Cement and Concrete Research 85 (2016) 111–121

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Cement and Concrete Research

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Influence of calcium to silica ratio on aluminium uptake in calcium

silicate hydrate
E. L’Hôpital a, B. Lothenbach a,⁎, D.A. Kulik b, K. Scrivener c
a
Empa, Laboratory for Concrete & Construction Chemistry, CH-8600 Dübendorf, Switzerland
b
Paul Scherrer Institute, Laboratory for Waste Management, 5232 Villigen PSI, Switzerland
c
EPLF, Laboratory of Construction Materials, CH-1015 Lausanne, Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: Aluminium uptake in calcium silicate hydrate (C–S–H) was studied at different Ca/Si ratios from 0.6 to 1.6
Received 11 April 2015 at 20 °C.
Accepted 10 January 2016 Aluminium incorporation in C–S–H depends on the total amount of aluminium present in the sample. At low Al/
Available online xxxx
Si ratio (≤0.05), the major part of the aluminium is taken up in C–S–H while at higher Al/Si ratio, the precipitation
of stratlingite and/or katoite limits the Al/Si ratio in C–S–H to ≈0.15, regardless of the Ca/Si ratio.
Keywords:
C–S–H
A strong correlation between the aqueous aluminium concentration and the aluminium uptake in the solid phase
Ca/Si ratio is observed. At high Ca/Si ratios, aluminium in C–S–H is observed mainly as octahedrally coordinated Al(VI)
Aluminium uptake in TAH and the aluminium uptake increases with the aqueous aluminium concentration. At low Ca/Si ratio
(≤0.8), aluminium is observed mainly as tetrahedrally coordinated Al(IV) and low aqueous aluminium concen-
trations (below detection limit) indicate a high affinity of aluminium towards C–S–H.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction tetrahedral aluminium(IV) in bridging positions of the “dreierketten”

chains [16,17], consistent with the increase of the mean chain length.
Calcium silicate hydrate (C–S–H) is the main hydration product At all Ca/Si ratios approximately 10% of five-fold coordinated aluminium
in Portland cements and contributes significantly to the physical, (Al(V)) and of six-fold coordinated Al(VI-a) are observed, possibly
chemical, and mechanical properties. C–S–H phase is poorly crystalline present in the interlayer space [16,18]. At higher Ca/Si ratio, the alumin-
(‘gel-like’) with variable calcium, silica, and water contents. C–S–H ium is mainly octrahedrally co-ordinated Al(VI). In addition to Al(VI-a),
can be described as a calcium oxide layer sandwiched by silica chains at high Ca/Si ratios Al(VI-b) is predominant, an amorphous aluminate
organized in a “dreierketten” structure, a repeating chain of three silica hydrate, the so-called third aluminate hydrate (TAH) [19], which is
tetrahedra, as shown in Fig. 1. Two of these silica units, called pairing associated with C–A–S–H precipitation. Based on 27Al [18] CP/MAS
tetrahedral, are linked to the calcium oxide layer, while the third one, NMR experiments, Andersen et al, [19] showed that the local aluminium
the bridging tetrahedron, links the two pairing tetrahedra. Water, environment in the third aluminate hydrate is similar to the environ-
calcium, alkalis or other ions are present in the interlayer between the ment of octahedrally coordinated aluminium in AFm or ettringite
layers. phases, possibly indicating that TAH is present either as aluminium
The chemical composition of cement determines the Ca/Si ratio in hydroxide or a calcium aluminate hydrate. Renaudin et al. [16] sug-
C–S–H. In Portland cements, where Ca/Si ratio is approximately 1.7 gested that TAH is incorporated in the interlayer of the C–S–H, which
[2], silica chains consist mainly of dimers and calcium (hydroxide) is could explain the increase of mean basal spacing from C–S–H to C–A–
present in the interlayer space [3–8]. The addition of silica-rich supple- S–H at higher Ca/Si ratios, while Andersen et. al. [19] proposed the
mentary cementitious materials (SCM) leads to a decrease of Ca/Si ratio formation of calcium aluminate hydrate on the surface of C–S–H or as
in C–S–H [9–12] due to the reaction with SCM. A decrease of the Ca/Si a separate phase. In this article, the Al(VI-b) associated with TAH is
ratio is associated with an increase of the dreierketten chain length considered as a part of C–S–H in agreement with Andersen et al. [19]
and of the interlayer spacing [6,13,14]. and Renaudin et al. [16], even though the exact nature and location of
In the presence of aluminium, a longer “dreierketten” chain, as well TAH are not known.
as a larger interlayer spacing, is observed compared to C–S–H without The composition of C–S–H is closely related to the dissolved calcium,
aluminium [13,15]. At low Ca/Si ratio, aluminium is mainly taken up as silicon, and hydroxide concentrations in the surrounding aqueous solu-
tion. Experimental investigations on the solubility of synthetic C–S–H
⁎ Corresponding author. Tel.: +41 58 765 47 88; fax: +41 58 765 69 35. show a strong decrease of dissolved calcium and hydroxide upon decal-
E-mail address: [email protected] (B. Lothenbach). cification of C–S–H, while the silicon concentrations increase [4,20–25].

