Cement and Concrete Research 168 (2023) 107156

Contents lists available at ScienceDirect

Cement and Concrete Research

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

Morphology-structural change of C-A-S-H gel in blended cements

Xiaohong Zhu *, Ian G. Richardson
School of Civil Engineering, University of Leeds, Leeds LS2 9JT, United Kingdom

A R T I C L E I N F O A B S T R A C T

Keywords: Pastes of white Portland cement (wPC) and wPC-30 % pulverized fuel ash (PFA), -60 % ground granulated blast
SCMs furnace slag (GGBS), -30 % or 60 % inert filler (anatase-type TiO2) blends were prepared to investigate the
Morphology dominant factors for morphological change of outer product (OP) C-A-S-H gel in blended cement systems. The OP
C-A-S-H gel
C-A-S-H gel in SCMs-blended cements changes its morphology from fibrillar-like to mixed fine-fibrillar/foil-like
Nano-structural change
when its Ca/(Si + Al) ratio < 1.30 and Al/Si ratio > 0.15. Meanwhile, the fine-fibrillar/foil-like C-A-S-H has the
mean length of the aluminosilicate chain longer than 7– 8, of which, the [SiO4] bridging site occupancy factor
(SOFBT) is higher than 0.6 and the [AlO4] SOFBT is higher than 0.3. The pore solutions show the characteristics of
effective saturation index (ESI) of CH < − 0.15 and ESI of jennite-based C-S-H gel < 0.10. The morphology of C-A-
S-H gel in inert filler blends remains fibrillar throughout the hydration.

1. Introduction partially replace the white Portland cement (wPC); one inert filler,
anatase-type TiO2, was used for comparison, replacing the same per­
Supplementary cementitious materials (SCMs) are used extensively centage of wPC. The pastes were examined using analytical transmission
in modern concrete to help reduce the carbon emission from cement electron microscopy (TEM), 29Si magic angle spinning (MAS) nuclear
industry and to enhance the durability of the concrete [1]. SCMs are magnetic resonance spectroscopy (NMR), X-ray diffraction (XRD) and
sources of additional Al (except for silica fume) and Si during hydration, thermal analysis.
which results in compositional changes of C-(A-)S-H gel [2]. The addi­
tion of SCMs such as pulverized fuel ash (PFA) [3] or ground granulated 2. Experimental
blast furnace slag (GGBS) [4] reduces the Ca/Si ratio and increases the
Al/Si ratio of C-A-S-H gel, and its morphology changes at the later age of A commercial white Portland cement (Hanson Castle, UK), anatase-
hydration [3,4]. The C-(A-)S-H gel – quantitatively the most important type TiO2 (Sigma-Aldrich, UK), PFA (Drax, UK) and GGBS (Francis
binding phase in cementitious materials – thus shows variable compo­ Flower, UK) were used in this study. Bulk oxide compositions are given
sition, morphology, and properties in blended cements [5–7]. The in Table 1. Iron-rich particles were hand-removed from PFA using a
morphology of outer product (OP) C-(A-)S-H gel defines the capillary magnet to reduce their impact on the NMR experiments (the detailed
pore structure of pastes, which affects the long-term mechanical and procedure is given in Ref. [3]). Other information on the raw materials is
transport properties that determine the durability [7]. Therefore, un­ given in the Supplementary materials.
derstanding the morphological changes of C-A-S-H gel due to the addi­ Five cement pastes were studied: neat wPC, 30 % PFA or TiO2-70 %
tion of SCMs is crucial for the assessment of the durability of the wPC, and 60 % GGBS or TiO2-40 % wPC. A water/binder (w/b) ratio of
materials. The OP C-(A-)S-H gel in either C3S or Portland cement shows a 0.50 was used for all pastes. The blended powders were pre-stirred for 5
typical fibrillar-like morphology [2,8,9], but will change to foil-like min. All five cement pastes were hand-mixed for 2 min and cast into 8
when PFA [3] or GGBS [4] react to a certain degree. The morpholog­ mL plastic tubes. These tubes were sealed with Parafilm and rotated
ical changes of C-(A-)S-H gel coincide with changes in its composition, continuously for 24 h at 9 r/min to avoid bleeding. The specimens were
nano-structure, and the solution environment [3,8,10]. The purpose of then cured in a water bath at 25 ◦ C for 1, 3, 7, 14, 28, 91, and 270 days
this paper is to demonstrate the morphological changes of C-A-S-H gel in (except for those used at 5 h). The samples were crushed and hydration-
blended cements after the reaction of SCMs and to identify the dominant stopped using solvent exchange with isopropanol (IPA), followed by
factors that affect this change. Two SCMs, PFA and GGBS, were used to drying in a vacuum desiccator. The treated samples were ground into

* Corresponding author at: Department of Civil and Environmental Engineering, the Hong Kong Polytechnic University, Kowloon, Hong Kong.
E-mail address: [email protected] (X. Zhu).

https://doi.org/10.1016/j.cemconres.2023.107156
Received 18 May 2022; Received in revised form 19 January 2023; Accepted 13 March 2023
Available online 28 March 2023
0008-8846/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

fine powder prior to analysis. hardened cement paste cylinders using a Buehler (USA) IsoMet™ low-
Isothermal conduction calorimetry (ICC) experiments were con­ speed saw with a diamond blade. The slices were hydration stopped
ducted at 20 ◦ C using a TAM-Air (TA Instruments, USA) with 8 twin- using isopropanol and dried in a desiccator. The dried slice was then
channels with quartz as the reference. Prior to the experiments, all of attached to a clean glass slide with cyanoacrylate glue and thinned by
the raw materials including DI water were placed in a room with con­ hand using progressively finer SiC papers (#500, #800, #1200, and
stant temperature of 20 ◦ C for around 3 h. 9 g of paste (6 g of binder and #2000, corresponding to the grain size of 30, 22, 15, and 10 μm) until a
3 g of DI water) was placed into a 20 mL ampoule. An external mixing thickness of approximately 30 μm. The thinned slice was removed by
method [3] (2 min shaken on an orbital shaker) was used and the am­ immersion into acetone and glued between two 3 mm diameter copper
poules were immediately moved to the equipment. Around 20 min was TEM grids using epoxy. The grid had a hole with dimensions of 2 × 1
used for equilibration, which was needed due to opening of the sample mm, which allowed the sample to be argon ion-beam milled in a Gatan
chamber. The measurements were carried out for 3 days. Two replace­ Precision Ion Polishing System (PIPS). The aim of ion milling is to form a
ment levels for GGBS, PFA and anatase were selected for comparison. hole in the centre of the specimen, with the region around the hole being
The CH content of the wPC, GGBS/wPC, PFA/wPC pastes was sufficiently thin to be electron transparent. The Gatan PIPS was vacuum-
determined by QXRD using the G-factor method with corundum worked at 3–4 keV with a milling angle in the range of 4–6◦ . The lower
(α-Al2O3) as the external standard [11]. The internal standard method milling angle (glancing incidence) vastly reduced the input energy,
was used for anatase (TiO2)-containing samples for all ages [12]. Hy­ preventing damage due to thermal affects. The whole PIPS process for
dration stopped samples were ground into fine powder and back-loaded each sample lasts for around 40–50 h. Samples were then stored under
into the sample holder. All data except those for 270 days blended wPC vacuum and carbon-coated using an Agar Scientific Turbo Carbon
samples were collected using a Bruker D2 Phaser (CuKα radiation; 30 Coater to prevent charging during TEM examination. The TEM experi­
kV; 10 mA) with a step size of 0.01◦ , dwell time of 1.0 s, rotation of 15 ments were carried out using a FEI Titan3 Themis 300 microscope
rot/min, and range of 5–70◦ 2θ. The 270 day samples were collected operating at 300 kV with a FEI Super-X 4-detector energy-dispersive X-
using a Philips X’Pert system with the same settings other than a range of ray analysis (EDX) system. Images were taken at magnifications ranging
5–80◦ 2θ. Patterns for corundum were collected using the same condi­ between ×5k to ×20k. EDX analyses were performed at ≈ ×20k with a
tions to determine the G-factor. The chemically bound water that was spot size of 3 and live time of 10 s. The OP C-A-S-H gel in blended wPC
used for the calculation of the mass attenuation coefficient (MAC) was systems (between 10 and 12 regions) were the main areas of interest.
calculated from the TGA data. Before each EDX analysis, the selected area electron diffraction (SAED)
The hydrated wPC samples (15–18 mg each) were analysed using a was used to check that the analysis region was C-A-S-H gel that was free
Stanton Redcroft Simultaneous Thermal Analyser STA 780 (UK) under of intermixture with crystalline phases. In addition, thinner parts were
N2 atmosphere with a heating rate of 20 ◦ C/min. An empty platinum chosen for EDX analysis to avoid the absorption of emitted X-rays and
crucible was used as the reference and the testing temperature range was allow straightforward quantification.
from room temperature (about 20 ◦ C) to 1000 ◦ C. The raw materials The pore solution of cylindrical paste samples (∅2.5 cm × 6.0 cm)
(20–40 mg) were analysed under the same conditions using a Netzsch was extracted under a constant pressure of 407.6 MPa (800 kN over
Simultaneous Thermal Analyser 449 F5 Jupiter (Germany) equipped 1962.5 mm2) for 45 min. A vacuum pump was used to avoid carbonation
with a mass spectrometer. The portlandite (CH) content was calculated of the collected solution. Extraction of pore solution from mature paste
using the tangent method with the consideration of mass loss from raw samples is very difficult and it was necessary to use 2 or more cylinders
materials. The details of the calculation methods for CH are provided in of each sample in order to obtain enough solution for analysis. The
the Supplementary materials. element concentrations in the collected solutions were tested by an ICP-
29
Si MAS NMR spectra were collected by a Bruker Avance III HD (WB OES (Perkin Elmer optima 8000, USA) using argon plasma. The equip­
magnetic field 9.4 T; operating frequency of 79.48 MHz for 29Si). All the ment was pre-heated for around 30 min to achieve a stable plasma
experiments were run at the magic angle of 54.74◦ , which was set by condition. The filtrated samples (0.45 μm PTFE Springe Filter) were
observation of 79Br resonance from KBr. Samples for NMR were freshly acidified with proper levels of 5 mol/L HNO3 and diluted with deionized
ground and packed into 7 mm zirconia rotors with KEL-F caps and spun water to end up with a pH value of around 1.0. Samples were filtered/
at 6 kHz. Since the natural abundance of 29Si is only 4.67 %, longer scans diluted prior to ICP-OES analysis because the equipment is very sensitive
are normally required for cement pastes to achieve quantitative spectra. to total solids and the alkali ions in the solution. Some important issues
In this work, the 29Si MAS NMR spectra were acquired over 4096 scans are summarised by Vollpracht et al. [15] and Dean [16]. The thermo­
(all PFA-containing samples except 91 days) or 2048 scans (all other dynamic modelling for the calculation of the saturation levels was per­
samples) using a pulse recycle time of 40 s, a pulse duration (width) of formed with PHREEQC V3.4.0 using the database provided by
5.5 μs (90◦ flip angle) for an RF field strength of 45 kHz, and an Lothenbach [17].
acquisition time of 40 ms. TMS (tetramethylsilane) was used as the
reference. Deconvolutions of 29Si MAS NMR spectra were performed 3. Results and discussion
using a user-made procedure for Igor Pro (WaveMetrics, USA) initially
developed by Brough [13]. The Voigt line shape (mixture of Cauchy- 3.1. Hydration process of blended wPC
Lorentz and Gaussian line shapes) was used for all peaks. Calculations
with the NMR results were carried out using the equations provided in Fig. 1 shows the effect of 30 % filler or SCMs on the hydration process
Refs. [2,14]. of wPC. In Fig. 1b and c, the black dash line represents the hydration
Samples used for transmission electron microscopy (TEM) were heat of neat wPC multiplied by 0.7. In the heat flow curves, it is very
prepared as follows. Slices (around 1–2 mm thick) were cut from the clear that three hydration peaks occur between 5 and 24 h. The

