Cement and Concrete Research 67 (2015) 93102

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Cement and Concrete Research

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Friedel's salt formation in sulfoaluminate cements: A combined XRD and

27
Al MAS NMR study
G. Paul a, E. Boccaleri a,, L. Buzzi b, F. Canonico b, D. Gastaldi b,
a
b

Dipartimento di Scienze ed Innovazione Tecnologica, Universit del Piemonte Orientale A. Avogadro, Viale T. Michel 11, 15121 Alessandria, Italy
Buzzi Unicem S.p.A., Via L. Buzzi 6, 15033 Casale Monferrato (AL), Italy

a r t i c l e

i n f o

Article history:
Received 29 April 2014
Accepted 19 August 2014
Available online xxxx
Keywords:
pH (A)
Spectroscopy (B)
X-Ray Diffraction (B)
Blended Cement (D)
Chloride (D)

a b s t r a c t
Four different binders based on calcium sulfoaluminate cements have been submitted to accelerated chlorination
through ionic exchange on hydrated pastes, in order to investigate their ability to chemically bind chloride ions
that might reduce chloride penetration. The composition of hydrated cements before and after the treatment was
evaluated by means of an X-Ray Diffraction27Al Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy combined study, allowing to take into account even partially amorphous phases and to make quantitative assumption on the relative abundance of the different aluminium-containing phases. It was found that low SO3
SulfoaluminatePortland ternary systems are the most effective in binding chloride ions and the active role
played by different members of the AFm family in chloride uptake was conrmed. Moreover, a peculiar behavior
related to the formation of Friedel's salt in different pH conditions was also established for the different cements.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The increased attention towards sustainable production and raw
material preservation highlights that nowadays the two main research
lines in the eld of cement chemistry and concrete technology are:
(I) the search for innovative high performing binders characterized by
a reduced CO2 footprint and low environmental impact and (II) the durability issues of concrete for buildings and constructions.
One of the potential alternatives to Ordinary Portland Cement (OPC)
is nowadays represented by Calcium Sulfoaluminate Cement (CSA), a
low-temperature binder produced from limestone, bauxite and gypsum
and based on ye'elimite (C4 A3 S) as main mineral phase [1,2]. Differently
from OPCs, CSA based systems are high-performance binders characterized by fast setting and rapid hardening as well as high chemical resistance and reduced shrinkage, that they can counteract thanks to an
expansive behavior [3,4]. These performances arise mostly as the consequence of the rapid formation of stable ettringite crystals during the
early hydration [5]. When CSA clinker/cement is mixed with OPC, a
wide range of products characterized by markedly different engineering
features, such as high early compressive strength, tunable time of workability depending on the use of different additives, high frost and corrosion resistance and limited shrinkage, can be obtained [68]. In both
cases the high amount of ettringite is mainly responsible for the lowporous structure [911], a peculiar feature making these cements also
Corresponding author. Tel.: +39 0131 360264.
Corresponding author. Tel.: +39 0161 809740.
E-mail addresses: enrico.boccaleri@mfn.unipmn.it (E. Boccaleri),
dgastaldi@buzziunicem.it (D. Gastaldi).

http://dx.doi.org/10.1016/j.cemconres.2014.08.004
0008-8846/ 2014 Elsevier Ltd. All rights reserved.

less sensitive to possible interaction with external agents and, therefore,

able to confer a highest durability to concrete structure.
Thanks to these peculiar properties in terms of performances and
sustainability, during the last 5 years CSA cements have been the subject of intense research and studies by the major companies operating
in the production of cement and concrete and in few cases a limited industrial production was also established. At the present state of
European standard regulations, binders based on CSA cements cannot
be used in structural concrete according to the EN 2061; nevertheless,
three formulations of CSA cements produced by Buzzi Unicem in Trino
(Italy) obtained in June 2013 a CE mark based on a ETA1 procedure, released by DIBt,2 also allowing the use for structural application [12,13].
Durability aspects of concrete based on CSA cements are still part of
ongoing research activity, and due to a very limited use of this binder in
Europe in the last decades, there is low in-eld practical experience
(mainly experienced by cement companies in internal tests) to support
laboratory tests.
CSA cements exhibit excellent resistance against sulfate attack and
freezethaw and good resistance against chloride migration, probably
as a consequence of the above mentioned reduced porosity; on the
other hand, due to a lower pH buffering potential they show a higher
carbonation compared to OPC [14].
In this paper the effect of chloride ions on different formulations of
sulfoaluminate cement (alone and in mixture with OPC) has been investigated through an accelerated ionic exchange method developed with

1
2

European Technical Approval.

Deutsches Institut fr Bautechnik.

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G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

the aim to deepen the knowledge about the mechanisms of degradation

by means of chloride attack in CSA cement based concrete.
Chloride attack is known to be one of the main external chemical
causes, together with carbonation and sulfate attack, of structural damages in concrete: free chloride ions, deriving from sea water, deicing
salts or even present inside the concrete itself, can reach reinforcement
steel bars and promote electrochemical corrosion. Generally, the evaluation of chloride penetration inside concrete is based on one of the following ionic diffusion tests [15]:
I. the steady state diffusion test, in which a thin slice of test specimen forms a barrier between a chloride source and another suitable sink solution free of the ion and the diffusion coefcient is
calculated once that the steady state has been reached (i.e. once
that the chloride concentration in the sink solution doesn't
change anymore);
II. the non-steady state diffusion test, in which one single surface of
the specimen is subjected to chloride treatment after sealing all
the other surfaces by immersion or by ponding the solution
over it and the results are evaluated by plotting the amount of
chloride as a function of the distance from the surface after a dened time of exposure;
III. the electric eld migration test, in which transport of ions is accelerated through the application of electrical potential gradient,
such as the widely diffused CTH method proposed by Tang and
Nilson [16].
From the physical point of view, the most widely known trick to reduce the ionic diffusion is to decrease the porosity of the system (and
this can be generally achieved) or by reducing the water-to-cement
ratio or by including a certain amount of ne llers in the mix design
[17].
From the chemical point of view, an autogenous protection of cements against chloride penetration is supplied by some mineralogical
phases able to bind chloride and prevent its further diffusion. Any mineral phase can potentially bind chloride ions at a different extent: calcium silicate hydrates (C-S-H) formed during Portland Cement hydration
can partially counteract chloride migration through a physical adsorption of some ions and a similar behavior is also reported for ettringite
[18]; differently, in phases such as AFm a chemical interaction has
been envisaged. AFm stands for Al2O3-Fe2O3-mono and describes a
family of few mineral phases having the general formula C4(A,F)
X2yH2O [19], being X a singly charged anion (like OH or Cl) or a
or CO2
half double charge anion (like SO2
4
3 ). From the mineralogical
point of view, AFm phases have a layered structure in which positively
charged main layers contain [Ca2Al(OH)6]+ units and the negatively
charged interlayers host the X anions. AFm phases in cement pastes
are characterized by a variable degree of disorder and their stability is
strongly dependent from the surrounding environment: the presence
of an excess of one or another anion in the pore solution, the water
amount, the pH condition, can inuence the stability equilibria and
modify the AFm composition and structure. The following abbreviations
will be used for the different AFm phases3:

Ms (monosulfate) = C3 ACSH14
Hc (hemicarbonate) = C3 A0:5CC0:5CHH12
Mc (monocarbonate) = C3 ACCH11
F (Friedel's salt) = C3A CaCl2 H10

Many theoretical studies have been performed regarding the chemical equilibria and the stability elds of the different AFm phases in
Portland cements: in most cases pure systems were articially prepared
[2023] and it was found that solid solution between the above mentioned phases was also thermodynamically allowed [24]; moreover, intermediate ordered compounds, such as Kuzel's salt (reported as
3
Note that standard cement nomenclature is followed here, whereby C = CaO,
S = SiO2, A = Al2O3, F = Fe2O3, S = SO3, C = CO2 and H = H2O.

C3 A0:5CaCl2 0:5CSH1011 ), can even form in specic concentration

range of anions [25,26].
In this paper, AFm phases forming in commercially available CSA
cementing systems are instead considered. The formation of ettringite
and AFm phases in hydrated cements and their ability to uptake chloride ions in different pH conditions are hereafter investigated through
a series of experiments aimed at verifying and understanding the role
of Friedel's salt with regard to chemical chloride binding.
The effect of accelerated chlorination on cement paste samples was
investigated by coupling X-Ray Diffraction (XRD) and Solid State Nuclear Magnetic Resonance spectroscopy (NMR).
X-ray diffraction is a well established technique largely diffused in
the eld of cement investigation and for hydration studies, but its application is limited to the analyses of crystalline mineral phases and, when
dealing with AFm phases, a high degree of disorder must be taken into
account.
Solid-state NMR spectroscopy is a powerful method for characterizing cements and cementitious materials [2729]: thanks to the nuclearspin selectivity, where only one nuclear-spin isotope of the NMR periodic table (e.g., 1H, 27Al, 29Si, ) is independently detected and analyzed
at a time, and to the fact that the resonances from these spins reect the
local structure, amorphous and crystalline phases, short and long range
ordered phases, are equally well detected. In particular, when investigating aluminate phases such as ettringite and AFm, 27Al MAS NMR
spectroscopy represents a valuable analytical tool: the high sensitivity
for the 27Al nucleus (e.g., 100% natural abundance and a high gyromagnetic ratio) allows to easily distinguish the tetrahedrally and octahedrally coordinated Al species [30,31]. Moreover, the multiple-quantum
magic-angle spinning (MQMAS) technique, developed in 1995 [32], allows the use of standard MAS probes to obtain well-resolved twodimensional NMR spectra that contain an isotropic dimension unperturbed by quadrupolar broadening: the application of this technique
to clearly resolve and assign spectral features to Al in tetrahedral, pentahedral and octahedral coordination has been nicely demonstrated
[3335]. In this study, a combination of one-dimensional and twodimensional 27Al solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) experiments has been used.
2. Experimental
Five different cements have been investigated:
One Ordinary Portland Cement CEM I 52.5 R (OPC), analyzed as a reference;
One sulfoaluminate cement (SAC) consisting in a mixture of CSA
clinker and anhydrite fullling ETA 13/04174;
Three sulfoaluminate cements (MIX A, MIX B, and MIX C) consisting
in ternary mixture of CSA clinker, anhydrite and Portland cement
fullling ETA 13/0418.5
All the materials were supplied by Buzzi Unicem S.p.A. The mineralogical compositions of the OPC (CEM I 52.5 R) and of the CSA clinker are
shown in Table 1 while in Table 2 the chemical analyses are reported together with the anhydrite's element content; the different compositions
and some main features of the sulfoaluminate cements are summarized
in Table 3.
40 g of each cement sample has been hydrated (w/c = 0.4) under N2
atmosphere by mixing on a vortex shaker for 2 min, then poured in
sealed plastic case ( = 40 mm; h = 60 mm) and stored at 20 C and
4
ETA 130417 requires the fullling of the following parameter: CSA clinker 83 7%,
Anhydrite 17 7%, SO3 13.8 5%, C4A3 S 52 7%, Strengths at 8 h N 10 MPa and at
28 days N 32.5 MPa, Cl b 0.1%, Density 3.0 0.2 g/cm3, Blaine 4640 500 cm2/g,
Soundness b 10 mm.
5
ETA 130418 requires the fullling of the following parameter: CEM I 52. 5 R 61 7%,
CSA clinker 28 7%, Anhydrite 11 7%, SO3 11.8 5%, C4A3S 14 7%, Strengths at
8 h N 10 MPa and at 28 days N 32.5 MPa, Cl b 0.1%, Density 2.7 0.2 g/cm3, Blaine
5175 500 cm2/g, Soundness b 10 mm.

G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

Table 1
Mineralogical composition of the reference CEM I 52.5R sample and of the CSA clinker detected by semi-quantitative Rietveld analyses on XRD patterns.