http://dx.doi.org/10.1016/j.cemconres.2016.01.014
0008-8846/© 2016 Elsevier Ltd. All rights reserved.
112 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121

katoïte, or aluminium hydroxides by TGA was difficult as the weight

loss of C–A–S–H and the different aluminium containing phases were
overlapped.
X-ray powder diffraction patterns were recorded on a PANalycatical
X'Pert Pro MDF diffractometer equipped with a X'Celerator detector.
The diffraction patterns were acquired from 5° to 70° 2θ with a step
size of 0.017° 2θ and a step measurement time of 459.74 s. Phase
composition was determined with X'Pert HighScore Plus. The Rietveld
analyses were carried out with calcium fluoride as external standard.
This method avoids the normalization to 100wt%; the quantification of
X-ray amorphous solids such as C–S–H can be determined by indirect
measurement [32]. To determine the exact peak position of d002 of
C–(A–)S–H, the samples were measured with anatase as internal
standard and a beam knife was used to lower the background in the
Fig. 1. Schematic structure of C–A–S–H. Grey circle: calcium ion; empty circle: ion in the low angle region.
interlayer (water or alkali); light grey tetrahedra: SiO4-, dark grey tetrahedra: AlO4; −: The 29Si NMR measurements were performed at room temperature
negative charge (compensated by proton, calcium, or other cations). Qn(mAl):
using a Bruker Avance 400 MHz NMR spectrometer with a 7 mm CP/
n indicates the numbers of Si neighbours and m the number of aluminium neighbours,
b: bridging position, p: pairing position [1]. MAS probe. The 29Si MAS NMR single pulse experiments were recorded
at 79.49 MHz using the following parameters: 4500 Hz spinning speed,
9216 scans, π3 pulses of 2.5 ms, 20 s relaxation delays, the 90° Pulse at
Similarly, the amount of aluminium in C–A–S–H is related to aqueous the decoupling power level of 8 dB is 7.5 μs. The RF field is calculated
concentrations [24,26,27]. A number of studies investigated the effect by 1/(4 * 7.5 μs) = 33.3 kHz. The chemical shifts of the 29Si MAS NMR
of varying Ca/Si and Al/Si ratios on the structure of C–A–S–H gel [13, spectra were referenced to an external sample of tetramethylsilane
16,28,29], but very limited information is available on the relation (TMS). The observed 29Si resonances were analysed using the Qn(mAl)
between aluminium, calcium, and silicon concentrations in solution classification, where a Si tetrahedron is connected to n Si tetrahedral
and the composition of C–A–S–H gels at different Ca/Si ratios. Such with n varying from 0 to 4 and m is the number of neighbouring AlO4
systematic information on both the aqueous and solid composition is tetrahedra. The 27Al NMR measurements were performed at room
needed to further develop thermodynamic models, used for calculating temperature with a 2.5 mm CP/MAS probe. The 27Al MAS NMR single
the composition of synthetic C–S–H systems (e.g. [4]) or the C–(A–)S–H pulse experiments were recorded at 104.26 MHz using the following
π
composition in hydrating cements [30,31]). parameters: 20 000 Hz spinning speed, 4000 scans, 12 pulses of 1 μs,
The present paper aims to provide and interpret the experimental 1.5 s relaxation delays, without 1H decoupling. The chemical shifts of
data on the aluminium uptake in C–S–H at different Ca/Si ratios from the 27Al MAS NMR spectra were referenced to an external sample of
0.6 to 1.6. Structure, chemical composition of the resulting C(–A)–S–H Al(acac)3.
gel-like phase, as well as the composition of aqueous solution were in-
vestigated after an equilibration time of 6 months or longer, to ensure
equilibrium conditions. 2.3. Solution analyses

2. Material and methods The elemental concentrations of calcium, silicon, and aluminium in
the filtrates were determined with a Dionex DP ICS-3000 ion chromato-
The C–S–H and C–A–S–H were synthesized by a one-step protocol graph. Each sample was diluted by a factor 1, 5, 10, 100, and/or 1000
at 20 °C, as described in detail in [1] and summarized below for the depending on the ion concentration and measured in duplicate. Stan-
convenience of the reader. dards from 0.1 to 50 mg/L were used. The error of the measurements
was ≈10% of the relative value.
2.1. Synthesis To quantify the hydroxide concentration, the pH measurements
were performed at room temperature with a Knick pH meter (pH-
Calcium oxide (CaO), silica fume (SiO2), and monocalcium alumi- Meter 766) equipped with a Knick SE100 electrode. The pH electrode
nate (CA: CaO.Al2O3) were used in different proportion to synthesize was calibrated against KOH solutions of known concentrations in
C(–A)–S–H with different Ca/Si ratios (see detail in Appendix A) at order to minimize the alkali error. The measurements were corrected
water to solid ratio equal to 45. Synthesis and all sample handling to correspond to 20 °C.
were done in a N2 filled glovebox to minimize CO2 contamination.

2.2. Solid phase analysis 2.4. Thermodynamic modelling

After filtration, the solid was washed with approximately 30 mL of a Thermodynamic modelling was carried out using the Gibbs free
50%–50% water–ethanol solution, afterwards with approximately 30 mL energy minimization program GEM-Selektor [33,34], a geochemical
of pure ethanol, dried for 7 days by freeze drying and then stored until modelling code that computes equilibrium speciation of the dis-
analysis in N2-filled desiccators in the presence of saturated CaCl2 solved species, as well as the amount and composition of stable
solutions (≈ 30% RH) and NaOH pellets as CO2 trap. The solid phases solid phases. Chemical interactions involving pure solids, solid solu-
were analyzed by thermogravimetric analysis (TGA), X-ray diffractom- tions, aqueous electrolyte, and gas mixture are considered simulta-
etry (XRD), and Rietveld analysis, as well as by 29Si and 27Al nuclear neously. The thermodynamic data for aqueous species, as well as
magnetic resonance (NMR). for many solids, were taken from the PSI-Nagra thermodynamic
TGA data were recorded with a TGA/SDTA851e Mettler Toledo. The database [35,36], while the solubility products for cement minerals
weight loss of the samples was recorded from 30 °C up to 980 °C with were taken from the Cemdata’07 database [37,38] updated with
a heating rate of 20 °C/min under nitrogen atmosphere. The total the recent solubility products of calcium aluminate hydrates and
water bound in C–A–S–H was quantified from the total water loss be- hydrogarnets [39,40]. C–S–H was modelled using the CSHQ thermo-
tween 30 and 550 °C. The quantification of solids such as strätlingite, dynamic solid solution model [4].
 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121 113