Table 1
Bulk oxide compositions of GGBS, PFA, and wPC (by mass %) determined by XRF.
Composition SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O SO3 LOI900◦ C

GGBS 35.07 12.43 0.41 8.41 40.67 0.38 0.58 0.78 − 0.15
Fe-removed PFA 51.26 25.27 6.80 1.78 2.47 1.98 3.57 0.48 4.03
Residual PFA 49.02 24.38 10.92 1.59 2.43 1.42 3.46 0.47 4.07
wPC 24.49 2.09 0.30 0.59 68.08 0.25 0.09 1.95 0.95

2
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 1. (a) Rate of heat evolution, (b) cumulative heat evolved (up to 100 h) and (c) cumulative heat evolved (0– 40 h) of neat wPC, 30%PFA-wPC, 30 % slag-wPC,
and 30%TiO2-wPC pastes.

dominant peak is due to alite hydration, with a first shoulder peak blended cements. In the current study, the cement slurry was mixed for
representing AFt formation and a second shoulder peak indicating AFm 2 min on a batch orbital shaker (~300 rpm), which was much slower
formation [18]. For all the samples with SCMs or filler replacement, than Berodier et al.’s work (1600 rpm–15,000 rpm). The differences in
both the first and second hydration peaks are reduced. This is due to the shearing rate may result in different heat evolution behaviours of
initial lower hydraulic properties of these fillers. The AFt formation peak blended cements. In contrast, GGBS has a totally different hydration
is accelerated by the addition of GGBS, but not by the PFA or TiO2. The curve compared to that of PFA or TiO2, which gives a much higher cu­
GGBS gives a higher and faster heat evolution curve when compared to mulative heat than the reference curve (i.e. wPC × 0.7). The main reason
that of PFA and anatase added samples, which is attributed to the self- is also due to the self-hydraulic property of GGBS [19]. The curves
hydraulic nature of GGBS [18–20]. The curves in Fig. 1c show that the passed the reference curve (i.e. wPC × 0.7) at around 20 h for the TiO2
heat evolution within 20 h for the 30 % PFA and TiO2 samples is the sample and at around 30 h for the PFA sample, which indicate the start
same and that it is lower than value for the 0.7 wPC curve, i.e. the heat of the ‘filler effect’ (i.e. a point where the hydration of wPC in the blends
that would be expected upon simple dilution. This result is not consis­ is accelerated). These results are similar to those summarised by
tent with Berodier et al.’s [21] view of the ‘filler effect’ during the early Richardson et al. [3] in which the cumulative heat curves of two PFA-
age hydration of cement; however, it is the same as Richardson et al.’s containing samples surpassed the reference at around 25 h. The same
results [3]. This shows that the PFA or TiO2 have an initial retarder effect effects are found in 60 % fillers or SCMs added samples, which are given
on wPC hydration. The ‘filler effect’ cannot be simply explained as the in the Supplementary materials.
increase of extra surfaces for nucleation, which should be the effects of
either a higher nucleation density or a higher growth rate of C-(A-)S-H
gels [21]. The microscopical observations by Berodier et al. [21] indi­ 3.2. Phases present in blended wPC and Ca(OH)2 content evaluation
cated that the filler showed little or no effect on the growth rate of in­
dividual C-S-H needles. Instead, the shearing between particles was The crystalline phases in all blended wPC pastes were identified by
found to be one of the dominant factors that can generate more nuclei in XRD (see the Supplementary materials), and included unreacted alite
and belite, CH, and AFt; additional hydrotalcite-like phase was found in

3
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

GGBS blends after 3 d of hydration; unreacted mullite (in PFA), melilite of TiO2 blends remain higher until 270 days, which means that TiO2
(in GGBS), and anatase remained in the blends throughout the does not consume CH and a higher hydration degree is achieved. This
hydration. result is also supported by the lower residual clinker peaks in TiO2
Fig. 2a and b shows how the CH content (percentage of ignited mass) blends in XRD patterns (see the Supplementary materials). As expected,
developed with age for the both 30 % and 60 % replacement level sys­ the PFA and GGBS consume CH and CHact/CHexp ratios in these two
tems determined by TG-DSC analysis. The CH content increased over systems gradually decrease with age to values that are lower than 1. The
hydration time. The unfilled circles in these two graphs represent the CH ‘changing ages’ (from >1 to <1) from TG for 30 % PFA and 60 % GGBS
of neat wPC multiplied by 0.7 or 0.4 for the purpose of comparison, blends are around 40 days and 14 days, respectively. The same infor­
which can be therefore regarded as the reference data (denoted as mation but obtained from QXRD analysis regarding CHact/CHexp ratios is
CHexp) for the SCMs/filler added samples based on simple dilution [3,4]. given in Fig. S12 in the Supplementary materials.
The measured CH contents in the blended system are denoted as CHact. Fig. 3 shows a plot of the bound water in hydrates against age
The ratios of CHact to CHexp were calculated for each blend and are calculated from TG-DSC analysis data. The unfilled circles represent the
plotted in Fig. 2c. expected chemically combined water (CWexp) multiplied by the wPC
Fig. 2c shows that the samples containing PFA and TiO2 have a lower content (i.e. ×0.7 and ×0.4) based on the simple dilution. The measured
CH content than expected at 5 h, indicating that initial hydration of wPC bound water in blends is denoted as actual bound water (CWact). The
in the blends is retarded. In contrast, the value of CHact/CHexp for 60 % ratio of CWact/CWexp was calculated and given in Fig. 3c. The chemically
GGBS is >1, indicating acceleration. These results are consistent with bound water is present in both C-A-S-H gels and crystalline phases. It is
the conduction calorimetry results shown in Fig. 1. The initial retarder notable that the CWact/CWexp ratio of GGBS blends is always higher than
effect of PFA was also observed by Richardson et al. [3], who noted that 1, which supports the acceleration of hydration of cement. This value is
there have been considerable differences in the effects of PFA on cement much higher than those for TiO2 and PFA blends. This is due to the self-
hydration reported in the literature: some studies report retardation of hydraulic property and higher reactivity of GGBS that can generate more
the hydration of the aluminate phase, some support retardation of the hydrate phases (including crystalline LDH phases; see XRD results in the
hydration of the silicate phases, and some consider that both aluminate Supplementary materials) and therefore more bound water [22,23]. An
and silicate hydration are retarded; on the other hand, some studies extreme high CW value for the 60 % TiO2 blend is found at 5 h, which is
report a totally opposite view. It is evident that the mechanism regarding perhaps due to flocs of the nano-scale particles (see the PSD in the
the effects of PFA particles on the hydration of cement is complex and is Supplementary materials) trapping water that is difficult to remove
affected by the characteristics of the materials and the hydration envi­ during the hydration-stopping process.
ronment. The results in the current study support the view that the Comparison between CWact/CWexp and CHact/CHexp is given in Fig. 4
aluminate reaction is not significantly affected by 30 % PFA but slightly for the purpose of identifying the reason for the increasing CWact/CWexp
retarded by 60 % PFA (see the Supplementary materials); whereas the ratio. The relationship between these two ratios is shown in Fig. 4a for
silicate reactions are initially retarded significantly by replacing 30 %– the TiO2 (inert filler) blends and in Fig. 4b for the SCMs (GGBS and PFA).
60 % PFA (see Fig. 1 and Fig. S6 in the Supplementary materials). These As confirmed by XRD (Supplementary materials), the hydration prod­
results are also supported by the CH data, which gives a CHact/CHexp ucts are the same in the TiO2 blends as in the neat cement, and so any
ratio lower than 1 at early age, indicating initial retardation of the sil­ additional bound water must be due to greater quantities of those phases
icate reactions. and thus to acceleration of the silicate reactions.
However, the values of CHact/CHexp for TiO2/PFA-containing sam­ A good correlation between CWact/CWexp and CHact/CHexp is
ples shown in Fig. 2c rise at intermediate ages, which indicates an ac­ observed for the TiO2 blends, as shown in Fig. 4a, which means that the
celeration of the silicate reaction during this period (the so-called ‘filler TiO2 accelerates the hydration of the cement at later ages and generates
effect’). After around 3 day hydration, the CHact/CHexp ratio of PFA more hydration products (i.e. CH and C-S-H gel). In comparison to the
blends drop down, which indicates the commencement of the pozzolanic TiO2 blends, the SCM blends give different relationships between CWact/
reaction of the glassy phase in the PFA; whereas the CHact/CHexp ratios CWexp and CHact/CHexp. GGBS generates more CH and more bound

Fig. 2. CH content evaluation from TG-DSC: (a) at 30 % replacement level; (b) at 60 % replacement level; (c) calculated parameter CHact/CHexp. where CHact is the
actual CH content in blended cement and CHexp is the expected CH content calculated by the percentage of wPC.

