w/c = 0.26.
The black one in particular deals with 0.32 w/c ratio
exactly crosses the point where the 0.32 curves di-
verge from the 0.5 ones. From [58].
K. Scrivener, et al.
Fig. 14. Schematic illustration of crystal growing into a small pore (adapted
from [84]). Note there is a thin liquid film between the growing crystal and the
pore wall.
distributed between outer and inner C-S-H this amounts to roughly
twice as much outer C-S-H than inner C-S-H. The inner C-S-H is a
function of the outer C-S-H produced: the outer C-S-H opens the gap,
which then controls the space in which the inner C-S-H can form.
2.3.4. Perspectives: the later ages kinetics are not controlled by a single
overwhelming mechanism but a combination of them
The dataset built by Ouzia (Fig. 12) leads to the rejection of the
diffusion layer theory and dissolution hypotheses as alone sufficient
to account for the kinetics at later ages. On Fig. 12, the continuous lines
(high w/c curves) always have a higher DoH and a steeper slope. This is
particularly visible for the 20 °C experiments. If the inner C-S-H acted as
a diffusion barrier controlling the reaction rate, then higher DoH
Fig. 15. The amount of mono (Mc) and Hemi (Hc) carbo aluminate phases formed in different LC3 blends from Avet et al. [80] (left). On the right image, calculation
of the minimum pore radius in which Mc would be expected to grow according to the measured pore solution 83 and Freundlich equation [83] is shown.
10
Cement and Concrete Research 124 (2019) 105823
Fig. 13. First image from the left: equatorial of a
10 μm spherical alite grain at w/c = 0.32. At w/
c = 0.32, the volume of water equals the volume of
alite. On the second image, a 1 μm gap opens. On the
third one, half of the initial water has flowed in: a
1 μm gap on a 10 μm grains means that the grain has
lost about half its volume, this equals half of the in-
itial volume of water at this w/c. Fourth image: the
water consumed by the hydration is then subtracted,
the remaining water is not sufficient to fill even the
inner space; this would mean that hydrates can no
longer grow in the outer space. From [58].
systems should have thicker C-S-H shells and therefore react more
slowly; they should release less heat and thus have smaller slopes. If the
inner C-S-H rim acted as a diffusion barrier there would be significant
concentration gradients across this layer, which would be reflected in
compositional gradients of the C-S-H. EDS maps for the C-S-H rim,
Fig. 16, do not indicate any compositional gradient across the rim.
Similarly, dissolution cannot be alone rate controlling. Because a
higher DoH implies a lower alite surface, high w/c systems should re-
lease less heat and exhibit a lesser slope than low w/c ones. This does
not mean that diffusion or dissolution have no influence on the later
ages kinetics, only that they are not alone rate-controlling.
On the other hand, the disappearance of the small grains becomes
more and more important in the later ages. By definition 100% DoH
means that all grains have reacted, so that the closer the system is to
complete hydration, the more significant the impact of the dis-
appearance of small grains.
This discussion indicates that, at least some of the stages of hydra-
tion, require a combination of mechanisms to account for the experi-
mentally observed kinetics. Space filling, precipitation and dissolution
surely influence the later ages kinetics; the role played by transport and
the pore solution concentration remain open questions. Models that
attempt to fully understand the later age should couple these different
phenomena. However, it will by complicated to determine how me-
chanism combine, since even with single mechanisms it is possible to fit
hydration kinetics by adjusting parameters. As discussed further at the
end or tis paper, a systematic approach and a broad data are critical to
avoid falling in the “fitting trap”.
3. From alite to cement
3.1. The microstructures are very different
Despite the focus of most work, and this review, on the mechanisms
governing the hydration of alite, alite is actually NOT an ideal model
for the hydration of cement, particularly where microstructure is con-
cerned. This is illustrated by Fig. 17, which compares the mature mi-
crostructure of pastes of alite and cement paste, both at a water to
cement ratios of 0.4. The main differences are the in the distribution of
K. Scrivener, et al. Cement and Concrete Research 124 (2019) 105823

Fig. 16. EDS mapping of Ca/Si ratio across C-S-H rim.

Fig. 17. Microstructure and mercury intrusion porosimetry curves comparing alite to Portland Cement. MIP curves from [89]

11
K. Scrivener, et al.
Fig. 18. Impact of sodium aluminate on the hydration of alite from [92].
the calcium hydroxide masses and in filling of the originally water filled
space. Large open pores remain in the case of alite as confirmed in the
MIP curves from Mota Gasso [89].