C3 S
C2 S
C3 A
C4AF
Yeelimite
Gypsum
Anhydrite
Calcite
Minor phases

ICSD

OPC (CEM I 52.5R)

CSA clinker

94472
963
1841
2842
80361
81650
16382
18165

66.9
7.2
13.7
3.6

3.6

0.5
4.5

25.6
8.0
1.1
56.7

3.9

4.7

95% relative humidity. After 28 days, the samples have been crushed
until all fragments were smaller than 2 mm and analyzed as reference.
20 g of each crushed sample were then treated with 100 ml of the different exchange solutions, respectively consisting in:
a. distilled water;
b. 3% w/w chloride solution at pH = 7;
c. 3% w/w chloride solution at pH = 1.
For the preparation of b. and c. solutions, Merck NaCl and Panreac
HCl 37% were used (reagent degree). The treatment with water was
performed in order to evaluate the global effects that the sample manipulation may have on the mineralogical structure of the hydrated cement
pastes and to eventually exclude effects that are not ascribable to chloride exchange.
The treatment consisted in mixing the cement paste fragments with
the exchange solution in 250 ml sealed glass bottle and shaking them
continuously on a horizontal shaker for four days.
The treated samples were recovered by ltering the solution on a
Buchner funnel under vacuum (KNF Neuberger vacuum pump, series
N 026.32, 20 mbar nal vacuum); in order to remove the residual
NaCl it was necessary to wash the samples twice with 50 ml of distilled
water. The fragments were then dried in a oven at 40 C for 24 h and
submitted to characterization, while the pH values on the ltered solutions were measured by means of a Seven Multi Mettler Toledo pHmeter using a HI1144 Hanna saturated calomel electrode. pH values
are summarized in Table 4.
All the samples were characterized by means of X-ray uorescence
(XRF), X-ray diffraction and Solid State NMR.
For XRF measurements, a Panalytical Axios Cement dispersive
spectrometer was used. Fused beads were prepared by means of a
Breithlnder autouxer mixing 0.9 g of calcined sample with Litethraborate resulting in a 1:10 dilution. The data treatment was
based on the IQ + Panalytical semi-quantitative software, a standardless application allowing to obtain the element content expressed as a
percentage in weight of the corresponding metal oxide. The chloride
Table 2
Chemical composition of the used materials detected by means of X-ray uorescence
expressed as % in weight (average error estimated for the different oxides b 2%).

LOI
SiO2
CaO
MgO
Al2O3
Fe2O3
SO3
K2O
Na2O
TiO2
SrO
P2O5
Cl

OPC (CEM I 52.5R)

CSA clinker

Anhydrite

2.3
19.6
64.7
1.7
5.1
1.8
3.6
1.0

0.2

9.7
43.0
3.7
29.8
2.4
8.9
0.5
0.4
1.2
0.1
0.1
b 0.1

0.7
0.1
44.6
b 0.1
0.1
0.1
54.3

95

amount of the different samples, as measured by XRF, is shown in

Table 5, together with the residual chloride amount measured on the ltered solutions by means of a Helios Aquamate Thermo Spectronic
spectrophotometer.
The XRD measurements, performed on pressed pellets prepared by
means of an APM Polab automatic pelletizer (Polysius), were obtained
on a Bruker AXS D4 Endeavor diffractometer working in Bragg
Brentano geometry, equipped with a ceramic X-ray tube KFF (Cu K radiation) and a Linx Eye dispersive detector. The acquisition of diffraction patterns was performed in the 855 2 range at 0.02 2 step size
and 0.5 s time/step; during the acquisition the sample was continuously
spinned at 30 rpm.
Mineral phase identication was carried out through the EVA software while renement for semi-quantitative mineralogical analyses
was conducted by Rietveld method using the Topas 2.0 package (both
software were commercially supplied by Bruker AXS). The renements
were conducted in the whole 855 2 range by using a 5 order
Chebychev Polynomium for the background calculation and allowing
renement of the sample displacement; crystal size of all structures
were set free to vary between 32 and 500 nm while preferred orientations were avoided thanks to automatic sample preparation; Rwp
(Residual weighted prole) value was in all cases lower than 10% and
estimated average error of renement was lower than 2%.
Solid state NMR spectra were acquired on a Bruker Advance III 500
spectrometer and a wide bore 11.7 T magnet with operational frequency for 27Al of 130.33 MHz. A 4 mm triple resonance probe with MAS was
employed in all the experiments and the samples were packed in a Zirconia rotor and spun at a MAS rate of 15 kHz, giving a sample temperature of 304 K. The 27Al 1D MAS spectra have been acquired on large
sweep width with small pulse angle (/12) to ensure quantitative reliable intensities, and with no 1H decoupling during acquisition. The relaxation delay, d1, between accumulations was 1 s and chemical shifts
are reported using scale and are externally referenced to Al(H2O)3+
6
ion in 1.0 M AlCl3 solution to 0.9 ppm.
All NMR spectra were tted with DMFIT functions for quantitative
deconvolution of overlapping peaks [36]. The lineshape of the peaks associated with ettringite, monosulfate, Friedel's salt and calcium aluminate hydrates were described by a Lorentzian function and/or the
Czjzek model: the Lorentzian lineshape was selected for the high symmetrical sixfold coordination of aluminum sites (as in ettringite or
Friedel's salt) that lead to no or weak quadrupolar effects; on the
other hand, poorly crystallized and/or amorphous species leads to
asymmetry in the lineshape that can be well described by the Czjzek
model [37,38].
3. Results
3.1. Ordinary Portland cement
Portlandite (CH) is the main crystalline phase appearing when
Portland cement hydrates, it forms as a by-product from the reaction
of C2S and C3S with water; the main hydration product is C-S-H, an
amorphous hydrate calcium silicate characterized by a CaO/SiO2 ratio
between 1.6 and 2.0 and H2O/SiO2 = 4 in a fully saturated cement
paste [19].
Ettringite (C6AS3H32) also forms during OPC hydration from the reaction between the aluminate clinker phases (C3A and C4AF) and gypsum; ettringite (belonging to the AFt family, in which Aft stands for
Al2O3-Fe2O3-tri, three anions per formula unit) is generally well crystallized even if crystal size and stability depend on the environment in
which it forms and grows. For lower SO3/Al2O3 ratio, monosulfate can
also become stable; however, in presence of carbonate ions, mono or
hemicarbonate tend to precipitate and stabilize ettringite [39].
The diffraction patterns of the 28 days aged OPC paste and of the
treated samples are shown in Fig. 1: only the region between 8 and
20 2 is reported, being the region in which main reections of