4
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 3. Chemically bounded water determined by TG-DSC: (a) at 30 % replacement level; (b) at 60 % replacement level; (c) calculated parameter CWact/CWexp.

Fig. 4. Relationships between CWact/CWexp and CHact/CHexp (calculated from TG-DSC analysis) in a. inert filler (TiO2) and b. SCMs-blended wPC systems.

29
water than ‘expected’, and the quantity of bound water is greater than 3.3. Si NMR analysis of blended wPC samples
that derived solely from the extra CH. This observation is supported by
the conduction calorimetry results, Section 3.1. The extra CH results 3.3.1. Experimental observations
from the accelerated hydration of the Portland cement and the extra Fig. 5 shows the 29Si MAS NMR spectra and the deconvolution of all
bound water is from the extra CH, C-A-S-H gel and also LDH phases blends hydrated for 270 days. Spectra for other ages (7, 14, 28, 91 days)
(AFm and Mg,Al LDH phases are identified on the XRD patterns; Sup­ are given in the Supplementary materials. The results from deconvolu­
plementary materials). The deviation from the slope that is observed for tion are shown in Figs. 6 to 10. The same peaks related to the possible
the TiO2 blends (when compared with GGBS blends) is due to the structural silicate units but with different intensities are assigned to
participation of the glassy GGBS in the hydration reactions. For the PFA these blended cements, which include monomer (belite, Q0) at ≈− 71.3,
blends, the values of CWact/CWexp and CHact/CHexp are both around 1 at chain-end tetrahedra (Q1) at ≈− 79.2, and middle-chain tetrahedra at
intermediate ages, the latter having risen from below 1, consistent with ≈− 81.5 for Q2(1Al) or ≈− 85.2 ppm for Q2(0Al) [2,20,24]. In addition, a
a slight acceleration effect of the PFA particles. Commencement of the small peak due to monomers in γ-C2S is present throughout all blends
reaction of the glassy phase in both SCM-blends is associated with the and samples. For GGBS and PFA blends, additional peaks that belong to
consumption of CH and formation of C-A-S-H gel, which results in values glassy PFA at ≈− 106.8 (Q4) and GGBS at ≈− 76.0 ppm are assigned to
of CHact/CHexp and CWact/CWexp that are respectively lower and higher remove the effect of unreacted SCMs [3,4,25,26]. A small Q0H peak
than 1. throughout the hydration has often been assigned at a chemical shift
quite close to γ-C2S [3,13] but this peak is ignored in this work due to its
small size and the overlap with the γ-C2S.
Fig. 6 shows the distribution of silicate anion units in the C-A-S-H

5
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 5. Examples of 29Si MAS NMR results of blended cements: (a) 270d wPC; (b) 270d 30Ti-70wPC; (c) 270d 30PFA-70wPC; (d) 270d 60Ti-40wPC; (e) 270d
60GGBS-40wPC. The deconvolution of other-age samples can be found in the Supplementary materials.

phase in different blends from 7 to 270 days. The data are normalized to paste and the TiO2 blends until 91 days and then remains stable until
100 % to indicate more clearly how the relative amounts of the silicate 270 days, accompanied by an increase in Q2(0Al) but stable Q2(1Al).
species change with age. This observation is caused by the limited alumina sources that are pre­
It is clear that the early-age (7 days) C-A-S-H is dominated by Q1 in sent in the wPC system. Overall, the TiO2 blends possess higher fractions
neat wPC and TiO2 blends (≈65–70 %), which is consistent with pre­ of Q2 compared with that of the neat wPC paste, which is consistent with
vious studies that concluded that the dominant silicate group is dimer at the lower intensity of Q0 that means a higher hydration degree of silicate
early hydration of either C3S paste [13] or neat wPC [3]. In the PFA phases is achieved throughout the testing ages. In contrast, PFA blends
blend at the same age (Fig. 6c), the fraction of Q1 is slightly lower at show a continuous decreasing trend of Q1 tetrahedra and an increasing
around 60 % but the Q2(1Al) is similar, which are consistent with ac­ trend of Q2(1Al) units, which shows evidence for the PFA reaction.
celeration of the alite reaction and no reaction of the PFA. In GGBS blend However, the fraction of Q2(0Al) remains quite similar to that in neat
at 7 days, the fraction of Q1 is lower at 50 % accompanied by a larger wPC and TiO2 blends. The silicate tetrahedra distribution, especially
fraction of Q2(1Al) (i.e. from ≈12 % in neat wPC to ≈ 20 %), which are Q2(1Al) units, is different in GGBS blends. Specifically, the fraction of Q1
consistent with some reaction of the glassy GGBS. tetrahedra drops dramatically between 7 and 14 days, accompanied by
The fraction of Q1 tetrahedra decreases with age in the neat wPC increased Q2(1Al) but limited change to Q2(0Al). This result indicates

6
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 6. Normalized silicate species distribution of blended cements against

time: (a) 270d wPC; (b) 270d 30Ti-70wPC; (c) 270d 30PFA-70wPC; (d) 270d
60Ti-40wPC; (e) 270d 60GGBS-40wPC.

that the reaction of GGBS is fast during the corresponding ages (7–14
days) but slows down thereafter. In comparison with neat wPC or TiO2
blends, the fraction of Q2(1Al) tetrahedra is significantly larger after 30
and 14 days in PFA and GGBS blends respectively.
An interesting observation is that the fraction of Q2(0Al) is quite
similar at 270 days in all of the samples (≈35–40 %, i.e. over 1 in 3),
which agrees with Richardson et al.’s study of water- and KOH-activated
PFA blends [3]. The main variation is the relative amounts of Q1 and
Q2(1Al) (i.e. the end-chain tetrahedra and the paired tetrahedra that are
adjacent to the Al–O ‘bridging’ tetrahedra (BT)). These data support the
Fig. 7. Hydration degree of silicate phases (alite + belite) of blended cements
view that the main difference in C-A-S-H between SCM blends and inert
calculated through quantitative NMR.
filler/neat cement blends is the incorporation of additional Al at
bridging sites only, which further lengthens the silicate chains of C-A-S-
H [3,27,28]. Thus, the increase in the fraction of Q2(1Al) tetrahedra is an occurs at around 14 days, when the reaction of the clinker is again
indicator for the reaction of SCMs, but not a sign of the start of the re­ retarded.
action. As shown in Fig. 6, it can be confirmed that PFA reacts contin­
uously and slowly between 30 days (i.e. the Q2(1Al) fraction is greater 3.3.2. Nanostructure development of C-A-S-H gel in blended wPC
than the highest value in 30TiO2 blends) to 270 days and GGBS reacts The increased polymerization of silicate tetrahedra results in up-field
between (but not starting at) 10 days (i.e. the Q2(1Al) fraction is greater chemical shifts in NMR spectra [29]. Many studies have confirmed a 6
than the highest value in 60TiO2 blends) to 270 days. ppm up-field difference in the chemical shift of Q2 tetrahedra when
Fig. 7 shows the hydration degree of the silicate phases in the clinker compared to Q1 (at ≈− 79 ppm) in 29Si NMR spectra e.g. [29–32]. The
(i.e. alite + belite) against age for different blends, as determined by chemical environments of Si–O tetrahedra are further affected by the
NMR. As expected, the inert filler (TiO2) blends give higher hydration replacement of Si by Al at bridging sites in an aluminosilicate chain [27],
degree all through 7 to 270 days, which is consistent with the results of which generates a down-field chemical shift of ≈3–5 ppm [3,27,33].
CHact/CHexp as shown in Fig. 2. This experimental phenomenon is Therefore, the peak at ≈− 82 ppm in 29Si MAS NMR spectra has been
believed to be brought about by the ‘filler effect’. Similarly, a higher assigned as Q2(1Al) in many studies [2,20,24,27,34,35], and the
hydration degree of (alite + belite) is achieved in the PFA blend at 7 assignment is supported strongly by the excellent agreement between
days, which can also be attributed to the ‘filler effect’. However, lower the Al/Si ratio of the C-A-S-H calculated from the results of the decon­
hydration degrees of PFA blends are found afterwards. The same results volution of the NMR spectra with the value measured directly by
are found in GGBS blends throughout 7 to 270 days. The decreased analytical TEM (as shown in Fig. 17 in [35] and Fig. 11 in [3]). More
hydration degree of silicate phases in PFA and GGBS blends is plausibly than three peaks have been used by some other workers. As an example,
related to the hydration of the glassy phases, which provide Si and Al for Yang et al. [36] assigned a peak at − 86.7 ppm to a second type of Q2P
the formation of C-A-S-H, thus decreasing the requirements of silicate (pair) site, but that peak was only observed with C-A-S-H that had a very
phases in the clinker. In summary, from the CH data, the crossover for low Ca/Si ratio (0.6 to 0.8) and extremely long Al–Si chains, and they
PFA happened at around 60 h (i.e. the ‘filler effect’ kicked in at around assigned peaks at around − 81 ppm and around − 82 ppm to Q2P(1Al [4])
60 h), whilst from the NMR data, it appears that a second crossover and Q2B (bridging) sites respectively. However, since it is not possible to

7
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 8. (a) Al/Si ratio (determined by NMR results) and (b) Ca/(Al + Si) ratio (calculated using the universal relationship in [3]) development against time.