The reasons for these pronounced differences were previously noted
by Kjellsen and Justnes [69] and investigated by Gallucci and Scrivener
in 2007 [90]. They showed that neither the addition of gypsum nor
alkalis to C3S significantly modified the microstructure, even though
these both modify the kinetics of hydration as studied in more detail by
Moto Gasso et al. [91]. The commercial cement microstructure could be
very well reproduced by a polyphase laboratory clinker of C3S and C3A
with the addition of gypsum (essential to control the C3A reaction). This
confirms that the difference cannot be attributed to some aspect of
commercial clinker production (such as quenching or grinding) and
indicates that the presence of alumina has an important impact on the
nucleation and growth of C-S-H.
Recent work of Pustovgar et al. [92] investigated the impact of
alumina in more detail by the addition of small amounts of NaAlO2. As
illustrated in Fig. 18, taken from this paper, NaAlO2 significantly en-
hances the main hydration peak. In the original paper the authors
propose that the effect of alumina is related to the existence of a frac-
tion of very fine reactive particles (< 0.2 μm). However, it is interesting
to note, that according to the needle model discussed above, this en-
hancement of the main hydration peak should correspond to the growth
of C-S-H outer product to a longer length in the fast growth phase.
Micrographs published in [93] do show that the C-S-H needles are
longer in the case of additions of aluminium, but more work would be
needed to distinguish between cause and effect.
The growth of longer C-S-H needles has two important effects: First
the infilling of the space between the grain occurs faster and is more
efficient. Second the formation of more outer product during the peak
will increase the size of the gap between the hydrate shell and the re-
acting grain, compared to the case of alite as has been frequently noted
experimentally [68,69].
3.2. New insights on the inhibition of C3A and factors affecting necessary
sulfate addition
Recently some nice studies by Geng, Myer, Monteiro and others
[94,95] have brought new insights on the inhibition of the C3A reaction
in the presence of gypsum. By a combination of synchrotron-based
methods, they were able to show that:
• Ettringite is the only (stable) hydration product in induction period
• Ettringite preferably nucleates on C A surfaces
3 Pourchet et al. [103] measured the variation of shear yield stress
• Ettringite grows to limited diameters and lengths
• There is no evidence that ettringite is a diffusion barrier.
This work indirectly supports the hypothesis of Minard et al. [96]
that the reaction of C3A is inhibited by the specific adsorption of the
sulfate and/or calcium ions on the surface of the grains of C3A which
12
Cement and Concrete Research 124 (2019) 105823
block dissolution sites.
This well-known inhibition of the C3A reaction by gypsum is im-
portant to have correct behaviour of a cement. It allows the main heat
evolution peak of alite to occur before the aluminate phase. Otherwise
the reaction of the alite is severely inhibited (undersulfation). When the
gypsum is exhausted, the reaction of C3A (and the ferrite phase) re-
starts. However, sulfate ions are absorbed on the C-S-H during the first
part of the reaction. So, after the depletion of gypsum, there is first a
new formation of ettringite, corresponding to the usually seen shoulder
peak and the AFm phases (mono sulfate or mono or hemi carbo alu-
minate) form later, usually after several days. This was detailed in the
previous ICCC paper [2], from the studies of Quennoz [97] and was
confirmed more recently by Jansen et al. [98]
It is known that the additions of supplementary cementitious ma-
terials, such as slag, fly ash or calcined clay require adjustment of the
level of sulfate addition in order to avoid undersulfation. It is usually
considered that this adjustment depends on the amount of alumina in
these additions. However recent work by Zunino [99] shows that the
fineness of the addition is also very important and that even an addition
of limestone changes the amount of sulfate needed. This is due to the
“filler” effect, whereby the addition of any fine material increases the
rate of reaction of the alite. This increased reaction of alite means more
sulfate is absorbed by the C-S-H during the main heat peak and there-
fore the sulfate depletion peak occurs earlier.
3.2.1. Influence of SCMS on hydration kinetics
Berodier and Scrivener [101] explained that the general trend of
acceleration of the hydration of the clinker in the presence of SCMs is
due to the shearing conditions generated in these systems. However,
limestone provides better conditions for the nucleation and growth of
C-S-H compared to other systems. From zeta-potential measurements,
Ouyang et al. [102 observed that the calcium ions have higher affinity
for adsorption on limestone filler, having a positive zeta-potential at
low concentrations of calcium compared to micronized sand particles
(quartz-like system). A calcite surface would favour chemical interac-
tions with Ca2+ ions thereby reducing its mobility possibly through
strong chemical bonds and increasing the probability of formation of
stable C-S-H nuclei. In the case of micronized sand, which according to
the authors have similar surface charge to C-S-H due to its similar iso
electric point (IEP), Ca2+ ions are not chemically adsorbed and here,
electrostatic and Van der Waals' forces are involved which reduces the
mobility of Ca2+ compared to the bulk, but still more mobile when
compared to chemically adsorbed species.
and zeta-potential on calcite particles as a function of concentration of
calcium ions in the solution. The authors observed a decrease in the
shear yield stress with an increasing zeta-potential measurement which
is a result of the stronger repulsive interaction forces exerted by the
adsorbed calcium inducing a better dispersion of the particles and thus
a lower yield stress. The authors observed that this is in accordance
K. Scrivener, et al.
Fig. 19. Heat flow measured for Portland cement (PC) compared with blended
systems with 50% replacement of limestone (L), quartz (Qz) and fly ash (FA).
