Influence of Pozzolana On Sulfate Attack of Cement Stone Affected by Chloride Ions

Materials and Structures (2014) 47:19011910
DOI 10.1617/s11527-013-0159-5
ORIGINAL ARTICLE
Influence of pozzolana on sulfate attack of cement stone

affected by chloride ions
Rimvydas Kaminskas Irmantas Barauskas
Received: 21 March 2012 / Accepted: 23 July 2013 / Published online: 15 August 2013
RILEM 2013
Abstract This study investigated the influence of

natural pozzolana (opoka) additive on the hydration of
Portland cement and the effects of pozzolana on
sulfate attack of cement stone affected by chloride
ions. In the samples, 25 % (by weight) of the Portland
cement was replaced with pozzolana. The specimens
were hardened for 28 days in water, and then one
batch was soaked in a saturated NaCl solution and
another in a 5 % Na2SO4 solution for 3 months at
20 C. After being kept for 3 months in a saturated
NaCl solution, samples were transferred to a 5 %
Na2SO4 solution and kept under these conditions for
3 months. It was estimated that under normal conditions, pozzolana additive accelerated the hydration of
calcium silicates and initiated the formation of
CO32-AFm; opoka also decreased the threshold pore
diameter of hardened Portland cement paste. It was
found that Cl ions penetrate to monosulfoaluminate,
form Friedels salt, and release SO42- ions, which
react with unaffected monosulfoaluminate and form
extra ettringite; when samples were transferred to the
5 % Na2SO4 solution, a greater quantity of new
ettringite was formed. Meanwhile, pozzolana additive
reduced the penetration of chloride and sulfate ions
into the structure of Portland cement hydrates and
R. Kaminskas (&) I. Barauskas

Department of Silicate Technology, Chemical
Technology Faculty, Kaunas University of Technology,
Kaunas, Lithuania
e-mail: rimvydas.kaminskas@ktu.lt
inhibited sulfate attack of cement stone treated in a

saturated NaCl solution.
Keywords Portland cement Additives
Pozzolana Chloride Sulfate Ettringite
Friedels salt Monocarboaluminate
1 Introduction
Chemical mechanisms of attack include leaching of
cement paste components, carbonation of calcium
hydroxide and CSH (calcium silicate hydrates), and
cement paste deterioration by exposure to aggressive
chemicals (acids, agricultural chemicals, sulfates).
Sulfate attack is the term used to describe a series of
chemical reactions between sulfate ions and the
components of hardened concrete, principally the
cement paste, caused by exposure of concrete to
sulfates and moisture. As is the case with other
aggressive chemicals, sulfates are potentially most
deleterious to concrete when present in gaseous or
liquid form, the latter situation being the most
common [23].
Studies of the effect of chloride on the durability of
cement stone are especially important in countries
with cold climates because mixtures of sand and either
salt or a saturated salt solution are used as road deicing
materials, and in marine environments. At present, to
1902
protect roads from climatic factors or to eliminate the

ice layer from the road surface quickly, wet salt
technology is used. Traditional and relatively new
materials are used as deicers: sodium chloride, magnesium chloride, calcium chloride, calcium magnesium acetate, potassium acetate, potassium formate,
sodium acetate, and others. The detrimental effects of
deicers on Portland cement concrete take three main
forms: (1) physical deterioration, such as salt scaling; (2) aggravation of aggregate-cement reactions
by the deicers; and (3) chemical reactions between
deicers and cement paste [21]. The long-term use of
NaCl can initiate and/or accelerate alkali-silica reactions (ASRs) by supplying additional alkalis to
concrete, whereas CaCl2 and MgCl2 do not have as
obvious an effect on ASRs [11, 12].
NaCl, NaCl-based deicers, and potassium acetatebased deicers are the most deleterious to concrete. In
addition to exacerbating physical distresses, each
chemical or diluted deicer investigated chemically
reacts with some of the cement hydrates and forms
new products in the pores and cracks. Such physiochemical changes in the cement paste induced by the
deicers pose various levels of risks for concrete
durability [22].
Chloride ions influences cement stone durability, an
effect that has been found to be related to the reaction
between the aluminous compounds and Cl ions [28,
30]. It is estimated that the primary compound that is
formed is Friedels salt [2426]. Friedels salt is a
chloride-containing calcium aluminate hydrate that
has been found to exist as a stable hydration product in
cement. It has the composition 3CaOAl2O3CaCl2
10H2O. There is interest in Friedels salt because of its
role as a diffusion barrier against chloride ions, which
causes corrosion of steel that is embedded in concrete
[20].
The attack by solutions containing sulfate can have
diverse effects on concrete. The nature of the sulfate
solution is important, since the influence of other
chemicals can affect the mechanism of the reaction.
This is especially true in the case of seawater, where
the presence of a very high concentration of chlorides
can have a bearing on the action of the sulfates.
However, there are very few studies specifically
explaining the process of sulfate attack under these
conditions.
In order to reduce the deterioration reactions of
cement stone, pozzolana additives can be used [8, 10,
19, 29]. Diverse and controversial opinions can be