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G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

Table 3
Main features of the investigated sulfoaluminate cement. In the C4 A3 S=CS ratio, calcium sulfate is the overall amount deriving from anhydrite, CSA clinker and OPC cement.
Sample name
Composition

OPC (CEM I 52.5R)

CSA clinker
Anhydrite

SO3 (%)
(EN 1962)
C4 A3 S=CS
(XRD)
Mechanical strength
8h
(MPa)
28 days
(EN 1961)
Reference document fullled by the cement

SAC

MIX A

MIX B

MIX C

84
16
16.2

54
35
11
11.1

54
29
17
13.8

59
35
6
8.5

2.47

1.38

0.82

2.09

40.1
70.3

15.4
55.3

25.2
66.1

11.5
50.5

ETA 13-0417

ETA 13-0418

ETA 13-0418

ETA 13-0418

ettringite, AFm phases and the main peak of Portlandite can be found.
The 28 days aged OPC paste shows the presence of the main XRD peak
of ettringite, corresponding to its (100) reection, at 9.3 2; moreover,
two wide and low intensity peaks appear at 10.2 and 10.6 2, respectively corresponding to the (003) reection of Ms and to the (006) reection of Hc [40,41]; nally, a sharp peak corresponding to the (001)
reection of Portlandite is present at 18.3 2. When the sample is treated with water, a decrease in intensity of the three peaks of ettringite, Ms
and Hc is observed, together with a widening of the Hc reection and
the appearing of a low peak probably corresponding to Mc. The treatments with the two chloride solutions give similar effects on the XRD
patterns, independently from the pH of the exchange solution: in both
cases a peak at 11.4 2 clearly appears, attesting the formation of
Friedel's salt [42].
27
Al MAS NMR investigation (Fig. 2) shows signicant contributions
in the range 1020 ppm and lower signals in the 5580 ppm region, respectively due to octahedrally and tetrahedrally coordinated aluminum
sites. In general, tetrahedral Al exhibits a broad asymmetric lineshape
characteristic of the combination of signicant distributions of isotropic
chemical shift and second-order quadrupolar broadening. Such effects
are also present in the case of the Al(VI) signals, however, depending
on the ordering and symmetries of the investigated systems.
The quadrupolar interaction parameters and isotropic chemical shifts
for different contributions, such as Al(IV) and Al(VI), can be derived from
the 3QMAS data and can be used to model and quantitatively interpret
the experimental 1D MAS spectra. In 3QMAS experiment, the 27Al resonances are spread in two dimensions, according to their isotropic chemical shifts and quadrupolar couplings [43]. Since the 2D 3QMAS NMR
(data not shown) technique was limited in the quantitative evaluation
of the signal intensities, the 1D MAS NMR technique was used for the
quantitative determination of the aluminum distribution in our samples.
The 27Al MAS NMR spectra of 28 days hydrated OPC paste is shown
in Fig. 2, together with the corresponding tted spectra and their individual components from each 27Al site, while the relative population
distribution of various sites is given in Table 6. In the octahedral region,
contributions due to ettringite at 14.5 ppm, monosulfate at 11.5 ppm,
hemicarbonate at 10.5 ppm and third aluminate hydrates (TAH) at
6.5 ppm are visible [44,45].

Table 4
pH values of the eluates collected after the treatment with the three different exchange solutions: a = water; b = 3% chloride solution at pH = 7; c = 3% chloride solution at
pH = 1 (estimated error b 0.5 units).
Sample name

OPC
SAC
MIX A
MIX B
MIX C

According to Andersen et al. [46], TAH represents phases and/or precipitates of calcium aluminate hydrates or aluminate hydrates on particle surfaces of C-S-H grains and they are not detected in the XRD
investigation probably because of a scarce crystalline degree or a too
small crystal size: nevertheless, they are quite important phases, as it
is calculated that in these phases the highest amount of octahedral aluminium is entrapped (see Table 6).
Al substituting for Si in C2S and C3S gives resonances at around
80 ppm. The resonance at 70 ppm originates from Al(IV) in the C-S-H,
incorporated in the bridging site (Q2B) of the silicate chains [44,47,48].
Considering the low amount of C4AF in the OPC and CSA clinker
(Table 1) and the results from an earlier 27Al MAS NMR study of pure
C4AF phases [49] it can in fact be ruled out that a contribution from
Al(IV) in C4AF is observed in the present spectra.
Upon treatment with water, tetrahedral as well as octahedral phases
undergo structural transformation with new distribution ratios of aluminum site intensities. Increased amount of hydrates indicates rehydration of the residual cement as well as the inter-conversion of various
phases. A new broad resonance centered at about 60 ppm in the tetrahedral region belongs to aluminum substituting silicon in the branching
positions (Q3) of C-A-S-H gel [31]. Further increases in the AFm phases
are clearly visible (Table 6) at the expenses of third aluminate hydrate
phase, while the amount of ettringite is unchanged. The wide signal
centered at approximately 10.6 ppm was associated with the presence
of monosulfate or hemicarbonate, for both compounds generate signals
at around 11/10 ppm. As a result, they overlap and their discrimination
is actually not possible. Comparing these data to the XRD results above
presented, it can be stated that the decrease of ettringite reection at
9.3 2 is due to a loss of crystallinity and not to a real decrease in its
amount.
The 27Al MAS spectra recorded after chloride exchange at pH = 7
and pH = 1 show the formation of Friedel's salt [50] and the disappearance of AFm phases, in agreement with XRD observation. 27Al chemical

Table 5
Chloride ions distribution after the treatment with the three different exchange solutions
(a = water; b = 3% chloride solution at pH = 7; c = 3% chloride solution at pH = 1).
From left: chloride amount (% in weight) as measured by XRF on the cement samples after
the treatment (estimated error b 2%); percentage of chloride bound calculated with respect to the initial added amount; residual chloride amount (in g/L) measured on the solution after ltering by means of UV spectroscopy (estimated error b 1%).
Sample name