Fig. 9 shows how the mean silicate chain length (MCL) and MCLSi (i.
e. the value for just the silicate portions) of the aluminosilicate chains in
the C-A-S-H vary with age for all the cements in this study (calculated
from the NMR results). A similar study on 30 % PFA blended cements [3]
showed that the MCL increased from an initial value of ≈3 before 28
days up to ≈10 after 1 year and 14 after 13 years, whereas the C-A-S-H in
the neat wPC also had a MCL of ≈3 before 28 days, but increased to only
4.4 after 1 year and ≈5 after 4 years. The results plotted on Fig. 9 are
consistent with the earlier work. Inspection of the figure shows that: (i)
neat wPC has an MCL ≈ 3 at 7 days and increases to ≈4.5 at 270 days;
(ii) the MCL for the TiO2 blends are slightly higher than for the neat
wPC, which is attributed to the higher hydration degree; (iii) the values
for the 30 % PFA blend are comparable with the neat wPC before 28
days (≈3–5) but then increase to ≈7.5 at 270 days; (iv) the MCL for the
60 % GGBS blend is significantly higher than for the neat wPC at all
measured ages, from ≈4.5 at 7 days, rising to ≈9.0 at 270 days; (v) the
values of MCLSi for the C-A-S-H in all the samples are similar and in­
crease slightly with age.
Fig. 9. MCL and MCLsi of blended samples at (a) 30 % replacement level and These results agree with previous studies that have shown that, in
(b) 60 % replacement level. general, the MCL increases with age and with increases in both Al/Ca
and Si/Ca ratios [3,14,24,35,37]. The increase in MCL with age is ach­
resolve these different peaks in the one-dimensional 29Si spectra ieved by the increased occupation of bridging sites in the aluminosilicate
collected in the present study, and given the general agreement between chains, and since at any given age the values of MCLSi are similar for the
Al/Si ratios determined by TEM-EDX and those calculated from 29Si C-A-S-H in the neat wPC pastes and in the blends, the higher value of the
NMR when using three peaks for C-A-S-H during the fitting procedure, MCL observed for the PFA- and slag-containing blends is achieved by
no attempt was made to use more than three peaks. additional Al[4] at the bridging sites. It is thus evident that the bridging
The Al/Si ratio calculated from the results of the quantitative NMR of site is occupied preferentially by Al[4], which is consistent with the
all blends is shown in Fig. 8a. Unsurprisingly the Al/Si ratios of the C-A- conclusion that Al[4] substitutes for Si[4] only in the bridging tetrahedra
S-H in the neat wPC and TiO2 blends are essentially the same and they of the dreierketten chains of C-A-S-H [27,38]. In a study of synthetic C-
remain stable in a range of ≈ 0.07–0.09, which corresponds to the stable A-S-H prepared with a high Ca/Si ratio, Kunhi Mohamed et al. [39]
value for Q2(1Al) in Fig. 6. The PFA and GGBS blends show a completely associated a peak at 5 ppm on an 27Al spectrum with low intensity at
different development trend of Al/Si ratio for the C-A-S-H. For the GGBS − 77 ppm on the 29Si spectrum; they assigned the − 77 ppm to paired
blend, the Al/Si ratio reached >0.10 at 7 days and rose to ≈0.17, which silicate tetrahedra adjacent to bridging sites occupied by Al[6]. If pre­
indicates that the glassy GGBS started to react before 7 days and sent, such a peak could not be observed in our one-dimensional 29Si
continuously hydrated until 270 days. The PFA blend initially possesses NMR because of the severe overlap with the Q1 peak, and in any case,
a comparable Al/Si ratio with neat wPC or TiO2 blends, followed by a the absence of significant amounts of Al[6] at bridging sites of the C-A-S-
steep increase to ≈ 0.15 at 270 days, which illustrates that PFA reacted H that is present in hardened cement pastes is indicated by the general
mainly after 2 weeks. These results agree with the CH content evaluation agreement between the Al/Si ratios determined by TEM-EDX with those
from TG-DSC analysis in Fig. 2. calculated from 29Si NMR when assuming the incorporation of only Al[4]

8
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 10. Site occupancy factor (total) for bridging sites (SOFBT), site occupancy factor for bridging sites by Si4+ (SOFBT(Si)) or by Al3+ (SOFBT(Al)). Values are
calculated by equations given in [14].

at bridging sites.
The C-S-H that forms in cement systems has linear silicate chains that
appear to follow the sequence of dimer, pentamer, octamer … (3n− 1) (e.
g. [35,40]). Since the removal of all, one half and one third of BT from an
infinite ‘Dreiereinfachketten’ silicate conformation results respectively in
linear dimer, pentamer and octamer chains, it is reasonable to assume
that lengthening of the chains in C-S-H is achieved by the insertion of BT
[2,13,14,28,35,41,42]. Fig. 10 shows how the occupancy factor for the
bridging site (SOFBT) [14] varies with age for the C-A-S-H that is present
in the samples in this study. The values of SOFBT for all the samples
increase with time but the values are significantly higher for the SCMs
blends. It is evident that the values for SOFBT(Si) increase gradually as
hydration progresses for all the blends, and that this value is comparable
with that for the neat wPC and TiO2 blends. The value of SOFBT(Si) for
the SCMs blends is initially slightly higher than for the wPC or TiO2
blends but at later age (270 days) it is similar (≈0.3). Thus, the
lengthening of the aluminosilicate chains (the increase in MCL shown in
Fig. 9) is primarily due to an increase in SOFBT(Al) – i.e. the increases in
both MCL and Al/Si (Fig. 8) are due to the presence of Al[4] in BT.
Fig. 11 is a plot of the Ca/(Si + Al) against reciprocal MCL for the C-
A-S-H present in all the blends examined in this study. The points C-D-E Fig. 11. Relationships between reciprocal mean chain length and the mean Ca/
and F-G-H correspond to dimeric jennite- and tobermorite-based struc­ (Si + Al) ratio of the C-A-S-H presented in this study (aged from 7 to 270 days)
tural units that have maximum (w/n = 2), intermediate (w/n = 1), and in blended samples. The Ca/(Si + Al) ratio of C, D, E is 2.50, 2.25, 2.00; for F, G,
minimum (w/n = 0) protonation levels. The points U-V-W and X-Y-Z are H is 1.50, 1.25, 1.00; for U, V, W is 1.675, 1.500, 1.325; for X, Y, Z is 1.0, 0.83,
the same but for infinite chain length [2,41]. Therefore, the quadrilat­ 0.67. The details of the explanations and schematic illustrations could be found
eral area C-E-W-U represents a mixture of jennite-based nanostructure, in [2]. The relationship between the mean chain length and the mean Ca/(Si +
whereas F-H-Z-X is for tobermorite-based nanostructure [2,41]. Most of Al) ratio of the C-A-S-H is given in Fig. S15.
the data points fall within the jennite-based area, which suggests that

9
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

the nanostructure of the C-A-S-H in those samples can be adequately aspect ratios of these fibres define the shape, size, and number of
described using a mixture of jennite-based structural units. However, the capillary pores [3,7,43–45], thus affecting the durability of the struc­
points for some SCM blends that have a longer MCL fall between the ture. Therefore, establishing the reason for the morphological change of
jennite- and tobermorite-based zones. This finding roughly agrees with OP C-A-S-H is a principal objective in this study.
the results for various metakaolin-, PFA-, and GGBS-blends that are Fig. 12 shows TEM images that illustrate the typical morphology of
summarised by Richardson et al. [3], but at earlier ages. In that work, OP C-A-S-H in blends containing TiO2-, PFA, and GGBS at different ages.
the C-A-S-H with a longer MCL tended to fall into the tobermorite-based The ages of the samples selected for the figures (PFA-91, 270d/GGBS-14,
nanostructural zone (F-H-Z-X). It is observed that the change in the 28d) correspond to be the ages where the morphological change of the
morphology of C-A-S-H in water-activated SCMs blends starts from the C-A-S-H occurs due to the reaction of the SCM. The OP C-A-S-H in the
intermediate zone in this figure. The change in morphology is important TiO2 blends always had a fibrillar-like morphology illustrated in Fig. 12,
for durability because of the reduction in the connectivity of the capil­ which is the typical morphology that is observed throughout the hy­
lary pores and thus reduced permeability. This is discussed in the next dration of neat cement or alite [2,7,44,46]. The unchanged morphology
section. indicates that the inert filler does not change the basic nanostructural
Based on the parameters above, Richardson and Groves’ model [41] element of the C-A-S-H gel. The morphology of OP C-A-S-H observed in
is used here to express the average composition of C-A-S-H gel at the PFA and GGBS blends at the ages of 91 and 14 days is similar – i.e. it
different ages based on minimum protonation assumptions. The is thin fibrillar-like. However, after each SCM had reacted to some
chemical-structural formulae can be found in the Supplementary extent, a change was observed, with the OP C-A-S-H having a much
materials. denser/finer fibrillar morphology and some totally foil-like regions. The
morphology at this stage is almost always described as ‘mixed fine-
3.4. Morphology and chemical composition of C-A-S-H gel in blended fibrillar/foil-like morphology’ [3]. OP C-A-S-H that has totally foil-like
wPC samples morphology has only been observed in water-activated pastes with
100 % GGBS [2–4,9,19,35], 80 % GGBS-20 % CH [9], or that have
The C-A-S-H that forms in the originally water-filled space (called relatively large additions of microsilica [47]. In contrast, the OP C-A-S-H
outer product, OP C-A-S-H) or within the original boundaries of the is always foil-like in alkali hydroxide-activated pastes, including those of
particles of cement or SCM (called inner product, IP C-A-S-H) have neat Portland cement as well as blends that contain GGBS and PFA
different morphologies. The IP C-A-S-H normally shows fine-scale and [2,3,34]. The micrograph for the PFA blend in Fig. 12 shows an example
homogenous morphology in either alite or blended cement systems [2]. of a small AFt relict embedded in OP C-A-S-H.
The morphology of OP C-A-S-H in GGBS-, PFA-, and metakaolin- The compositions of the C-A-S-H in the pastes studied in this work
blended cements changes from fibrillar at low Si/Ca and Al/Ca ratios to are represented on Fig. 11 using mean values, but it is instructive in
foil-like at high ratios [3], which is believed to be the reason for terms of nanostructural models to also examine the distributions of in­
permeability improvement in these systems. Indeed, the morphology of dividual TEM-EDX chemical analyses of OP C-A-S-H on Al/Ca vs. Si/Ca
OP C-A-S-H directly determines the connectivity of capillary pores that atom ratio plots. For the purpose of direct comparison with the data
are interlaced by these gel phases. The space constraints, fineness, and from this work, Figs. 13 to 15 show the distributions from previous