All the curves are normalized to the mass of PC in the system with an effective
water to solid ratio of 0.75. Adapted from [100].
with the model of Scales [104] which predicts a linear decrease of shear
yield stress with the square of zeta-potential. However, beyond a cer-
tain limit of calcium concentration, zeta-potential plateaus and the
yield stress slightly increases due to the screening effect induced by the
resulting high ionic strength of the solution. As Pourchet et al. [103]
and Ouyeng et al. [102] worked on model systems, blended cements
bring even more complexities than these simple cases as observed by
Schöler et al. [105] (Fig. 19). Here, for the systems with limestone, the
dominating mechanism can still be attributed to the high affinity of
Ca2+ providing an ‘easy’ pathway for C-S-H nucleation.
4. Summary and perspectives
4.1. Period I
• There is more and more evidence against the existence of any in-
hibiting layer forming by dissolution and precipitation of a type of
C-S-H on the surface.
• Nevertheless, the first C-S-H precipitates may be metastable and
influence the pore solution concentration.
• This leaves the theory of dissolution controlled by undersaturation
as the most plausible explanation for the induction period.
• Work is still needed to determine the state, and effective interfacial
energy of alite upon contact with water.
• The formation of etch pits also needs to be studied in more detail,
particularly the very deep and regular erosion seen on certain alite
surfaces, as illustrated in Fig. 2.
4.2. Period II
• Neither diffusion, nor impingement, nor the dissolution of small
grains, explain or control the transition from the acceleration to the
deceleration period.
• The growth rate of outer C-S-H dominates this period.
• More work is need to understand the factors affecting the growth of
C-S-H, why does it slow down and why can some elements like zinc
and aluminium have such a great impact on the length of the
“needles” at the slow down.
• Dissolution and growth are coupled through the pore solution and
this coupling should be better incorporated into quantitative
models.
• As in period I the role of etch pits and surface roughness needs to be
better understood in this period.
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Cement and Concrete Research 124 (2019) 105823
4.3. Period III
• The filling of space becomes a key factor in this period.
• More work is needed to understand how the progressive filling of
space impacts the rate of reaction.
• There is no strong evidence that the diffusion of ions through pro-
duct layers is rate limiting.
• Neither is the rate of dissolution rate limiting in this period.
• It would be very interesting to know more about spatial variations in
the composition of the pore solution (diffusion gradients), but this
does not seem experimentally possible at present.
4.4. From alite to cement
• The main difference between the microstructure from the hydration
of cement compared to C3S is the more even and efficient filling of
the originally water filled space. This leads to much finer pores in
cement pastes.
• The presence of alumina seems to be implicated in these differences.
One explanation could be that its presence leads (directly or in-
directly) to the growth of longer needles during the main heat
evolution peak, which would also explain the formation of much
larger gaps between the hydrate shells and the reacting grains.
• Nevertheless, there is considerably more work to be done, which
considers the effect of all the other ionic species, including, for ex-
ample sulfate.
• The depletion of sulfate after the main heat peak of alite is impacted
by the amount of C-S-H formed, as sulfate ions are absorbed on C-S-
H during the first hours of hydration and later released leading to
the formation of ettringite in the shoulder aluminate peak, before
formation of AFm phases.
4.5. The importance of models
The complexity of the phenomena occurring during cement hydra-
tion requires models to be built to validate or refute the hypotheses
advanced to explain hydration. Hypotheses that are not expressed in
quantitative form in a model have only a very weak force of conviction.
However, so far, most publications dealing with hydration models
only show their model to satisfactorily fit a few calorimetry curves with
a “relatively” small variations of the input parameters. The mechanisms
may completely be wrong, like the Avrami or diffusion-based models
for instance, and still the model fits the calorimetry curves.
Alternatively, existing models based on completely different mechan-
isms are still able to fit the exact same set of calorimetry experiments.
Therefore, the ability for a model to fit calorimetry curves is necessary
but not sufficient to validate the underlying hypothesis.