Treatment
a

12.3
12.0
12.2
11.8
13.0

11.8
11.8
12.3
12.0
13.2

11.4
9.7
11.4
10.3
12.5

OPC
SAC
MIX A
MIX B
MIX C

Chloride amount
(% in weight) as
measured by
XRF

Bound chloride
(%) with respect
to the initial
added amount

Residual chloride
in the solution
after ltering (g/L)

0.1

1.9
0.6
1.9
2.0
3.3

2.2
0.6
1.4
0.7
4.0

b1

12.7
4.0
12.7
13.3
22.0

14.7
4.0
9.3
4.7
26.7

26.8

23.3
25.2
23.6
22.9
19.9

23.6
25.9
23.1
25.7
19.1

G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

97

Table 6
Population distribution of tetrahedral and octahedral 27Al sites in different samples.
Values reported for tetrahedral 27Al sites are the sum of aluminates and/or aluminosilicates
and/or C-S-H/C-A-S-H (estimated error b 2%). (E = ettringite; Ms = monosulfate;
Mc = monocarbonate; Hc = hemicarbonate; F = Friedel's salt; AH3 = aluminum hydroxide; T = third aluminate hydrate; C-A-S-H = Calcium aluminium silicate hydrates;
S = strtlingite).
27

Al Species (%)

Sample

AlIV

OPC

SAC

MIX A

Fig. 1. X-ray diffraction patterns of the OPC samples (HP = hydrated paste; a = treated
with water; b = treated with 3% chloride solution at pH = 7; c = treated with 3%
chloride solution at pH = 1): E = ettringite; Ms = monosulfate; Mc = monocarbonate;
Hc = hemicarbonate; G = gypsum; F = Friedel's salt; P = Portlandite.

shift of Friedel's salt in chloride exchanged paste appeared at 9.9 ppm

with a very sharp resonance. Actually, this chemical shift value is slightly down-eld shifted compared to the values reported in the literature
(9.2 and 9.5 ppm at 28 C): this is probably due to the fact that in the investigated sample there is still a residual fraction of AFm phases which
has a downeld chemical shift of 11.5 ppm and contributed to the
peak at 9.9 ppm; another possibility is that the well-known
phase transition that Friedel's salt undergoes at 33 C contributes to
the difference in chemical shift [51]. After the chloride ion introduction,
the aluminum phase distributions were similar in both the samples
(Table 6) independent of the fact that different pH values were used
for the treatment. Overall, an identical chloride binding mechanism as
well as binding capacity can be envisaged in OPC paste under wide pH
ranges, as also attested by the similar chloride amount detected on the
treated samples by XRF (Table 5). The high amount of chloride which
is bound in these systems, in spite of the relatively low amount of
AFm phases that is supposed to be present, lead to think that other
mechanisms intervene in chloride uptake, probably involving the well

Fig. 2. 27Al MASNMR spectra of OPC samples (HP = hydrated paste; a = treated with
water; b = treated with 3% chloride solution at pH = 7; c = treated with 3% chloride
solution at pH = 1). Each spectra includes experimental and its deconvoluted spectrum
with individual contribution from each 27Al sites: E = ettringite; Ms = monosulfate;
Hc = hemicarbonate; F = Friedel's salt; T = third aluminate hydrate.

MIX B

MIX C

HP
a
b
c
HP
a
b
c
HP
a
b
c
HP
a
b
c
HP
a
b
c

AlVI

Aluminate
Aluminosilicate
C-A-S-H

Ms/Mc/Hc

AH3

16
23
17
17
12
10
11
15
3
11
15
9
10
17
11
20
8
12
11
9

b1

5
b1

14
14
19
18
33
23
26
22
50
54
60
54
66
67
75
59
23
19
37
41

20/23
52

37
25

10
10

16
63
63

55
67
63
63

48
50

20
30

12

47
46

27
11
16
15

5
10
5
7
14
6
2
5
4
6
5
4

known physical adsorption from calcium silicate hydrates C-S-H and

C-A-S-H [18,52,53].
3.2. Sulfoaluminate cement
In the pure sulfoaluminate cement paste, a large amount of
ettringite, in the shape of large prismatic and extremely stable crystals,
is formed during early hydration, according to the following reaction:
C4 A3 S 2CS 38HC6 AS3 H32 2AH3

As by-product, aluminium hydroxide is formed [7], a phase characterized by gel-like structure containing a high and variable amount of
water molecules in the surrounding. As hydration goes on, also silicate
hydrates start to precipitate (C2S hydration): according to thermodynamics [54] it can react with Al(OH)3 gel forming strtlingite
(C2ASH8), lling up the pores and giving rise to the very dense structure
typical of sulfoaluminate cement paste.
X-ray diffraction pattern of SAC hydrated paste reveals, after
28 days, a high content of ettringite, as attested by the high intensity
of its main reection at 9.3 2 (Fig. 3). Apart from traces of residual gypsum, identiable through the small signal at 11.7 2, and a tiny broad
peak ascribed to Hc, no other hydrated phases are detected in the XRD
pattern.
When the hydrated cement sample is exchanged with water, no signicant effects are observed and the same happens after chloride ionic
exchange: no interaction between ettringite and chloride seems to
take place. The results of XRD measurements nd a further conrmation
when chemical analyses shown in Table 5 are considered: a very limited
amount of chloride ions is captured in these samples after ionic exchange, since the amount of chloride detected in both the samples is
very low.
The 27Al MAS NMR spectra of 28 days hydrated SAC paste is shown
in Fig. 4 and the pattern is very different from that of OPC paste: a contribution due to ettringite at 14.2 ppm is visible in the octahedral region,
together with a very broad peak with cg at 10.9 ppm, the dominant