3. Results and discussion

3.1. Solid phase composition

3.1.1. Influence of time

In aluminium-free samples, only C–S–H is observed by XRD and TGA
at 0.6 ≤ Ca/Si ≤ 1.4 (see Appendix B). At a Ca/Si of 1.6, portlandite pre-
cipitates in addition to C–S–H (Fig. 2), which limits the Ca/Si ratio in C–
S–H to 1.38 after 182 days (see Appendix B). After 1 year, portlandite is
no longer present and a maximum Ca/Si ratio of 1.47 is reached for the
sample with a target Ca/Si ratio of 1.6. Even in the absence
of portlandite, the “real” Ca/Si ratio in the solid C–S–H is 1.47, lower
than the nominal 1.6 due to the high water-to-solid ratio used in the
experiments (w/s = 45) and the higher aqueous calcium than silicon
concentrations.
Fig. 2 shows that with time, the intensity of the d002 peak at ~7° 2θ
related to the mean basal spacing between C–S–H sheets sharpens, as
previously observed in [1]. In addition, the d002 peak shifts with time
Fig. 2. XRD measurements of C–(A–)S–H (target Ca/Si =1.6) as a function of time (C: C–S–H,
also to slightly higher 2θ values, showing a small decrease of the mean
P: portlandite, K: katoite, A: CO3-AFm).
basal spacing for the samples with Ca/Si ≥ 1.2 as summarised in Fig. 3.
This decrease of the basal spacing could be related to a better ordering
of the C–S–H with time leading (i) to a sharpening of the peaks and
13.5
(ii) to the presence of more calcium in the interlayer as the interlayer
13 distance of C–S–H decreases with increasing Ca/Si ratio. The mean silica
Mean basal spacing (Å)

12.5 chain length of C–S–H has been observed to increase with time [41,42],
12 which may be responsible for the presence of more calcium in the inter-
11.5 Ca/Si=1.0 layer. At Ca/Si = 1.6 the presence of additional calcium in the C–S–H
interlayer is also related to the disappearance of portlandite with time
11 Ca/Si=1.2
(see Fig. 2).
10.5 Ca/Si=1.4
10 Ca/Si=1.6 3.1.2. Solids present and basal spacing in C–A–S–H
9.5 Fig. 4 shows that at Ca/Si = 0.6 to 1.3, only the broad peaks related
9 to C–S–H can be observed by XRD while portlandite is observed for a
0 100 200 300 400 500 600 Ca/Si ≥ 1.38. A decrease of Ca/Si ratio from ~1.4 to 1.0 results in a shift
of the d002 diffraction peak from 8.9 to 7.3° 2θ indicating an increase
Time (Days)
of the basal spacing of C–S–H from 9.9 to 12.1 Å (Appendix B). At
Fig. 3. Mean basal spacing e of C–S–H as a function of time for target Ca/Si ratios from 1.0 to
low Ca/Si ratio ≤ 0.8, no well-defined d002 diffraction peak can be
1.6. Empty symbols: measurement without standard, filled symbols: measurement with identified in our samples. Other studies reported a d002 diffraction
anatase as a standard. peak of ≈14 Å at Ca/Si = 0.6 and 0.8 [6,13], consistent with the d002

Fig. 4. XRD of C–S–H (black line) and C–A–S–H with Al/Si = 0.05 (dashed line) after 182 days. C: C–S–H, P: portlandite.
114 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121

study are slightly lower than many of those values, as the drying
procedure used here (freeze drying and re-equilibration to 30% R.H.)
is more harsh than the drying methods used in [13,45–47] (e.g. drying
over silica gel [13]) or drying at 60 °C [46]). As discussed in previous
studies [48,49], the mean basal spacing of C–S–H decreases at harsher
drying conditions.
The addition of aluminium leads to its incorporation into the C–S–H.
As observed previously in [1], in addition to C–A–S–H, also small quan-
tities of katoite and/or stratlingite precipitate at Al/Si ratio greater than
to 0.1 (Appendix B). No hydrogrossular (C3ASyH6-2y) was observed,
although the solutions are oversaturated with respect to C3AS0.84H4.32,
as discussed further below. In the presence of aluminium (Al/Si =
0.05), an increase of the C–S–H interlayer spacing from ~ 12.1 to
~ 12.7 Å is observed for Ca/Si = 1.0. A similar distinct increase of the
mean basal spacing from 12.7 to 14.4 Å has been observed by Renaudin
Fig. 5. Variation of the mean basal spacing as a function of the total Ca/(Si + Al) ratio in et al. [13] for similar Ca/Si ratios. At low Ca/(Si + Al) ratio, the increase
C–S–H and C–A–S–H (Al/Si = 0.05). Measured with anatase as internal standard. of the mean basal spacing due to the incorporation of aluminium in
Lines are intended as eye guides only.
C–S–H is less distinct than at high Ca/Si ratios. At high Ca/(Si + Al)
ratio, the observed increase in the interlayer spacing where alumin-
distance of 14 Å tobermorite [43]. The increase of the mean basal spac- ium is incorporated in C–S–H seems to be related to the presence of
ing has been related to the presence of bridging tetrahedra at lower aluminium in the interlayer space. Renaudin et al. [16] suggested
Ca/Si ratios [44]. A similar increase of the basal spacing for C–S–H that this increase is due to the formation of calcium aluminate
with lower Ca/Si ratio has also been reported previously [13,44–47]. hydrate layer within the interlayer space of the C–A–S–H. Whether
Fig. 5 shows the variation of the mean basal spacing as a function of such an additional calcium aluminate hydrate layer would have
C–S–H and C–A–S–H. The mean basal spacing reported in the present space in the interlayer of C–S–H at a total distance of 12–14 Å and