Fig. 12. Bright-field TEM images that show the morphology of C-A-S-H in different samples: 30TiO2–70wPC at 270 days; 60GGBS-40wPC at 14 and 28 days; 30PFA-
70wPC at 91 and 270 days. The TiO2-containing samples showed unchanged C-A-S-H morphology until 270 days, whilst GGBS/PFA containing samples showed C-A-
S-H morphology change between the testing ages.

10
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 13. Summary of TEM-EDX data for OP C-

A-S-H in wPC or OPC hydrated for 1 m
(month) to 20 y (years). The cross (blue)
stands for the wPC hydrated for 1 m at 25 ◦ C;
the empty circles stand for OPC hydrated for
14 m and 20 y. Although the Al2O3 content
for OPC is 6.19 % much higher when
compared to that of wPC (2.35 %), the Al/Si
ratio did not significantly increase. Additional
Al should present in Al-bearing phases such
like AFt, AFm, and TAH. Data were taken
from [4,48,49]. (For interpretation of the
references to color in this figure legend, the
reader is referred to the web version of this
article.)

Fig. 14. Summary of TEM-EDX data for OP C-A-S-H in PFA blends hydrated for 28 days to 13 years. The empty circles stand for 30PFA-70wPC blends hydrated for 1
m, 1 year and 13 years; the black cross stands for 50PFA/50wPC hydrated for 13 years.
Data were taken from [3,49,51].

studies of the analyses of OP C-A-S-H in neat OPC pastes, and in blends of single chain are BT, the saturation condition is Al/(Al + Si) = 3/11,
OPC with PFA or GGBS [3,4,19,25,34,48,49]. Points are also included which is labelled here simply as T11. The points in the figures for the T11
that represent the compositions of tobermorite (T-) or jennite-based (J) units that have 1, 2 and 3 BT occupied by Al are connected by dash lines.
structural units with the chain lengths of 2, 5, 8, 11, 14, 17, and ∞ Data for neat Portland cement pastes and for blends that involve PFA
[2,28,41]. Three ideal protonation (Si-O-H) levels of the silicate chains or GGBS are collated separately on Figs. 13, 14 and 15 respectively. All
are also given: the maximum level (Si/Ca highest; w/n = 0), an inter­ three figures show the Al/Ca-Si/Ca plots from both the T/J and T/CH
mediate level (Si/Ca medium; w/n = 1), and the minimum level (Si/Ca approaches. The points include pure wPC and OPC hydrated from 1 m
lowest; w/n = 2). Most of the T3n-1 units are saturated with Al at bridging (month) to 20 y (years) and the Al2O3% content for wPC is 2.4 % and for
sites (i.e. all bridging tetrahedra in the silicate chain are AlO4). The OPC is 6.2 %. The circles correspond to OPC and the crosses are points
exceptions include T11(1Al) or T11(2Al), where only 1 or 2 bridging sites for wPC. The scatter points tend towards the points for the J2 units. The
are occupied by Al (i.e. the silicate chain is not saturated with Al; Al/(Al distribution is therefore consistent with the T/J model and may further
+ Si) = 1/11 or 2/11). Since 3 of the 11 tetrahedra in an undecamer be associated to fibrillar morphology [2,3]. In addition, the Al/Ca atom

11
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 15. TEM-EDX data for OP C-A-S-H in GGBS blends hydrated for 14 m to 20 years. The black cross stands for the GGBS/OPC blends hydrated for 14 m; the empty
circles stand for the same samples but hydrated for 20 years. The GGBS replacement levels range from 10 % to 100 %. Data were taken from [4,20,34,54].

ratio of C-A-S-H in all pure cement samples is under 0.10 regardless of GGBS in blends reduces the overall CaO content, and this is reflected in
hydration time or Al content. This can be attributed to there being suf­ the simultaneous increase in the Al/Ca and Si/Ca ratios of the C-A-S-H.
ficient Ca in the systems to allow the formation of C-A-S-H with higher This also happens with hydration time (from 14 m to 20 years) because
Ca/Si ratio. Accordingly, the MCL of these C-A-S-H gels will not increase of continued reaction of the glassy slag (e.g. see Fig. 18 in [4], which
to a higher level and the incorporation of Al3+ is low because of the shows the reduction in mean Ca/Si ratio).
limited availability of tetrahedral bridging sites in the silicate chains The distributions on Figs. 13 to 15 of data from previous studies all
(experimental results show that the MCL for C-S-H gel in high-Ca sys­ tend towards to the points for the J2 units, which means that the TEM-
tems is short, e.g. values of ≈2.75, ≈3.40, and ≈3.60 for C-S-H in β-C2S, EDX data for C-A-S-H gels that are present in water-activated pastes of
OPC, and C3S pastes hydrated for ≈1 year with an average Ca/Si ratio neat wPC/OPC, PFA blends, or GGBS blends are all consistent with the
ranges from ≈1.7 to 1.9 [9]). Al is instead present in phases such as AFt, T/J nanostructural model. This is different from those in alkali-activated
AFm, and perhaps TAH [3,50]. The existence of TAH has been ques­ pastes, which show distributions on Al/Ca-Si/Ca plots that tend towards
tioned recently with the peak on 27Al NMR spectra previously assigned the origin [3], and are thus consistent with a T/CH structural model
to it attributed instead to Al[6] present at bridging sites in C-A-S-H instead of T/J.
[36,39]. As noted above, this cannot be a significant mechanism for the The TEM-EDX data collected during the present study are compared
incorporation of Al in the C-A-S-H that is present in hardened cement on Fig. 16 with those from previous studies that have already been
pastes because of the general agreement that has been observed between presented and discussed. Again, many of the new data are consistent
the Al/Si ratios determined by TEM-EDX with those calculated from 29Si with a T/J model with those at higher Al/Ca and Si/Ca values also
NMR when assuming the incorporation of only Al[4] at bridging sites. compatible with a T/CH model [4]. The TiO2 blends exhibit similar Al/
The Al/Ca-Si/Ca data for OP C-A-S-H in PFA-containing pastes are Ca-Si/Ca plots to those for neat wPC. The Al/Ca ratio is always lower
shown in Fig. 14 on plots again representing both the T/J and T/CH than 0.10 and remains stable with age. The structure of C-A-S-H gel in
points of view. The data are for a 50PFA-50wPC blend (black crosses) TiO2 blends can be explained by the combination of T2/T5 and J2/J5
hydrated for 13 years, and 30PFA-70wPC blends (unfilled circles) hy­ structural units, which is consistent with the observed short MCL (≈3.0),
drated for 1 m (green), 1 year (dark blue), and 13 years (light blue). A as shown in Fig. 9. It is evident that for PFA and GGBS blends, most of
general trend of increasing Al/Ca ratio along with Si/Ca ratio can be the points are in agreement with the previous studies.
observed as hydration time increases. Also, a higher PFA content results The Al/Si ratios obtained from NMR and TEM-EDX are compared in
in higher Al/Ca and Si/Ca ratios. Comparison of the two plots shows that Fig. 17 (left). The black-dash diagonal line (y = x) is used as a guideline
the TEM-EDX scatter points can be explained by both T/J and T/CH for the relationship. It is clear that all the data are distributed close to the
models including data for 30PFA blend hydrated for 1 year and 13 years. line, indicating a good relationship between the results from TEM-EDX
In addition, only limited change in Al/Ca ratio is observed for the 30PFA and NMR. This is consistent with results from previous studies
pastes hydrated from 1 year to 13 years, which indicates the hydration involving PFA and GGBS [3], and thus further supports the assumption
degree of PFA is mostly achieved before 1 year. A higher degree of hy­ that is used in the calculation of the Al/Si ratio from 29Si NMR data that
dration of PFA is reached when cured at a higher temperatures (55 and there cannot be significant amounts of chain-terminating Al (because
85 ◦ C) [25,49,52,53], which results in a slightly higher Al/Ca ratio of OP that would result in a value from NMR that is greater than that deter­
C-A-S-H. mined by TEM) [27]. Previous studies [3,28,34,55] have shown that
Fig. 15 shows TEM-EDX data for OP C-A-S-H present in PC-GGBS there is a universal compositional relationship for the C-A-S-H that is
blends hydrated for 14 m (average values, black cross) and 20 years present in cement blends that incorporate aluminosilicate-rich supple­
(scatter points, empty circles) with GGBS loading ranging from 10 % to mentary cementitious materials. This means that in the absence of data
100 %. In this case, all data points at lower replacement levels (<10 %) from TEM-EDX, it is possible to estimate the Ca/(Si + Al) ratio of C-A-S-
are consistent with the T/J model, whereas those at higher levels can be H in a PFA- or GGBS-containing cement using that relationship and the
explained by both the T/J and T/CH models. Increasing the content of value of the Al/Si ratio calculated from the deconvolution of a 29Si NMR