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G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

chemical shift and line width, even if it is presence in too low amount
and is not detected in the XRD pattern.
It is then noticed that nearly identical spectra are observed for the 3
exchanged systems, namely, SAC paste treated with water and saline
solution at different pH values (Fig. 4a, b, c): only slight differences in
the 27Al population distribution in the octahedral region are found
(Table 6). What is important to note is the absence of chloride binding
octahedral 27Al phases in SAC paste, in agreement with the consideration based on X-ray diffraction pattern evaluation.
These observations conrms that ettringite and AH3 are stable in
presence of chloride: their scarce interaction with chloride ions suggests
that the investigated formulation has a limited capacity to chemically
bind chloride ions.
3.3. SulfoaluminatePortland ternary systems

Fig. 3. X-ray diffraction patterns of the SAC samples (HP = hydrated paste; a = treated
with water; b = treated with 3% chloride solution at pH = 7; c = treated with 3% chloride
solution at pH = 1): E = ettringite; G = gypsum; Hc = hemicarbonate.

contributor in SAC hydrated paste. Many considerations suggest that aluminium hydroxide (AH3) is responsible for this contribution [55,56].
AH3 is distinguished from octahedral AFm phases based on its chemical
shift and line width: generally, AFm phases have much narrower line
width and are detected by XRD as well. Moreover, it is important to
note here that the AH3 is different from TAH above discussed [46]
which resonates around 6.5 ppm and is usually detected among OPC hydration product. The highly disordered feature of AH3 is probably the
reason why it is not detectable by means of XRD, even if it accounts
for more than half to the overall amount of Al nuclei within the SAC system. A comparison between the narrow linewidth of ettringite and the
very broad peak detected for AH3 phase underlines the contrast between the ordered (ettringite) and disordered (aluminium hydroxide)
nature of the hydration products as well as the impact of aluminate
phases in SAC paste. Furthermore, trace amount of strtlingite (narrow
resonance at 62 ppm) was observed in this sample as well [57]: the attribution to strtlingite, a well crystalline phase, is deduced based on the

Fig. 4. 27Al MASNMR spectra of SAC samples (HP = hydrated paste; a = treated with
water; b = treated with 3% chloride solution at pH = 7; c = treated with 3% chloride solution at pH = 1). Each spectra includes experimental and its deconvoluted spectrum with
individual contribution from each 27Al sites: E = ettringite; AH3 = aluminum hydroxide;
S = strtlingite.

The X-ray diffraction patterns collected on the three mixed systems

before and after treatments are shown in Figs. 5, 7 and 9 respectively for
MIX A, MIX B and MIX C, while the corresponding 27Al MAS NMR spectra are reported in Figs. 6, 8 and 10.
In a sulfoaluminate cement mixed with Portland cement, a different
reaction mechanism is expected, mainly due to the fact that the large
availability of Ca2+ ions, deriving from OPC hydration, and, subsequently, the different composition of the pore solution, modies the hydrated
phases precipitation equilibria. For what concerns the formation of
ettringite, a reaction involving calcium hydroxide which forms from
the early dissolution of Portland silicates is proposed, having the following stoichiometry [58]:
C4 A3 S 6CH 8CS 90H3C6 AS3 H32

In this reaction, differently from the pure sulfoaluminate cement, no

aluminium hydroxide is supposed to form, and the ratio ettringite-toyeelimite is 3 against 1: this means that, when enough Ca2+ is available,
a higher amount of ettringite is formed. The hydration of the Portland
component of the mixed systems, namely C2S and C3S, proceeds towards the formation of C-S-H and, depending on the availability of
Al3+ and on the Ca/(Si + Al) ratio, C-A-S-H. Strtlingite can also form
in mixed systems in absence of both Portlandite and calcium sulfate

Fig. 5. X-ray diffraction patterns of the MIX A samples (HP = hydrated paste; a = treated
with water; b = treated with 3% chloride solution at pH = 7; c = treated with 3%
chloride solution at pH = 1): E = ettringite; Ms = monosulfate; Hc = hemicarbonate;
Mc =monocarbonate; F = Friedel's salt; P = portlandite.

G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

Fig. 6. 27Al MASNMR spectra of MIX A samples (HP = hydrated paste; a = treated with
water; b = treated with 3% chloride solution at pH = 7; c = treated with 3% chloride
solution at pH = 1). Each spectra includes experimental and its deconvoluted spectrum
with individual contribution from each 27Al sites: E = ettringite; Ms = monosulfate;
Mc = monocarbonate; Hc = hemicarbonate; F = Friedel's salt; T = third aluminate hydrate; S = strtlingite.

99

Fig. 8. 27Al MASNMR spectra of MIX B samples (HP = hydrated paste; a = treated with
water; b = treated with 3% chloride solution at pH = 7; c = treated with 3% chloride
solution at pH = 1). Each spectra includes experimental and its deconvoluted spectrum
with individual contribution from each 27Al sites: E = ettringite; Ms = monosulfate;
F = Friedel's salt; T = third aluminate hydrate.

[59], which means, referring to the reaction (2) when the amount of
yeelimite is high enough to consume all the CH and CS.
The XRD data obtained on 28 days hydrated pastes suggest a similar
hydration behavior for MIX A and MIX B (Figs. 5 and 7), the two samples
having the lowest C4 A3 S=CS ratio: in both samples ettringite is clearly
formed while the typical reections of AFm phases are absent. As peculiar feature, MIX A reveals traces of portlandite, absent in the MIXB in
which the higher availability of SO3 maximizes the amount of ettringite
with respect to all other hydrated phases. Finally, the weak shoulder
around 9.0 2 observed in MIX A could be ascribed to monosulfate containing a higher amount of interlayer water [41].
The behavior of the MIX C sample is completely different: in this
case, a wide and intense peak centered at 10.2 2, corresponding to
monosulfate, appears as main band in the low angle diffraction region
(Fig. 9); the peak of ettringite is also visible on the left side of the
main peak, while a shoulder on the right side suggests the presence of
some hemicarbonate; nally, traces of portlandite are also visible.