3
A TGA (Al/Si=0)
2.5 TGA (Al/Si=0.03)

TGA (Al/Si=0.05)
2
Cong 1996 (total H2O)
H2 O/Si

Cong 1996 (>110°C)

1.5
Beaudoin 1990 (total H2O)

Fujii 1981 (total H2O)

1
Muller 2012 (H NMR, PC)

0.5
0.6 0.8 1 1.2 1.4 1.6 1.8
Ca/(Si+Al)
2,5
2,3 B
2,1
1,9
Al/Si=0
1,7
H2 O/Ca

Al/Si=0.03
1,5
1,3 Al/Si=0.05
1,1
0,9
0,7
0,5
0,6 0,8 1 1,2 1,4 1,6
Ca/(Si+Al)

Fig. 6. Water content of C–(A–)S–H after 182 days. A) molar H2O/Si and B) H2O/Ca. Determined by the weight loss measured by TGA between 30 and 550 °C, by to H-NMR and sorption
isotherm data [54] on samples equilibrated to 30% relative humidity (H2O/Si ± 0.3), compared the similar measurements from the literature [21,22,56] for synthetic C–S–H (grey circle
refer to harshly dried samples (drying at 110 °C), empty circle signs to lightly dried C–S–H (water content after solvent extraction) and for cement paste (referring to H/(Si + Al)
and Ca/(Si + Al) ratios) [55].
 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121 115

how it would be connected to the silica dimers of the main layers The presence of aluminium in C–S–H tends to increase the water up-
remains a matter of debate. take. On average, 2 (±0.3) additional H2O per aluminium in the C–S–H
is measured.
3.1.3. Bound water
Upon heating, the main weight loss of C–S–H occurs at 80–150 °C 3.1.4. Structure of the C–S–H and C–A–S–H.
(Appendix C), which is related mainly to the loss of interlayer water. Previous studies (e.g. [6,20,28,44,57,58]) indicate that silica in C–S–
As discussed above and in [50–52], the mean basal spacing [48,49] H can be present at the end of the dreierketten chain as Q1 (with a
and the water content of C–S–H depend strongly on the drying condi- chemical shift of −79.4 ppm in the 29Si NMR); within the “dreierkette”
tions. However, as all the samples have been dried using the same dry- as bridging silica Q2b at −83.4 ppm; as pairing Q2p at −85.3 ppm or as
ing procedure, a comparison between samples is possible. The samples a bridging tetrahedra connected to another bridging silica tetrahedra by
presented here have been freeze-dried to remove the capillary and gel hydrogen bonding, Q2u at –88.5 ppm [59–61]. Fig. 7 shows that an
water [50] and re-equilibrated to ~30% RH. The weight loss determined increase in the Ca/Si ratio leads to an increase in the fraction of the
by TGA between 30 and 550 °C (corrected by the mass balance in case of end-of-chain silica (Q1) and a corresponding decrease in the fraction
presence of other phases) is used to calculate the water content per sil- of pairing and bridging tetrahedra, Q2p, Q2b, and Q2u. Thus, the mean
icon in synthetic C–S–H samples. The water content, H2O/Si, increases chain length shortens (Fig. 8), which agrees with previous observations
strongly from 1.1 ± 0.3 at Ca/Si = 0.6 to 1.8 ± 0.3 at Ca/Si = 1.4 [20,44]. At a target Ca/Si ratio of 0.6, in addition a broad Q3 peak is ob-
(Fig. 6, Appendix B). The H2O/Si of 1.1 ± 0.3 measured at low Ca/Si served at ~−95 ppm (Table 1), which is assigned to Q3 sites at surface
ratio is consistent with the water contents determined for 11 Å of amorphous SiO2 [62]. In addition, the presence of a small amount of
(C0.67SH: 4CaO∙6SiO2 ∙6H2O [53]) and 14 Å (C0.83SH1.3 [43]) tobermorite Q3 in C–S–H is possible. As the peak is badly defined and very broad
structures. The limited increase of the H2O/Si between Ca/Si ratio from (width = 10 ppm), no deconvolution of the peak was attempted as it
0.6 to ~1 (Fig. 6A) is related to the decrease of the amount of silica per was not considered as part of C–S–H.
structural unit, as the bridging tetrahedra are removed resulting in At higher Ca/Si ratios, a slight change of the chemical shift obtained
~ CSH1.5 (4CaO ∙ 4SiO2 ∙ 6H2O). The more pronounced increase of the by 29Si NMR to less negative values is observed (Fig. 9 and Table 1) due
H2O/Si ratio at high Ca/Si ratio indicates that the uptake of additional to the increased shielding from the presence of more calcium in the in-
calcium in the interlayer is associated with the uptake of additional terlayer [63]. The shift observed in the present study agrees with other
H2O: ~C1.5SH2 (6CaO∙4SiO2 ∙8H2O), consistent with the presence of cal- measurements reported in literature [20,64,65].
cium hydroxide in the interlayer space [4]. The H2O/Ca ratio (Fig. 6B) The incorporation of aluminium into C–S–H leads to an additional
shows the opposite trend and decreases from H2O/Ca = 2.0 at Ca/ signal between −81.05 to −82.20 ppm, which corresponds to a pairing
Si = 0.6 to H2O/Ca = 1.4 at high Ca/Si ratio. These different trends result silica tetrahedra neighbouring aluminium in the bridging position
in a constant water content of 18±1 wt% in C–S–H independent of the as shown by [18,44,66–68]. The measurements confirm the uptake of
Ca/Si ratio. Comparable values and a similar increase of the H2O/Si ratio aluminium in the bridging position and show a decrease of the Q1
with increasing Ca/Si ratio has also been measured by sorption iso- sites (end of chain silica) as shown in Table 1, which results in longer sil-
therms measurements (at 30% RH) and by 1H-NMR measurements ica chain lengths. Based on the relative fraction of silica neighbouring
[54] on samples prepared using the same procedure as in the present aluminium (Q2(1Al)), in all samples an AlIV/Si ratio of 0.05 is obtained,
study. The measured water contents of the dried synthetic samples indicating that under these experimental conditions, the main part of
are comparable to the interlayer water of 1.8 H2O/Si measured by 1H aluminium in C–S–H is bound in the bridging position.
NMR in a white Portland cement at Ca/Si = 1.7 [55]. The data measured The 27Al-NMR spectra (Fig. 10) recorded on the samples incorporat-
in the present work are consistent with H2O/Si ratio reported in the lit- ing aluminium (Al/Si = 0.05) shows the presence of IV-, V-, and VI-fold
erature as shown in Fig. 6A. coordinated aluminium, in agreement with the literature [16,18,28,44].