found in the literature on the addition of pozzolana
containing limestone. It has been found that the
addition of pozzolana to neat cement pastes and
mortars reduces the diffusion coefficient of chloride
ions [4].
Lithuania contains abundant natural pozzolana
(opoka), which consists of amorphous SiO2 and finely
dispersed CaCO3. Pozzolana contains over 41 wt% of
calcite, which is evenly distributed in opal in form of
dispersed parties and rests of microorganisms. Quartz
is in form very fine particles. The aim of this work was
to investigate the influence of natural pozzolana
(opoka) on the hydration process of Portland cement,
the effect of Cl ions on the hydrates formed, and the
influence on sulfate attack of cement stone treated in a
2 Materials and methods

Samples (20 9 20 9 20 mm) were formed of pure
ordinary Portland cement (OPC) CEM I 42.5 and
Portland cement with 25 % replacement by pozzolana.
The ratio of water to cement was 0.3. For the first day,
the samples were kept in moulds at 20 1 C and
100 % humidity. After 24 h of formation, the samples
were transferred to water and stored there for 27 days
at 20 1 C. The specimens were hardened for
27 days in water, and then one batch was soaked in a
saturated NaCl solution (358 g/L) and another in a
5 % Na2SO4 solution for 3 months at 20 C. After
being kept for 3 months in a saturated NaCl solution,
samples were transferred to a 5 % Na2SO4 solution
and kept under these conditions for 3 months. For
instrumental analysis (XRD, STA, FT-IR) hydration
of samples was stopped using acetone: three samples
were kept under the conditions described; samples
were then crushed separately, milled together using a
laboratory vibrating disc mill, passed through an 80
micron sieve, washed with acetone, and dried in a
CO2-free atmosphere at 80 5 C for 8 h. A representative amount was selected from the lot to be
analyzed, which upon further quartering (EN 196-2,
EN 196-7) was reduced to a manageable amount for
appropriate sample preparation. Powder samples were
stored in sealed bags to prevent carbonation and
hydration.
1903
The composition of raw materials is given in

Tables 1 and 2 (the hydraulic activity of pozzolana is
220 mg of CaO/g).
The x-ray diffraction (XRD) data were collected
with a DRON-6 powder X-ray diffractometer with
BraggBrentano geometry using Ni-filtered CuKa
radiation, operating at a voltage of 30 kV and an
emission current of 24 mA. The step-scan covered the
angular range 560 (2h) in steps of 2h = 0.02. The
reliability of method98 %.
Simultaneous thermal analysis (differential scanning calorimetry [DSC] and thermogravimetry [TG])
was carried out on a Netzsch 409 PC Luxx simultaneous thermal analysis instrument with ceramic sample handlers and crucibles of PtRh. At a heating rate
of 15 C/min, the temperature ranged from 30 to
1000 C under a nitrogen atmosphere. The uncertainty
in measurements for the DSC was 0.2 C, and for
TG it was 0.3 %.
Infrared spectra have been measured using a
PerkinElmer Fourier transform-infrared (FT-IR) system Spectrum X spectrometer. Samples were prepared
by mixing 1 mg of the sample in 200 mg of KBr. The
Table 1 Oxide composition of raw materials
Component
Opoka (wt%)
Clinker (wt%)
SiO2
54.1
20.1
Al2O3
2.7
5.32
Fe2O3
1.3
3.75
23.2
62.80
CaO
MgO
0.62
4.54
Na2O
0.24
0.14
0.87
0.93
K2O
Loss on ignition
16.97
Table 2 Mineral composition of pozzolana (opoka)