12
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 16. TEM-EDX data for OP C-A-S-H present in 30TiO2, 30PFA, and 60GGBS blends hydrated from 14 to 270 days compared with data from previous studies. The
black filled circles stand for short-age samples and the red ones stand for long-age samples in individual blend; the symbols for the data from previous studies are
explained in the captions for Figs. 13 to 15. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 17. Relationships of Al/Si ratio (left), Ca/(Si + Al) ratio (middle), and Al/Si-Ca/(Si + Al) (right) calculated from NMR (by using the Al/Si ratio as stated in
Fig. 8) and TEM-EDX. The black dash lines stand for y = x function. The error bars stand for the standard deviation from the mean value of each scatter point. It
should also be noticed that the 29Si MAS NMR should be collected using quantitative conditions (i.e., sufficient scans and delay time) to ensure the precision of the
NMR values.

spectrum. This process is demonstrated for the data from the current The Ca concentration in the pore solution is highly dependent on its
study in Fig. 17: the graph in the middle shows the Ca/(Si + Al) ratio counterpart-silicate groups (HxSiO(4-x)
4 ) and hydroxide ions (OH− ). In
from TEM-EDX plotted against the value from NMR, and the right-hand most cases, the long-term Ca concentration is below 10 mmol/L,
graph is a plot of the Al/Si v Ca/(Si + Al), with points either from TEM- consistent with most previous studies [15,17,23,56–62]; however, in the
EDX (unfilled symbols) or NMR (solid symbols). cement pore solution (wPC) with low pH value, this concentration can
reach ≈30 mmol/L and then stabilise at ≈10 mmol/L [56,57]. The data
for the pore solution in wPC in this study fall between ≈1 and 10 mmol/
3.5. Pore solution analysis and thermodynamic calculations L. These values are slightly higher than that of ordinary PC but lower
than the wPC in Refs. [56,57]. The reason should still attribute to the
Fig. 18 shows the main element concentrations in pore solutions alkali content of starting cements, where the high Ca concentration is
extracted from the blended cement pastes together with the reference
achieved by 0.13 wt% N2O and 0.02 wt% K2O in the starting wPC
lines of chemical compositions from CEM I pore solutions that were [56,57]. The general trend of decreasing Ca is identified, which is
compiled by Vollpracht et al. [15]. Since the ICP-OES mainly gives the
attributed to the increased alkali concentrations.
element concentrations, elements are used in the figures or discussion The Al concentration is low and hard to detect due to the lower
instead of ions. The Na and K concentrations are crucial for the main­
content of C3A present in wPC (2.1 wt% Al2O3) and the high stability of
tenance of alkalinity of the pore solution but depend mostly on the Al/S-bearing phases [63]. Therefore, the Al concentration remains low
original chemical compositions of cement. Fig. 18a–b shows that the Na
at ≈0.1 mmol/L and shows a stable trend against time. The addition of
and K concentrations in the current study are lower than the reference GGBS gives a higher concentration of Al.
CEM I sample. This is attributed to the lower N2O% and K2O% contents
The Si concentration is crucial for the stability of C-S-H, which is a
(0.249 wt% and 0.087 wt%) of the starting wPC when compared to those counterpart to Ca in the pore solutions. The slight increase in the trend
of CEM I (0.20–0.31 wt% and 0.76–1.03 wt%) [15]. Whilst only limited
can be observed, which is opposite to that of Ca concentration, as ex­
pore solution data were generated in this study, Fig. 18 shows that the pected [64,65]. Moreover, the addition of SCMs will increase the Si
values are in general consistent with the compilation of Vollpracht et al.
concentration.
[15].

13
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 18. Chemical compositions of pore solution from blended cement pastes: (a) Na; (b) K; (c) Ca; (d) Al; (e) Si; and (f) hydroxide ion. The concentrations of
hydroxide ion refer to the free concentrations based on the measured pH values [58,60,61,66]. The black solid line in each figure stands for the average concentration
of individual ion (element) in CEM I system and the red dash lines stand for the 95 % confidence interval as summarised by Vollpracht et al. [15], which is used for
comparison with the data generated during the present study. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)

14
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Finally, the hydroxide ion (OH− ) concentration obtained from the pH perhaps the critical value of the morphological change discussed in
values increases as the hydration progresses. This is because the alkali- Section 3.4.
ions are released from the clinker phases as they react. Therefore, the Fig. 20 gives the ESI values of T/J-type C-S-H gels in both pure and
OH− should roughly be charge-balanced with that of the sum of free Na blended cement systems. The equilibrium of C-S-H gel depends on the
and K concentrations. In addition, the increased alkalinity affects the Ca Ca, Si, and OH− concentrations in the pore solution. For the T-based C-S-
concentration. The relatively lower OH− concentration when compared H, the higher Ca and OH− concentrations will result in a lower IAP (ionic
to that of CEM I also results from the lower alkali content of the starting activity product) value and thus a lower ESI value. The decreasing trend
cement. of ESI-T-C-S-H can be confirmed in pure cement system, which results
Fig. 19 shows the values of effective saturation index (ESI) for CH in from the increased pH values of pore solutions. However, for the
both pure cement systems and blended cements; data from the current blended cements, the lower pH values and possible higher Si concen­
study are combined with others compiled from the literature. The gen­ tration will maintain a relative higher ESI-T-C-S-H value than that of
eral trend of ESI-CH seen in pure cement system starts at ≈0.15 and then pure cements. However, no significant trend can be identified from the
stabilises at ≈0.05 at later age. The values drop steeply between 0.2 and available values. The experimental data from the current study (solid
1 day and then gradually decrease until around 10 days. The experi­ symbols) support the presence of T-based C-S-H in the blended systems.
mental values from the current study (filled symbols) fall around the Fig. 20c–d gives the same information but for J-based C-S-H in both
stable value after 10 days. In contrast, the SCMs-contained samples have systems. Unlike T-based C-S-H, the higher Ca, Si, and OH- concentra­
the ESI-CH values that change from positive to negative at long age as tions will result a higher IAP and thus a higher ESI value. Therefore, the
hydration progresses as shown in Fig. 19b. The GGBS-containing sam­ decreasing trend of ESI-J-C-S-H must result from the decreasing Ca
ples show a higher ESI-CH value than that of pure cement before 1 day, concentration against time in the pore solution. Similar deceasing trends
which should be attributed to the initial low pH value of the pore so­ can be plotted in both pure and blended systems in the range of 0.1 to ≈
lution that results in a higher Ca concentration. However, as the hy­ 0.4 and 0 to ≈ 0.3 respectively. Some of these values even fall below
dration goes on, this value drops quickly below zero, showing that the zero. However, the data in this study gives a relatively higher value,
continuous consumption of CH happens in such systems. The general which may be due to the lower pH values obtained by using wPC. One
tendency gives a linear decrease trend against logarithm of time. It possible link between the morphology-change and the ESI of C-S-H gels
should be noticed that the ESI-CH values at 14 and 28 days are lower may be that the fine-fibrillar/foil-like morphology is associated to the
than zero, and this coincides with changed morphology (from fibrillar/ ESI-J-C-S-H < 0.1.
foil mixture to fine-fibrillar/foil) of C-S-H gels in the system. The black
dash-line suggests that the ESI-CH drops down to − 0.15 at around 28 3.6. Discussion on the dominant factors affecting C-A-S-H gel morphology
days. in blended cements
Unlike the ESI-CH values in GGBS blends, those in PFA blends stay
positive at ages before ~40 days as shown by the red dash line in 3.6.1. C-A-S-H gel morphology vs. solid phase composition
Fig. 19b. But at later ages, the trend again suggests a value of − 0.15 as The Ca/(Si + Al) ratio of C-A-S-H gel remained at ≈1.7–1.9 in the

Fig. 19. Effective saturation index (ESI) of CH in different (a) pure cements and (b) blended cements: empty/half-filled symbols are data taken from the literature
and solid symbols are data from the current study. The references [1–4] shown in this figure stands for Refs. [11,56,60,67].

15
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 20. ESI of different C-S-H gels in pure or blended cements: (a) T-type C-S-H in pure cement; (b) T-type C-S-H in blended cements; (c) J-type C-S-H in pure
cement; (d) J-type C-S-H in blended cements. The T-type stands for tobermorite type C-S-H (Ca/Si ratio = 0.83) and the J-type stands for jennite type C-S-H (Ca/Si
ratio = 1.67) [17].

pure wPC system (Fig. 8), regardless of the increased CH content (Fig. 2) content in the systems studied in this work in combination with the data
as the hydration proceeded. The situation is the same in the blends with compiled in [3]. In the SCM blends, the Ca/(Si + Al) ratio decreases as
the TiO2, whereas in the blends with the SCMs, CH is consumed by the the CH content decreases. The black dash line shows the general trend as
reactions of the glassy slag or fly ash. The presence of fibrillar C-S-H a guide for the eye. The data from the current study fall around the line
morphology in the TiO2-blends therefore shows that the absolute CH and are centred in the area that is associated with the mixed fibrillar/
content in the system is not a direct factor that affects the morphological foil-like morphology. In contrast, the Ca/(Si + Al) ratio does not
change of C-A-S-H gel from fibrillar to foil-like. On the other hand, the change with the reduced CH content that occurs with an increase in the
value of CHact/CHexp can be a reliable factor, which gives information amount of inert TiO2 filler (it remains at ≈1.80), and so those data do not
about the amount of CH that is consumed by the SCMs. The critical value follow the guide line. The C-A-S-H has coarse fibrillar-like morphology
for the morphological change appears to be around 0.85 in both the PFA regardless of the absolute CH content.
and GGBS blends, which is the same value as reported previously [3]. The DoH of the clinker (alite and belite) shows no direct influence on
Fig. 21 shows the changes of Ca/(Si + Al) ratio of C-A-S-H against CH the morphology-change of C-(A-)S-H gel, as shown in Fig. 7. For