Fig. 7. 29Si NMR of C–S–H equilibrated for a) 91 days, b) 1 year, c) 1.5 years or d) 2 years. The target Ca/Si ratios or the C–S–H are indicated. Solid curve: C–S–H, dashed curves: C–A–S–H
with (Al/Si = 0.05).
116 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121

100
C-S-H
C-A-S-H
C-S-H (Kunther 2014)
C-S-H (Chen 2004)
MCL

10
C-S-H (Cong 1996)

1
0.6 0.8 1 1.2 1.4 1.6
Ca/(Si+Al) in C-S-H

Fig. 8. Mean chain length of C(–A)–S–H as a function of Ca/(Si + Al) ratio measured in the
present paper compared to MCL reported by Chen et al. [20], Kunther et al. [69], and Cong
et al. [21]

There are two Al(VI) signals, a main signal centred at ≈ 5 ppm and Fig. 9. Measured 29Si chemical sift of end of chain (Q1) [square], briding (Q2b) [triangle]
a broad signal at about ≈ 9 ppm, an Al(V) with a maximum at and pairing (Q2p) [diamond] silica tetrahedra in C–S–H as a function of the measured
≈ 35 ppm and three Al(IV) signals at ≈ 55, ≈ 63, and ≈ 70 ppm. At Ca/Si ratio compared with literature: Chen et al. [20], He et al. [64], and Popova et al
[65]. Lines are intended as eye guides only.
low Ca/Si ratios, predominately Al(IV) is observed indicating an uptake
of the aluminium in the bridging position of the silica chain [16,44],
which agrees with 29Si NMR findings discussed above.
The increase of Ca/Si ratio influences the Al(IV) chemical shift. An increase of the Ca/Si ratio of C–S–H without aluminium leads
At low Ca/Si ratio, the Al(IV) signal is observed at ≈ 55 ppm, at to an increase of the calcium and hydroxide concentrations, while the
≈62.6 ppm, at Ca/Si = 1.0, and at ≈70 ppm at Ca/Si = 1.6. The signal silicon concentrations decrease as shown in Fig. 11, which is in agree-
at low Ca/Si has been attributed to a bridging Al(Q3) [16,44,70], the ment with previous data reported in the literature [20,22,71–73].
signal at 63 ppm to bridging Al(IV) charge balanced by calcium, sodium, The addition of aluminium leads, over the whole range of Ca/Si ratios
or hydrogen [16,44] and the signal at ≈70 ppm to aluminium balanced studied, to an increase of the silicon concentrations, while the calcium
by interlayer Al(V) or Al(VI) [16,44]. At all Ca/Si ratios, a low fraction concentrations and pH values decrease, as shown in Fig. 11 for C–S–H
of Al(V) and of Al(VI-a) is observed, which has been assigned to alumin- and C–(A–)S–H (Al/Si = 0.05).
ium ions present in the interlayer [16,18,28,44]. At Ca/Si ≥ 1 a decrease The increase of total aluminium content in the system leads to a
of the relative intensity of the Al(IV) in favour of Al(VI) is observed. The gradual increase of the dissolved aluminium and silicon concentrations
signal at 10–12 ppm can be assigned to a small quantity of stratlingite while the dissolved calcium and hydroxide concentrations decrease as
(≈10 ppm and an additional signal at ≈62 ppm [44]) or hydrogarnet illustrated in Fig. 12 for Ca/Si = 1.2. For Al/Si ratio N 0.1, the dissolved
(≈10.3 ppm [28]), the signal ≈5 ppm to the presence of the third alu- aluminium concentrations reach a plateau as other aluminium contain-
minate hydrate (TAH) phase [16,19], Al(VI-b). Although the 27Al-NMR ing phases such as katoite and stratlingite precipitate, as reported previ-
indicates the presence of katoite at Ca/Si = 1.6 (Fig. 10), it could not ously for Ca/Si = 1.0 in [1]. This precipitation of these other hydrates
be detected by XRD (Appendix B) due to its small quantity (b 1wt.%). limits the Al/Si ratio in C–A–S–H to about 0.15 ± 0.05 under equilibrium
The incorporation of Al(V) and Al(VI-a) in the interlayer as sug- conditions. Higher aluminium uptake in C–A–S–H is only reached either
gested by [16,18,28,44] is consistent with the increased interlayer in short-term experiments where pre-synthesized C–S–H has been
spacing by ~2 Å of the C–A–S–H compared to C–S–H shown in Fig. 5. added to calcium aluminate solutions resulting in higher aluminium
concentrations [18,24,26] or in the presence of alkali hydroxides,
where the increase of pH results in higher dissolved aluminium concen-
3.1.5. Aqueous concentrations trations and thus in a higher Al/Si ratio in C–A–S–H [1].
The solid composition described above is in equilibrium with the The measured aqueous concentrations as a function of pH (Fig. 13)
composition of the aqueous phase. A compilation of all measured con- show comparable trends in the absence and in the presence of alumin-
centrations is given in the Appendix D. ium, although, as discussed above, somewhat higher silicon

Table 1
Relative fraction of Qn (±5%), chemical shift (± 0.5 ppm) and mean chain length (MCL ± 5%). AlIV/Si: Aluminium in bridging position obtained from Si NMR; Al/Si*: total Al/Si
ratio in C–S–H (mass balance).