Therefore, in our opinion, the methodology to move forward needs
to be sharpened and new criteria put forward such as:
i) The ability to fit a large enough dataset. As a rule of thumb
models should at least be able to fit twice the number experiments
than input parameters. It is also important to study several different
variables in a dataset. For example, it was not enough to vary just
the particle size of alite as in the experiments of Costoya [48], only
by varying also the water to cement ratio and the doping of alite
was it possible to refute different hypotheses and develop the C-S-H
growth (needle) mode, which could explain all the experimental
data.
ii) All the key experimental parameters that are known to influence
the reaction and commonly vary in real life applications should be
considered. At least the PSD for alite and amount and PSD each
phase assemblage for cement. Models dealing with the later ages
should additionally take the w/c into account as it has a strong
effect on the reaction [106].
iii) The ability to explain simultaneously results from several
K. Scrivener, et al.
techniques such as SEM, ICP, NMR, XRD or MIP instead of only
calorimetry. For example, nucleation and growth rates found by
fitting the calorimetry curve that are within the confidence inter-
vals measured by SEM reinforce the model and/or the underlying
hypothesis credibility. In the opposite case, as exemplified in
Section 2.2, the model and/or underlying hypothesis should be
rejected.
iv) An objective fitting process. Fitting requires an error function to
be defined followed by a standard fitting method such as the gra-
dient method, the simplex method or genetic algorithms. In all
cases, the uniqueness of the solution should be addressed.
v) Cross-comparison by testing the model on a common dataset.
So far Costoya [48] PSD experiment has served such a purpose for
alite hydration but only deals with five curves. Thermkhajornkit
et al. [107] has been used for testing cement hydration [53].
However, the field is still lacking a big enough dataset dedicated to
properly test either alite or Portland cement hydration.
Finally, a word on microstructural models, which seek to re-
present explicitly the entire microstructure. Microstructural models
such as CEMHYD3D, Hymostruc, μic [55, 57,108, have been very
popular since the late 1980s. the idea that we can simulate the entire
microstructure in a computer is very seductive. However, we feel it is
now time to take stock and clearly identify the limitations of this ap-
proach. First it is clear that even with the dramatic improvement in
computer power over the past decades, we are very far from the power
and speed which would be required to have a realistic representation of
a cementitious microstructure on the 100 μm scale. Voxel approaches
quickly run into problems of the size range of particles which can be
represented. Vector approaches necessitate the assumption of simplistic
grain shapes, such as spheres. However, the major limitations of these
models is the inability to represent the pore structure in any meaningful
way.
To understand this limitation, we need to return to the purpose of
microstructural models. Other than being just a nice visualisation, the
key purpose should be to predict the properties of a cementitious ma-
terial from its microstructure. Broadly speaking the properties of ce-
mentitious materials which are of interest are mechanical properties
and transport properties which determine durability.
For mechanical properties from the very first days of Concrete
Technology it was shown that after a few days mechanical properties
depend overwhelmingly just on the amounts of the different phases e.g.
Powers [77]. This either means that the way these phases are dis-
tributed in space does not matter or that the process of hydration means
that the way they are distributed is always statistically the same. We
feel that it is this later explanation which is most likely to be correct,
but in any case, it means you do not need a numerical microstructure to
better predict mechanical properties.
Regarding transport properties, there is now overwhelming evi-
dence that these are controlled by small pores below about 10 nm in
size. 1H NMR shows that there are no water filled pores above this size
after a few days [109]. MIP confirms that the connected porosity has
pore entries in this range after a few days and the limitations of space of
hydrate grow indicate that water filled pores above this size should fill
with hydrates in systems with reasonably low w/c ratios (< ~0.5). If a
microstructural model is to consider a reasonable particle size dis-
tribution of the anhydrous cement grains: on the order of 10s of μm
then the minimal system dimension of a microstructural model should
be at least 100s of μm. This is at least four orders of magnitude larger
than the size or pore which need to be considered for transport prop-
erties. In three dimensions, this means a digital representation would
need to have at least 1012 voxels which is well beyond the capacity of
today's computers (by comparison the atomic simulations on the most
powerful computers can only handle around 109 particles 110). But in
fact, the situation is much worse than that as, to be meaningful, we
need to consider the pore solution composition and, in each voxel, and
14
Cement and Concrete Research 124 (2019) 105823
interfacial effects, means that the concentration of species at interfaces
varies of a scale of < 1 nm.
In conclusion models are very important, but, when it comes to
hydration and microstructure, we need to be much more rigorous about
why and how we are using them.
Acknowledgements
Scrivener, Ouzia and Kunhi Mohamed are grateful for the support of
EPFL for their work. We also thank numerous friends and colleagues for
insightful discussions over the years, particularly Paul Bowen.
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