16
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

Fig. 21. Relationship between CH content (%) and the Ca/(Si + Al) of C-A-S-H
gels that were calculated from the 29Si MAS NMR data as outlined in Section 3.4 Fig. 22. Further information calculated from 29Si MAS NMR: (a) hydration
and Fig. 17. The data (together with the error bars) were compiled with those degree of SCMs (ignoring the sidebands, which will result a lower value than
from Fig. 24 in [3] together with the guide line. The labels follow those in the expected, see Fig. S14 (Supplementary materials)). The filled square (30PFA-
literature, i.e. water/KOH-activated PFA (circles), metakaolin (diamond), or 91d) was not connected in the curve because it was affected by the sideband-
GGBS (triangle) (open symbol = entirely fibrillar morphology; half-filled sym­ effect of PFA, which resulted in experimental error during the deconvolution;
bol = mixed fibrillar/foil-like morphology; filled symbol = entirely foil-like). (b) Q2(total)/Q1 ratio; (c) Q2(1Al)/Q2(total) ratio (proportion of Q2(1Al) units
Data from the current study are labelled with the symbols with a cross inside. in all Q2 units); and (d) Q2(1Al)/Q2(0Al).
Only data from mature blends are used for comparison, i.e. wPC and TiO2
blends hydrated for 270 days; PFA blends hydrated for 91 days and 270 days;
GGBS blends hydrated for >14 days. used as the indicator for morphological change when SOFBT > 0.60 or
SOFBT(Al) > 0.30.
example, the DoH of clinker in TiO2-containing samples were much
4. Summary
higher than those in samples containing SCMs at later ages; however, the
morphology of C-A-S-H remained fibrillar. Whilst the morphology-
The factors that affect the morphological change of C-A-S-H gel that
change is affected by the DoH of the SCMs, it depends on the replace­
occurs in blended cements were investigated. Two SCMs (PFA, GGBS)
ment ratio, reactivity, and chemical compositions of the SCM used.
and one inert filler (TiO2) were blended with wPC. It was found that the
Fig. 22a gives the DoH of PFA and GGBS in the blends from NMR (but
morphology of C-A-S-H in cements containing the SCMs changed from
ignoring the sidebands); both increase with time and thus contribute to
fibrillar-like to mixed fine-fibrillar/foil-like, whilst in pure or inert-filler
the change in the composition of the C-A-S-H.
blended cements it remained fibrillar throughout hydration. The solid
and liquid phases were characterised using multiple techniques to better
3.6.2. C-A-S-H morphology vs. its nanostructure
understand the reasons for the change in morphology. The main ob­
As shown by the experimental observations given in Sections
servations are summarised as follows:
3.3–3.4, the nanostructure of C-A-S-H has crucial effects on its
morphology. The foil-like morphology is linked with the long MCL of ≈
(a) The C-A-S-H morphology-change happens in 60%GGBS blends
7–8 and with increased incorporation of Al (average Ca/(Si + Al) ratio
within 14–28 days and in 30%PFA blends within 91–270 days.
< 1.30 and Al/Si > 0.15), which are both associated with increased T-
(b) The C-A-S-H morphology-change is dominated by its chemical
based structure. A value of Q2(1Al) > 30 % appears to be associated with
composition, nanostructure, and solution environment.
the change in morphology. Fig. 22b–d shows some further comparison of
(c) The morphology-change happens when CHact/CHexp < 0.85.
Q2(1Al) and other Q2 units, which give more parameters related to the
(d) The foil-like morphology appears when the C-A-S-H gels show the
above value. Specifically, Q2(total)/Q1 ratio > 2.0, Q2(1Al)/Q2(total) >
following characteristics: Ca/(Si + Al) ratio < 1.3 and Al/Si ratio
0.45, and Q2(1Al)/Q2(0Al) > 0.80 are three related parameters that
> 0.15; the MCL ≈ 7–8; the SOFBT > 0.6 or SOFBT(Al) > 0.3; the
affect the morphological change. In addition, the SOF factors can also be

17
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

proportion of Q2(1Al) > 30 %; Q2(total)/Q1 ratio > 2.0; Q2(1Al)/ [10] E. Tajuelo Rodriguez, et al., Composition, silicate anion structure and morphology
of calcium silicate hydrates (C-S-H) synthesised by silica-lime reaction and by
Q2(total) ratio > 0.45; Q2(1Al)/Q2(0Al) ratio > 0.80.
controlled hydration of tricalcium silicate (C3S), Adv. Appl. Ceram. 114 (7) (2015)
(e) The foil-like morphology appears when the pore solutions show 362–371.
the following characteristics: ESI of CH < − 0.15 and ESI of J- [11] S. Adu-Amankwah, et al., Influence of limestone on the hydration of ternary slag
based C-A-S-H gel < 0.1. cements, Cem. Concr. Res. 100 (2017) 96–109.
[12] K. Scrivener, R. Snellings, B. Lothenbach, in: K. Scrivener, R. Snellings,
(f) The DoH of clinker (alite + belite) and the absolute CH content B. Lothenbach (Eds.), A Practical Guide to Microstructural Analysis of
are not direct factors related to foil-like morphology. The DoH of Cementitious Materials, CRC Press, Boca Raton, 2016.
SCMs depends on their replacement ratio, activity, and chemical [13] A.R. Brough, et al., In situ solid-state NMR studies of Ca3SiO5: hydration at room
temperature and at elevated temperatures using 29Si enrichment, J. Mater. Sci. 29
compositions. (1994) 3926–3940.
[14] I.G. Richardson, Model structures for C-(A)-S-H(I), Acta Crystallogr. Sect. B: Struct.
CRediT authorship contribution statement Sci. Cryst. Eng. Mater. 70 (Pt 6) (2014) 903–923.
[15] A. Vollpracht, et al., The pore solution of blended cements: a review, Mater. Struct.
49 (8) (2015) 3341–3367.
Xiaohong Zhu: Conceptualization, Methodology, Investigation, [16] J.R. Dean, in: D.J. Ando (Ed.), Practical Inductively Coupled Plasma Spectrocopy
Data curation, Formal analysis, Writing – original draft, Writing – re­ Analytical Techniques in the Sciences (AnTS), John Wiley & Sons Ltd, England,
2005.
view & editing. Ian G. Richardson: Conceptualization, Methodology, [17] B. Lothenbach, Thermodynamic equilibrium calculations in cementitious systems,
Supervision, Project administration, Funding acquisition, Resources, Mater. Struct. 43 (10) (2010) 1413–1433.
Validation, Writing – review & editing. [18] I.G. Richardson, C.R. Wilding, M.J. Dickson, The hydration of blastfurnace slag
cements, Adv. Cem. Res. 2 (8) (1989) 147–157.
[19] I.G. Richardson, G.W. Groves, Microstructure and microanalysis of hardened
Declaration of competing interest cement pastes involving ground granulated blast-furnace slag, J. Mater. Sci. 27
(1992) 6204–6212.
[20] I.G. Richardson, J.G. Cabrera, The nature of C-S-H in model slag-cements, Cem.
The authors declare that they have no known competing financial
Concr. Compos. 22 (2000) 259–266.
interests or personal relationships that could have appeared to influence [21] E. Berodier, K. Scrivener, G. Scherer, Understanding the filler effect on the
the work reported in this paper. nucleation and growth of C-S-H, J. Am. Ceram. Soc. 97 (12) (2014) 3764–3773.
[22] J. Skibsted, R. Snellings, Reactivity of supplementary cementitious materials
(SCMs) in cement blends, Cem. Concr. Res. 124 (2019).
Data availability [23] B. Lothenbach, K. Scrivener, R.D. Hooton, Supplementary cementitious materials,
Cem. Concr. Res. 41 (12) (2011) 1244–1256.
Data will be made available on request. [24] I.G. Richardson, The calcium silicate hydrates, Cem. Concr. Res. 38 (2) (2008)
137–158.
[25] A.V. Girão, et al., Composition, morphology and nanostructure of C-S–H in 70%
Acknowledgements white Portland cement–30% fly ash blends hydrated at 55◦ C, Cem. Concr. Res. 40
(9) (2010) 1350–1359.
[26] I.G. Richardson, S. Li, Composition and structure of an 18-year-old 5M KOH-
The first author gratefully acknowledges the financial support of the activated ground granulated blast-furnace slag paste, Constr. Build. Mater. 168
CSC-Leeds Joint Scholarship (Grant No. CSC2017050152). The facilities (2018) 404–411.
provided by UKCRIC National Centre for Infrastructure Materials at the [27] I.G. Richardson, et al., Location of aluminum in substituted calcium silicate
hydrate (C-S-H) gels as determined by 29Si and 27Al NMR and EELS, J. Am.
University of Leeds are highly appreciated. The first author also would
Ceram. Soc. 76 (9) (1993) 2285–2288.
like to thank Ms. Victoria Leadley for the help on the NMR experiments [28] I.G. Richardson, G.W. Groves, The incorporation of minor and trace elements into
and Ms. Lucy Leonard and Mr. Leslie Arkless for the trainings on XRD, calcium silicate hydrate gel in hardened cement pastes, Cem. Concr. Res. 23 (1993)
131–138.
STA, and glovebox. The suggestions during the experimental design and
[29] E. Lippmma, et al., Structural studies of silicates by solid-state high-resolution
the revisions of this manuscript from Prof. Phil Purnell (University of silicon-29 NMR, J. Am. Ceram. Soc. 102 (1980) 4889–4893.
Leeds) are highly acknowledged. [30] E. Lippmma, et al., A high resolution 29Si NMR study of the hydration of
tricalciumsilicate, Cem. Concr. Res. 12 (1982) 597–602.
[31] X. Cong, R.J. Kirkpatrick, 17O and 29Si MAS NMR study of β-C2S hydration and
Appendix A. Supplementary data the structure of calcium-silicate-hydrates, Cem. Concr. Res. 23 (1993) 1065–1077.
[32] X. Cong, R.J. Kirkpatrick, 29Si MAS NMR study of the structure of calcium silicate
Supplementary data to this article can be found online at https://doi. hydrate, Adv. Cem. Based Mater. 3 (1996) 144–156.
[33] M.D. Andersen, H.J. Jakobsen, J. Skibsted, Incorporation of aluminum in the
org/10.1016/j.cemconres.2023.107156. calcium silicate hydrate (C− S− H) of hydrated Portland Cements_ a high-field 27Al
and 29Si MAS NMR investigation, Inorg. Chem. 42 (2003) 2280–2287.
References [34] I.G. Richardson, G.W. Groves, The structure of the calcium silicate hydrate phases
present in hardened pastes of white Portland cement GGBFS, J. Mater. Sci. 32
(1997) 4793–4802.
[1] M.C.G. Juenger, R. Snellings, S.A. Bernal, Supplementary cementitious materials:
[35] I.G. Richardson, The nature of C-S-H in hardened cements, Cem. Concr. Res. 29
new sources, characterization, and performance insights, Cem. Concr. Res. 122
(1999) 1131–1147.
(2019) 257–273.
[36] S.-Y. Yang, et al., Incorporation of sodium and aluminum in cementitious calcium-
[2] I.G. Richardson, Tobermorite/jennite- and tobermorite/calcium hydroxide-based
alumino-silicate-hydrate C-(A)-S-H phases studied by 23Na, 27Al, and 29Si MAS
models for the structure of C-S-H: applicability to hardened pastes of tricalcium
NMR spectroscopy, J. Phys. Chem. C 125 (51) (2021) 27975–27995.
silicate, β-dicalcium silicate, Portland cement, and blends of Portland cement with
[37] J.J. Chen, The Nanostructure of Calcium Silicate Hydrate, in Feild of Materials
blast-furnace slag, metakaolin, or silica fume, Cem. Concr. Res. 34 (9) (2004)
Science and Engineering, Northwestern University USA, 2003.
1733–1777.
[38] M.D. Andersen, H.J. Jakobsen, J. Skibsted, Characterization of white Portland
[3] I.G. Richardson, et al., Hydration of water- and alkali-activated white Portland
cement hydration and the C-S-H structure in the presence of sodium aluminate by
cement pastes and blends with low-calcium pulverized fuel ash, Cem. Concr. Res.
27Al and 29Si MAS NMR spectroscopy, Cem. Concr. Res. 34 (5) (2004) 857–868.
83 (2016) 1–18.
[39] A. Kunhi Mohamed, et al., The atomic-level structure of cementitious calcium
[4] R. Taylor, I.G. Richardson, R.M.D. Brydson, Composition and microstructure of 20-
aluminate silicate hydrate, J. Am. Chem. Soc. 142 (25) (2020) 11060–11071.
year-old ordinary Portland cement–ground granulated blast-furnace slag blends
[40] J. Hirljac, Z.-Q. Wu, J. Young, Silicate polymerization during the hydration of alite,
containing 0 to 100% slag, Cem. Concr. Res. 40 (7) (2010) 971–983.
Cem. Concr. Res. 13 (6) (1983) 877–886.
[5] J. Li, et al., Influences of cross-linking and Al incorporation on the intrinsic
[41] I.G. Richardson, G.W. Groves, Models for the composition and structure of calcium
mechanical properties of tobermorite, Cem. Concr. Res. 136 (2020), 106170.
silicate hydrate (C-S-H) gel in hardened tricalcium silicate pastes, Cem. Concr. Res.
[6] J. Li, W. Zhang, P.J.M. Monteiro, Synchrotron X-ray raman scattering shows the
22 (1992) 1101–1110.
changes of the ca environment in C-S-H exposed to high pressure, Cem. Concr. Res.
[42] E. Tajuelo Rodriguez, et al., Thermal stability of C-S-H phases and applicability of
132 (2020), 106066.
Richardson and Groves’ and Richardson C-(A)-S-H(I) models to synthetic C-S-H,
[7] Z. Zhang, G.W. Scherer, A. Bauer, Morphology of cementitious material during
Cem. Concr. Res. 93 (2017) 45–56.
early hydration, Cem. Concr. Res. 107 (2018) 85–100.
[43] T.D. Ciath, E.G. Swenson, Morphology and microstructure of hydrating Portland
[8] J. Li, et al., Fibrillar calcium silicate hydrate seeds from hydrated tricalcium silicate
cement and its constituents I. Changes in hydration of tricalcium aluminate alone
lower cement demand, Cem. Concr. Res. 137 (2020), 106195.
and in the presence of triethanolamine or calcium lignosulphonate, Cem. Concr.
[9] I.G. Richardson, The nature of the hydration products in hardened cements, Cem.
Res. 1 (1971) 143–158.
Concr. Compos. 22 (2000) 97–113.