Target Q1 Q2p Q2b Q2u Q2 (1Al) Q3* AlIV/Si Al/Si* MCL

Ca/Si ppm % ppm % Ppm % ppm % ppm % ppm %

Al/Si = 0
0.6 −79.60 4 −85.78 49 −82.40 17 −88.4 7 – – −95 30 37
0.8 −79.95 10 −86.15 60 −83.25 24 −88.6 6 – – – – 19
1 −79.55 38 −85.30 42 −83.35 21 – – – – – – 5
1.2 −79.28 71 −85.08 20 −83.55 10 – – – – – – 3
1.4 −79.85 86 −85.40 9 −82.75 5 – – – – – – 2
1.6 −79.20 81 −85.15 13 −82.80 6 – – – – – – 2

Al/Si = 0.05
1 −79.90 24 −85.78 44 −83.93 19 −89.0 3 −82.20 10 – – 0.05 0.05 9
1.4 −75.50 59 −85.00 21 −82.80 10 – – −81.05 10 – – 0.05 0.05 4
⁎ Mainly Q3 in silica gel + Q3 in C–S–H, −: not observed.
 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121 117

Dissolved concentration (mmol/L)

Al(VI-b) 100
TAH
Ca
10

Al(VI) 1
Katoite
Al(IV)
0.1
Al(V) Si
Ca/Si=1.6

0.01
Al
Ca/Si=1.4 Detection limit
0.001
Ca/Si=1.0 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0
Al(VI-a)
Ca/Si=0.6 pH

100 90 80 70 60 50 40 30 20 10 0 -10 Fig. 13. Evolution of measured silicon (squares) and calcium (diamonds) concentrations
ppm with (empty symbols; target Al/Si = 0.03 to 0.33) and without aluminium (filled
symbols) as a function of the pH values upon variation of the Ca/Si ratio. Equilibrated for
182 or 365 days. Trend lines for C–S–H have been added as eye guide.
Fig. 10. 27Al NMR on C–A–S–H with Al/Si = 0.05. Equilibration times: 182 days (solid
curves), 91 days (dashed curve).
concentrations are measured for C–A–S–H. These similar trends indicate
that the uptake of aluminium in C–S–H leads to comparable solu-
bility of C–A–S–H as of C–S–H without aluminium and thus to
relatively minor stabilisation of C–A–S–H. Similar observations
have been reported for C–A–S–H with Ca/Si = 1.0 equilibrated at 7,
20, 50, and 80 °C [74].

Fig. 11. Dissolved silicon (squares), calcium (diamonds), aluminium (triangles),

and hydroxide (circles) concentrations in equilibrium with C–S–H (empty symbols) and
C–A–S–H (filled symbols, Al/Si = 0.05) as a function of the Ca/Si ratio of the C–(A–)S–H
after 182 days of hydration.

Fig. 12. Evolution of the silicon (squares), calcium (diamonds), and aluminium (triangles) Fig. 14. Aluminium uptake in C–S–H (molar Al/Si including Al(VI) in TAH) after 182 days
concentrations in the solution as a function of the total Al/Si at a target Ca/Si of 1.2. Empty as a function A) of the total Al/Si ratio (black line shows theoretical total aluminium uptake
symbols: 182 days, filled symbols: 365 days. in C–S–H) and B) of the dissolved aluminium concentrations.
118 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121