When 27Al MAS NMR spectra of the same samples are considered, an
important contribution from AFm is discovered in the MIXA (Fig. 6),
even accounting for 37% to the overall aluminium, contrarily to XRD;
moreover, the existence of third aluminate hydrates in very small
amount is also visible. Furthermore, a supplementary narrower resonance at 62 ppm is visible in the tetrahedral region, which accounts
for 5% of overall Al contributions (Table 6). This resonance is attributed
to strtlingite [57]: the attribution to strtlingite and not to C-A-S-H, a
well crystalline phase, is deduced based on the chemical shift and line
width differences.
Focusing on the remaining ternary systems, namely MIX B and MIX
C, 28 days hydrated pastes show complimentary 27Al MAS NMR spectra
as can be seen in Figs. 8 and 10: ettringite dominates the MIX B system,
while AFm phases are predominant in MIX C with minor contributions
from ettringite. A more precise indication of the relative amount of
each phase is supplied by the Al sites quantication reported in
Table 6: more than half of the overall aluminium amount in MIX B is

Fig. 7. X-ray diffraction patterns of the MIX B samples (HP = hydrated paste; a = treated
with water; b = treated with 3% chloride solution at pH = 7; c = treated with 3% chloride
solution at pH = 1): E = ettringite; Ms = monosulfate; G = gypsum; F = Friedel's salt.

Fig. 9. X-ray diffraction patterns of the MIX C samples (HP = hydrated paste; a = treated
with water; b = treated with 3% chloride solution at pH = 7; c = treated with 3%
chloride solution at pH = 1): E = ettringite; Ms = monosulfate; Hc = hemicarbonate;
F = Friedel's salt; P = portlandite.

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G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

Fig. 10. 27Al MASNMR spectra of the MIX C samples (HP = hydrated paste; a = treated
with water; b = treated with 3% chloride solution at pH = 7; c = treated with 3% chloride
solution at pH = 1). Each spectra includes experimental and its deconvoluted spectrum
with individual contribution from each 27Al sites: E = ettringite; Ms = monosulfate;
Hc = hemicarbonate; F = Friedel's salt; T = third aluminate hydrate; S = strtlingite.

in ettringite, while a similar amount is in the AFm phases in the sample C.

This can be explained by the availability of sulfate ion sources: the higher
is the sulfate content for a given amount of cement (low C4 A3 S=CS)
the greater is the development of ettringite over monosulfate and
a reverse mechanism is plausible when there is a deciency of sulfate
source in the hydrated cement paste, according to the following
equation:
C4 A3 S 6CH 2CS 36H3C4 ASH14

MIX C system contains about 2% of strtlingite, while no signicant

contribution of this phase is observed in the MIX B. It is important to underline, when considering MIX B and MIX C hydrated pastes, that there
is a good agreement between the results obtained by XRD and 27Al MAS
NMR: both techniques reveal the presence of ettringite in MIX B and of a
high amount of AFm in MIX C. Such agreement was not found in MIX A,
in which AFm was not detected in the XRD pattern (apart from the weak
shoulder around 9.0 2): this lead to argument that AFm formed in the
ternary system MIX A is different from the one formed in the MIX C system, the latter being characterized by a higher crystalline degree; this
behavior can also be ascribed to the formation of solid solution, as described in the introduction.
When the ternary systems were treated with water a general increase of the AFm phase amount in MIX A and MIX B is suggested by
the observation of XRD data, but while in MIX B the higher availability
of sulfate ions allows the formation of new monosulfate, in MIX A
hemicarbonate and monocarbonate are formed.
No compositional changes are observed in the MIX C after water
treatment for what concerns the sulfate hydrates; these data cannot
be conrmed by 27Al MAS NMR investigation, as far as the signal of
Ms, Hc and Mc cannot be discriminated. The more signicant variation
are the increase of the portlandite peak and, subsequently, the decrease
of strtlingite content below the detection limits. Among the three
mixed systems, MIX C contains the highest amount of Portland cement
and the lowest sulfate content: the relatively low availability of sulfate is
a limiting factor in the development of reactions (2) and (3); when
some more portlandite forms (for example, as a consequence of the
water treatment), but no free sulfate is available anymore, then CH is
free to precipitate.
Turning now the attention to what happens when the samples are
submitted to chloride ionic exchange, the following observation arises.
X-ray diffraction patterns of chlorinated mix A samples (Fig. 5) suggest that Friedel's salt forms both in the sample treated at pH = 7 and in
the one treated at pH = 1. It is quite evident that the crystal degree of
the formed mineral is different in the two cases: at acidic pH a sharp