18
X. Zhu and I.G. Richardson Cement and Concrete Research 168 (2023) 107156

[44] M. Collepardi, B. Marchese, Morphology and surface properties of hydrated [56] D. Rothstein, et al., Solubility behavior of ca-, S-, Al-, and si-bearing solid phases in
tricalcium silicate pastes, Cem. Concr. Res. 2 (1972) 57–65. Portland cement pore solutions as a function of hydration time, Cem. Concr. Res.
[45] P.C. Fonseca, H.M. Jennings, The effect of drying on early-age morphology of C- 32 (2002) 1663–1671.
S–H as observed in environmental SEM, Cem. Concr. Res. 40 (12) (2010) [57] J.J. Thomas, et al., Effect of hydration temperature on the solubility behavior of ca-
1673–1680. , S-, Al-, and si-bearing solid phases in Portland cement pastes, Cem. Concr. Res. 33
[46] E.T. Rodriguez, Relation between Composition, Structure and Morphology in C-S- (12) (2003) 2037–2047.
H, in School of Civil Engineering, University of Leeds, UK, 2015. [58] B. Lothenbach, F. Winnefeld, Thermodynamic modelling of the hydration of
[47] G.W. Groves, S.A. Rodger, The hydration of C3S and ordinary Portland cement Portland cement, Cem. Concr. Res. 36 (2) (2006) 209–226.
with relatively large additions of microsilica, Adv. Cem. Res. 2 (8) (1989) 135–140. [59] B. Lothenbach, et al., Effect of temperature on the pore solution, microstructure
[48] I.G. Richardson, G.W. Groves, Microstructure and microanalysis of hardened and hydration products of Portland cement pastes, Cem. Concr. Res. 37 (4) (2007)
ordinary Portland cement pastes, J. Mater. Sci. 28 (1993) 265–277. 483–491.
[49] A.V. Girao, The Nanostrructure and Degradation of Csh in Portland and Blended [60] B. Lothenbach, et al., Influence of limestone on the hydration of Portland cements,
Cements, in School of Civil Engineering, University of Leeds, UK, 2007. Cem. Concr. Res. 38 (6) (2008) 848–860.
[50] S. Jia, I.G. Richardson, Micro- and nano-structural evolutions in white Portland [61] B. Lothenbach, et al., Thermodynamic modelling of the effect of temperature on
cement/pulverized fuel ash cement pastes due to deionized-water leaching, Cem. the hydration and porosity of Portland cement, Cem. Concr. Res. 38 (1) (2008)
Concr. Res. 103 (2017) 191–203. 1–18.
[51] S. Jia, Micro/Nano-Structural Evolution in Blended Cement Paste Due to [62] D. Damidot, et al., Thermodynamics and cement science, Cem. Concr. Res. 41 (7)
Prograssive Deionised Water Leaching, in School of Civil Engineering, University of (2011) 679–695.
Leeds, UK, 2014. [63] R.J. Myers, et al., Solution chemistry of cubic and orthorhombic tricalcium
[52] A.V. Girao, et al., Morphology and nanostructure C-S–H in white Portland aluminate hydration, Cem. Concr. Res. 100 (2017) 176–185.
cement–fly ash hydrated at 85◦ C, Adv. Appl. Ceram. 106 (6) (2007) 283–293. [64] B. Lothenbach, A. Nonat, Calcium silicate hydrates: solid and liquid phase
[53] A.V. Girão, et al., Composition, morphology and nanostructure of C-S–H in white composition, Cem. Concr. Res. 78 (2015) 57–70.
Portland cement pastes hydrated at 55 ◦ C, Cem. Concr. Res. 37 (12) (2007) [65] H.M. Jennings, Aqueous solubility relationships for two types of calcium silicate
1571–1582. hydrate, J. Am. Ceram. Soc. 69 (8) (1986) 614–618.
[54] R. Taylor, I.G. Richardson, R.M.D. Brydson, Nature of C-S–H in 20 year old neat [66] B. Lothenbach, E. Wieland, A thermodynamic approach to the hydration of
ordinary Portland cement and 10% Portland cement–90% ground granulated blast sulphate-resisting Portland cement, Waste Manag. 26 (7) (2006) 706–719.
furnace slag pastes, Adv. Appl. Ceram. 106 (6) (2013) 294–301. [67] K. De Weerdt, et al., Hydration mechanisms of ternary Portland cements containing
[55] I.G. Richardson, et al., The characterization of hardened alkali activated slag paste limestone powder and fly ash, Cem. Concr. Res. 41 (3) (2011) 279–291.
and the nature of the calcium silicate hydrate phase, Cem. Concr. Res. 24 (5)
(1994) 813–829.

19