3.1.6. Aluminium uptake in C–S–H which results in a distinct increase of the chain length. At high Ca/Si
Fig. 14A shows that the Ca/Si ratio has a minor effect on the total ratios, octahedrally coordinated Al(VI-b) is predominately present in
amount of aluminium taken up in C–S–H, although the coordination calcium aluminate hydrate (TAH). In addition, smaller fractions of
environment of aluminium changes as shown in Fig. 10. The fraction Al(V) and Al(VI-a) have been observed at all Ca/Si ratio; these alumini-
of aluminium in C–S–H increases up to Al/Si = 0.12, i.e. ,at relatively um species have been suggested to be present in the interlayer of C–S–H
low aluminium concentrations where the solutions are undersaturated [16,18,28,44]. The presence of aluminium in the interlayer is consistent
with respect to strätlingite or katoite. At higher total Al/Si ratios (N0.1) with the increase of interlayer spacing by ~ 2 Å of the C–A–S–H com-
the aluminium uptake does not increase further as in addition katoite pared to C–S–H shown in Fig. 5. Comparison between the aqueous alu-
and stratlingite precipitate at all Ca/Si ratios. Fig. 14B shows the Al/Si minium concentrations and the molar Al/Si in C–S–H points towards
ratio in C–S–H as a function of the dissolved concentrations and indi- two different uptake mechanisms. At Ca/Si ≥ 1 aluminium is taken up
cates two different uptake regimes at high and at low Ca/Si ratios. At mainly in TAH. The exact nature and location of TAH is not known, but
Ca/Si ≥ 1.0, the Al/Si ratio in C–S–H increases gradually with the aque- its formation is associated with the presence of C–A–S–H. A clear depen-
ous aluminium concentrations, as reported previously for synthetic C– dence between aqueous aluminium concentrations and the molar Al/Si
S–H gels [18,24,26] and for ordinary Portland cements and Portland ce- in C–S–H including TAH can be observed. At Ca/Si = 0.6 and 0.8, where
ments blended with silica fume or fly ash [31,75]. At low Ca/Si = 0.6 and aluminium is bound in the bridging tetrahedra, low aqueous aluminium
0.8, similar maximum Al/Si ratio is observed as at higher Ca/Si, although concentrations are observed in the presence of Al/Si ratio up to 0.2,
the aqueous concentrations are lower (below the detection limit of which indicates a higher affinity of aluminium uptake in the bridging
0.0037 mmol/L). This observation indicates a higher affinity of alumini- tetrahedra than in TAH.
um uptake at low Ca/Si, i.e. a preferential uptake of aluminium in the
bridging tetrahedra, resulting in very low aluminium concentrations.
Acknowledgments
At higher Ca/Si ratio, the further uptake of aluminium in bridging
sites is not favourable such that aluminium is in equilibrium with
The financial support of Swiss National Foundation grant no. 130419
TAH, resulting in higher aluminium concentrations. If at intermediate
is gratefully acknowledged. The authors would like to thank Daniel
Ca/Si ratio two or three different aluminium binding sites with different
Rentsch, Salaheddine Alahrache, Angela Steffen, Luigi Brunetti, and
affinity are present in C–S–H, sorption isotherms recorded as function of
Boris Ingold for the helpful advice and support during the measure-
the aluminium concentration could indicate the relative amount of such
ments. Andre Nonat, Rupert, Myers, Celine Cau-dit-Coumes, Jeremy
sites. Such measurements, however, are presently hampered by the
Haas, and Gilles Plusquellec are acknowledged for many helpful discus-
small experimental window between the analytical detection limit of
sions on the topic of C–A–S–H. The thanks are extended to the re-
the ionic chromatography used (0.0037 mmol/L) and the aluminium
viewers, whose comments helped to improve the manuscript.
concentrations until stratlingite or katoite precipitates, which limits
the aluminium concentrations to 0.01–0.05 mmol/L, depending on the
Ca/Si ratio. The use of alkali hydroxides and/or of measurements Appendix A. Mixing proportions used to prepared C–S–H and
methods with lower detection limits such as ICP-MS may allow in the C–A–S–H
future the record of sorption isotherms over a reasonable range of
aluminium concentrations.
Ca/Si Al/Si Initial composition
4. Conclusions CaO (g) SiO2 (g) CaO.Al2O3 (g)

0.6 0 0.718 1.282 0.000

In synthetic C–S–H equilibrated up to 1 year, Ca/Si ratios in the solid 0.03 0.689 1.261 0.050
from ≥0.67 to 1.5 are observed; the upper Ca/Si ratio is limited by the 0.05 0.670 1.248 0.082
formation of portlandite, the lower Ca/Si ratio by the presence of amor- 0.1 0.624 1.216 0.160
phous silica; the measured silicon and calcium concentrations mirror 0.2 0.540 1.156 0.304
0.33 0.441 1.087 0.472
the composition of the solid phase in agreement with previous data,
0.8 0 0.855 1.145 0.000
e.g. [24,25]. A low Ca/Si ratio leads to high dissolved silicon concentra- 0.03 0.827 1.129 0.045
tions (3–4 mmol/L) and low calcium concentrations (1 mmol/L) and 0.05 0.809 1.118 0.074
pH values, while at Ca/Si = 1.5 and in the presence of portlandite, a 0.1 0.764 1.092 0.144
pH of 12.5 and 20 mmol/L calcium and 0.01 mmol/L silicon are typically 0.2 0.682 1.044 0.275
0.33 0.585 0.987 0.428
measured.
1.0 0 0.966 1.034 0.000
In the presence of aluminium, comparable variations of the solid 0.03 0.939 1.021 0.040
and aqueous compositions are observed. In C–S–H with a Ca/Si ≥ 1, 0.05 0.921 1.012 0.067
the aluminium uptake in C–S–H depends on the total amount of alumin- 0.1 0.879 0.991 0.130
0.2 0.799 0.951 0.250
ium present in the sample and a close relation between aqueous
0.33 0.704 0.904 0.392
aluminium concentrations and the molar Al/Si ratio in C–A–S–H is 1.2 0 1.057 0.943 0.000
observed up to an Al/Si of approximately 0.1. At Al/Si N 0.1, in addition 0.03 1.031 0.932 0.037
to C–A–S–H also stratlingite, katoïte, and/or monocarbonate are present 0.05 1.014 0.925 0.061
in long-term co-precipitation experiments, as used in the present study, 0.1 0.974 0.907 0.119
0.2 0.897 0.873 0.230
which limits the Al/Si ratio in C–S–H to 0.15 ± 0.05 in the absence of
0.33 0.805 0.833 0.362
alkali hydroxide. Higher Al/Si ratios for synthetic C–S–H have been ob- 1.4 0 1.133 0.867 0.000
tained either in short-term experiments where pre-synthesized C–S–H 0.03 1.109 0.858 0.034
was added to calcium aluminate solutions resulting in higher alumini- 0.05 1.093 0.851 0.056
0.1 1.054 0.836 0.110
um concentrations [18,24,26], or in the presence of alkali hydroxides,
0.2 0.980 0.808 0.212
which increase the pH values, supress the precipitation of stratlingite 1.6 0 1.198 0.802 0.000
and katoite, and thus increase the aluminium concentration in solution 0.03 1.175 0.794 0.031
and also the amount of aluminium incorporated in C–A–S–H [1]. 0.05 1.159 0.789 0.052
In low Ca/Si C–S–H, aluminium is taken up mainly as tetrahedrally 0.1 1.122 0.776 0.102
0.2 1.051 0.751 0.198
coordinated Al(IV) in the bridging position of the dreierketten chain,
 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121 119