Component
Amount (wt%)
Amorphous (SiO2nH2O)
22.2
Ancerite (Ca(Fe, Mg, Mn)(CO3)2)
1.3
Calcite (CaCO3)
36.1
Cristobalite (SiO2)
19.2
Muscovite (KAl2(AlSi3O10)(F, OH)2)
4.1
Plagioclase (NaAlSi3O8)
1.1
Quartz (SiO2)
12
Tridymite (SiO2)
spectral analysis was performed in the range of

4000400 cm-1 with a spectral resolution of 1 cm-1.
The pozzolanic activity was assessed using the
modified Chapelle method [18]. This test consisted of
placing 1.000 g of mineral admixture and 1.000 g of
calcium oxide in a water volume of 250.0 ml. The
solution was kept for 16 h in an oven at 90 C. At the
end of the period, the CaO content was determined for
titration with hydrochloric acid (HCl) solution and
using phenolphthalein as an indicator. The results
were expressed by fixed CaO, which is equal to the
difference between 1.000 g and the mass of CaO
obtained from titration.
3 Results and discussion

3.1 The effect of opoka on the hydration
of Portland cement under normal conditions
XRD analysis of OPC samples hydrated in water for
28 days (Fig. 1, curve 1) showed patterns characteristic of portlandite (d-spacing: 0.494, 0.263, 0.193,
0.180 nm, etc.) and still unhydrated C3S (3CaOSiO2)
diffraction peaks (d-spacing: 0.304, 0.297, 0.278,
0.219, 0.193). In the samples with opoka (Fig. 1, curve
2) together with portlandite (CHCa(OH)2), calcium
silicate hydrates (d-spacing: 0.304, 0.279 nm, etc.)
could also be identified, whereas peaks characteristic
of C3S could not be seen. Along with these compounds, monocarboaluminate CO32-AFm (Ca4Al2O6CO311H2O) (d-spacing: 0.758, 0.379 nm, etc.)
was identified. Monocarboaluminate formed as a
result of CO32- penetration of the AFm compound
structure [5, 7]. Thus, under normal conditions,
pozzolana additive accelerated the hydration of
calcium silicates and initiated the formation of
CO32-AFm. In addition, x-rays showed the remaining patterns of ettringite (d-spacing: 0.972, 0.561,
0.387 nm.) in samples with pozzolana. It can be
concluded that CaCO3 (CC), which is a component of
opoka, increases the stability of ettringite and that
this process is associated with the formation of
monocarboaluminate.
After 28 days of hydration under normal conditions, a threshold pore diameter of 0.019 lm was
identified for pure OPC samples, whereas that of
samples with opoka was 0.013 lm (Fig. 2). Thus,
opoka decreased the threshold pore diameter. Larger
1904
CH
CH CH
CC
CC
CH
CH
CH
CH
CHC3S
10
20
30
1 86111
702
CH
C3S
CH
40
50
CH
CH CH
458
200
400
600
800
1000
Temperature, oC
60
70
Diffraction angle 2 , deg
Fig. 1 X-ray diffraction (XRD) patterns of samples cured for

28 days in water: 1pure ordinary Portland cement (OPC); 2
OPC with opoka. Abbreviations: CH Ca(OH)2, CC CaCO3,
C3S Ca3SiO5, E (CaO)3(Al2O3)(CaSO4)332H2O, Q SiO2, CSH
CSH, CAFm Ca4Al2O6CO311H2O
Log Differential intrusion
dV/dlogD, ml/g
754
105
CC
447
CC CC
exo
endo
E CAFm
E EQ E
CC
CH
CH CSH
Q
Heat flow, a.u.
Relative intensity, a. u.
Fig. 3 Differential scanning calorimetry (DSC) curves of