peak indicates a strong orientation for the main Friedel's salt reection,
thus suggesting a higher crystallinity than in the paste treated at
neutral pH. The different crystal structure is not related to a
great difference in the amount of bound chloride ions, as attested by
the similar chloride content highlighted by XRF analyses (Table 5).
The 27Al MAS spectra shows that the contribution of AFm phases
completely disappear (Table 6) and conrms the fact that Friedel's salt
forms at expenses of AFm phases through ionic exchange between sulfate and chloride. Table 6 suggests also that the released sulfate contributes to the formation of new ettringite in neutral condition, while in
acidic conditions it is supposed to dissolve and is washed away during
ltering.
In mix B (Fig. 7) Friedel's salt forms only when the sample is submitted to ionic exchange in neutral solution, not when the acidic solution is
used: in this latter case, the 11.4 2 peak completely disappears from
the corresponding diffraction pattern and the amount of chloride is signicantly lower (Table 5). Even in this case, the distribution of octahedral 27Al amount (Table 6) agree with the XRD data in the fact that
only when the neutral exchange solution is used, Friedel's salt is formed.
The absence of Friedel's salt in acidic condition suggests that this system
is less able than the previous one to counteract the acidity of the exchange medium and the chemical binding of chloride is inhibited: as a
matter of fact, the pH value of the sample after the treatment with the
acidic solution is much lower than that of the MIX A sample when submitted to the same treatment (Table 4).
As above mentioned, in the mix C sample the amount of AFm phases
is consistently higher than in MIX A and in MIX B and a signicant
amount of Hc is clearly evident in the XRD pattern. When the sample
is exchanged with the chloride solution, a similar XRD pattern is obtained independently from the pH of the exchange solution: in both cases
the Friedel's salt 11.4 2 peak appears as a very strong and rather
large reection. The behavior of this sample and, at a certain extent,
even the shape of the peaks, recall what has been observed for Portland
cement, even if, of course, on a different scale: as a matter of fact, in the
Portland cement paste both Ms and Hc were also present and Friedel's
salt was observed in both the exchanged samples, apart from the pH
of the exchange solution. The 27Al MAS spectra recorded after chloride
treatment at pH = 7 and pH = 1 for MIX C conrm the formation of
Friedel's salt and the disappearance of AFm phase.
Particularly worth to be noticed is, in this case, that the amount
of Friedel's salt is much higher than in all the other samples (Table 6)
and the same consideration is also valid for the amount of chloride detected by XRF (Table 5); the sulfate ions released from Ms contribute
to the signicant increase of the amount of ettringite.
Overall, the contribution of strtlingite to chloride binding in mixed
system can be considered irrelevant, with respect to the efciency of
AFm phases in the capture mechanisms, but in the investigated system
this can be mainly due to the reduced amount of this phase.
The results obtained on the mixed samples indicate that two different factors affect the formation and stability of Friedel's salt in ternary
systems. On one hand, the amount of available sulfate ions inversely inuences the amount of Ms which is formed and, subsequently, the
amount of Friedel's salt in chloride treated samples: the higher the C4 A3
S=CS ratio in the blend, the more Ms is formed in the hydrated paste and
the more Friedel's salt in the exchanged samples, this is the case of MIX
C. On the other hand, the pH is also signicant as far as it inuences the
conditions in which Friedel's salt is allowed to form: when the pH values
measured on the resulting solution collected after ionic exchange are
considered (Table 4), it is possible to notice that in all cases the acidic
treatment lead to a decrease in pH, but this is much more consistent
in the samples SAC and MIX B; the other samples are more effective in
counteracting the pH reduction caused by the treatment with acidic solution, thanks to portlandite which acts as a buffer and preserves the alkaline environmental condition in which Friedel's salt can form. In the
latter case, Mc and/or Hc are observed in hydrated pastes as well as in
the water exchanged samples, it can be therefore also adduced a

G. Paul et al. / Cement and Concrete Research 67 (2015) 93102

relation between the presence of these phases, their buffering ability

and the possibility of binding chloride in acidic condition.
4. Conclusions
A further step towards the comprehension of the complex equilibria
regulating the formation of Friedel's salt and the role played by different
AFm phases has been done through the study of different real
sulfoaluminate systems, in which ettringite, aluminium hydroxide,
AFm phases are the main hydration products and C-S-H, C-A-S-H and
strtlingite may be present in lower amount.
Even if ettringite and AFm phases are generally detected by X-ray
diffraction, they can be characterized by a strongly different crystallization degree, mainly depending on the recipe of the cement and, therefore, on the different precipitation/dissolution mechanisms happening
during early hydration. A quantication through Rietveld analysis on
the diffraction patterns is not possible: rstly, it has been demonstrated
that in some cases AFm phases are partially or totally invisible to X-ray
diffraction, and its presence has been veried only by means of 27Al MAS
NMR; moreover, other amorphous phases such as aluminum hydroxide
or third aluminate hydrate are also present and not visible in the X-ray
diffraction pattern. Coupling XRD with 27Al MAS NMR resulted in a
powerful method particularly suitable for the study of such systems,
in which the evaluation of the distribution of aluminium within the different mineral phases can be even used for quantitative evaluation.
In an ordinary Portland cement paste, chloride ions can be chemically captured by AFm phases through ionic exchange: this phenomenon
has clearly been demonstrated both by XRD and 27Al MAS NMR data.
Ms and Hc/Mc can both contribute to the Friedel's salt formation and
the amount of entrapped chloride is the same independently from the
more or less acidic conditions used for the exchange, even if other
phases, probably C-S-H and C-A-S-H, also contribute to the chloride
capture.
On the contrary, a pure sulfoaluminate cement paste shows limited
ability to capture chloride ions through chemical interaction: ettringite
formed in these systems is particularly stable from the chemical point of
view, chloride ions do not react with it and the same can be assumed for
what aluminium hydroxide is concerned. The absence of Ms in the hydrated paste of the pure sulfoaluminate cement plays a fundamental
role in the inefciency of the system to chemically bind chloride anions;
the small amount of uptaken chloride is probably adsorbed in C-S-H and
C-A-S-H and no Friedel's salt is formed.
Finally, ternary cementing systems consisting in mixtures of ordinary Portland cement, sulfoaluminate cement and anhydrite show a different attitude towards the interaction with chloride ions depending
both on the amount of CS and on the pH.
Firstly, it was found that the lower is the C4 A3 S=CS ratio, the lower is
the ability to capture chloride through chemical reaction, as far as more
ettringite over monosulfate is formed.
Secondly, it was observed that the buffer ability of a ternary system
is strictly dependent on the composition of the hydrated phases and on
the presence of portlandite and Hc/Mc beyond Ms. The formation of
Friedel's salt in acidic conditions which probably moves through ionic
exchange from Hc/Mc phases and carbonate ions released during exchange, together with the presence of portlandite, are responsible for
the higher pH value recorded in MIX A and C with respect to MIX B
after the exchange with the acidic solution.
Overall, the following observations can be drawn about the investigated ternary systems:
Friedel's salt always forms in presence of large amount of chloride in
neutral exchange solution when Ms is present among hydrated
phases;
Friedel's salt is stable in acidic conditions (i.e. when using an acid
exchange solution) only when Hc/Mc are identied among the hydrated phases (or formed during water treatment);

101

Friedel's salt never forms if AFm phases are totally absent in the hydrated cement paste;
When chloride binding is effective, the ionic exchange leads to the
release of sulfate ions that contributes to the formation of new
ettringite in neutral condition, while they are supposed to be
washed away when acidic treatment is performed;
Ettringite and aluminum hydroxide, the other common phases
forming in CSA hydrated cements, are not able to chemically bind
chloride anions.
Acknowledgments
One of the authors (GP) acknowledges CRT Foundation for granting
his research through the Lagrange Project.
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