Appendix B. C–A–S–H composition in molar ratio determined from mass balance (hydrated for 182 days). Mass balanced Al in C–S–H includes
Al(VI) assigned to TAH

Target ratio C–S–H composition (molar ratio) Mean basal spacing Other solid (%wt)
(Å) ± 0.1
Ca/Si Al/Si Ca/Si1 Ca/(Si + Al) 1 Al/Si1 H2O/Si ± 0.3 C3AH6 C2ASH8 CO3 AFm CH

0.6 0 ≥0.67 ≥0.67 – 1.1 – – – – –

0.03 ≥0.67 ≥0.67 0.031 1.2 nd – – – –
0.05 ≥0.67 ≥0.67 0.052 1.4 – – – – –
0.1 ≥0.67 ≥0.67 0.068 1.3 – 2.2 3.3 – –
0.2 ≥0.67 ≥0.67 0.11 1.4 – 2.3 12.4 – –
0.33 ≥0.67 ≥0.67 0.23 1.5 – 1.3 15.9 – –
0.8 0 0.80 0.80 – 1.3 – – – – –
0.03 0.81 0.79 0.031 1.4 nd – – – –
0.05 0.81 0.77 0.051 1.5 – – – – –
0.1⁎ 0.80 0.73 0.10 1.4 – Trace – – –
0.2⁎ 0.80 0.73 0.10 1.4 – 5.7 6.9 – –
0.33⁎ 0.70 0.63 0.11 1.5 – 1.2 27.7 – –
1.0 0 0.98 0.98 – 1.2 12.6 – – – –
0⁎⁎ 0.98 0.98 – 12.1+ – – – –
0.03 0.97 0.95 0.030 1.3 12.5 – – – –
0.05 0.99 0.94 0.05 1.4 12.70+ – – – –
0.1 0.95 0.88 0.08 1.5 – 2.8 – – –
0.1⁎⁎ 0.99 0.90 0.10 12.13+ – – – –
0.2 0.94 0.85 0.11 1.6 – 5.9 13 – –
0.33 0.88 0.84 0.05 1.5 – 7.2 25 – –
1.2 0 1.17 1.17 – 1.5 10.2 – – – –
0⁎⁎ 1.17 1.17 – 10.36+ – – – –
0.03 1.17 1.14 0.030 1.5 nd – – – –
0.05 1.18 1.12 0.050 1.9 – – – – –
0.05⁎ 1.17 1.12 0.05 12.73+ – – – –
0.1 1.2 1.1 0.10 1.5 nd Trace – – –
0.2 1.13 0.99 0.14 1.8 – 5.2 5 – –
0.33 1.02 0.93 0.10 1.7 – 5 21 – –
1.4 0 1.29 1.29 – 1.6 9.8 – – – –
0⁎ 1.31 1.31 – 9.65+ – – – –
0.03 1.32 1.28 0.030 1.5 – – – – –
0.05 1.32 1.26 0.050 1.5 12.2 – – – –
0.05⁎ 1.32 1.26 0.05 11.41+ Trace – – –
0.1 1.11 1.03 0.078 1.5 12.5 1.6 – – –
0.2 1.28 1.14 0.12 1.9 – 5.3 3.4 – –
1.6 0 1.38 1.38 – 1.8 10.0 – – – 2.0
0⁎ 1.47 1.47 – 9.94+ – – – –
0.03 1.43 1.39 0.03 1.9 12.0 – – – 2.2
0.05 1.43 1.37 0.05 1.9 12.4 – – – 1.8
0.05⁎ 1.40 1.33 0.05 1.9 12.14+ – – – 2.2
0.1 1.35 1.28 0.06 2.0 – 1.6 – 3.5 trace
0.2 1.38 1.22 0.13 2.0 – 3 3 1.9 –
1
Error ±0.01 in the absence of other phases, ±0.1 in the presence of the other phases. nd: not determined as no well-defined peak within the 2θ range measured. –: not observed.
⁎ 364 days.
⁎⁎ 546 days.
+
Measurement realised with anatase as internal standard.

Appendix C. TGA of C–A–S–H at different Al/Si ratio

TGA of C–S–H after 182 days TGA of C–A–S–H with an Al/Si ratio =0.1 after 182 days (*1 year).
120 E. L’Hôpital et al. / Cement and Concrete Research 85 (2016) 111–121

Appendix D (continued)
(continued)

Target Ca/Si Target Al/Si Time Si Ca Al OH pH

ratio ratio (days)
(mmol/L) –

364 0.14 13 ≤0.0037 23 12.5

0.05 182 0.16 12 0.0039 29 12.6
364 0.16 12 ≤0.0037 18 12.4
0.1 182 ≤0.0036 12 0.040 17 12.3
364 0.16 12 ≤0.0037 15 12.3
0.2 182 ≤0.0036 8.3 0.040 14 12.2
364 0.03 5.8 0.040 13 12.2
1.6 0 182 0 26 – 35 12.6
364 0.01 19 – 26 12.5
0.03 182 0.0095 17 0.0039 29 12.6
364 0.0095 17 ≤0.0037 28 12.6
0.05 182 0.019 18 ≤0.0037 26 12.6
364 0.019 18 ≤0.0037 30 12.6
0.1 182 ≤0.0036 25 0.010 38 12.6
364 0.019 18 ≤0.0037 28 12.5
0.2 182 ≤0.0036 19 0.040 29 12.5
TGA of C–A–S–H with an Al/Si = 0.2 after 182 days. 364 0.019 12 0.034 21 12.4

Measurement error: aqueous silicon, calcium and aluminium concentrations ± 10%;

pH ± 0.1 unit. -: no aluminium in the sample.
Appendix D. Measured dissolved concentrations and saturation
index after different equilibration time at 20 °C as a function of time
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