samples cured for 28 days in water: 1 pure ordinary Portland
cement (OPC); 2 OPC with opoka
Table 3 TG analysis results of ordinary Portland cement
(OPC) and OPC with opoka samples after 28 days of hydration
under normal conditions
Sample
0.200
0.160
Mass loss, %
Temperature range, C
100200
0.120
0.080
OPC
OPC with opoka
440460
700760
8.18
3.57
1.37
13.15
1.70
5.43
0.040
0.000
1000
100
10
0.1
0.01
0.001
Pore diameter , m
Fig. 2 Mercury porometry curve patterns (log differential

intrusion, ml/g) of ordinary Portland cement (OPC) (1) and
OPC with opoka (2) samples cured for 28 days in water
pores contribute to mass transport by diffusion, ion

migration, capillarity, and permeability, whereas
smaller pores aggravate diffusion process and ion
migration. Therefore, the reduction of pore size causes
the diffusion of sulfate or chloride ions into cement
stone to be mitigated [17, 27].
In the DSC curves of samples of both OPC and OPC
with opoka (Fig. 3), three significant endothermic
peaks at temperature ranges of 100200 C,
440460 C, and 700730 C were observed. The
endothermic peak at 100200 C is due to the
dehydration of most cement hydration products (calcium silicate hydrates, calcium aluminates, ettringite,
etc.) [15], whereas those at 440460 C and
700730 C indicate the decomposition of portlandite
and calcium carbonate, respectively. TG analysis
results are shown in Table 3.
In the samples with opoka, the mass loss characteristic of calcium carbonate was greater than that in
the pure OPC samples, because calcium carbonate is
the one of the main components of opoka.
It should be noted that the quantity of portlandite
was less in samples with opoka than in the pure OPC
samples (Table 3), because only approximately half as
much mass loss was identified, even taking into
account that in the OPC with opoka there was a smaller
quantity of hydrating cement. These data show the
pozzolanic reaction in the samples with opoka:
portlandite reacts with amorphous SiO2 from additive
to produce an additional amount of calcium silicate
hydrates. This occurs because the mass loss at
100200 C, attributed to dehydration of calcium
silicate hydrates, in the samples with opoka was much
higher.
of Portland cement after 3 months
of treatment in a 5 % Na2SO4 solution
No essential deterioration was identified of both
samples after 28 days of hydration in water and
1905
CH
CC
CH
Q
E
CSH
CC
CC
CC
CH CH
CH
CC
CH
10
G E
20
CSH
CH G
30
CH
CH
40
CH CH
50
exo
445
748
141
113
714
140
108
0
200
endo
452
400
600
800
1000
Temperature, oC

samples cured for 3 months in a 5 % Na2SO4 solution: 1pure
ordinary Portland cement (OPC); 2OPC with opoka
(OPC) and OPC with opoka samples after 3 months of curing
in a 5 % Na2SO4 solution
Sample
Mass loss, %
100200
*140
440460
700760
OPC
9.43
2.01
2.53
1.17
OPC with opoka
9.09
1.57
1.51
4.29
reduced by one-third compared with samples that had

been cured under normal conditions (Table 3). Moreover, mass loss of portlandite was reduced only
approximately 10 % in samples with opoka. These
data indicate that the in OPC sample, a much greater
amount of portlandite was involved in the reactions,
which could promote formation of ettringite and
gypsum [15].
of treatment in a saturated NaCl solution
CH
Heat flow, a.u.
3 months of treatment in a 5 % Na2SO4 solution. XRD

analysis (Fig. 4) shows peaks characteristic of ordinary OPC hydration products: portlandite and calcium
silicate hydrates. On the other hand, this analysis also
identified an increase in the diffraction peaks characteristic of ettringite and the new peaks due to formed
gypsum (d-spacing: 0.7622, 0.428, 0.306 nm), which
are more intensive in the OPC samples. The main
compounds resulting from sulfate attack are ettringite
and gypsum [9, 16]. Sodium sulfate reacts with
calcium hydroxide in the paste to form gypsum, which
may cause damage in itself or react with monosulfate
to form ettringite [9].
DSC analysis (Fig. 5) shows four main thermal
effects identified at temperatures of *110 C,
*140 C, 440460 C, and 700730 C. The endothermic effect at *140 C is attributed to dehydration
of ettringite [14].
TG analysis (Table 4) shows that mass loss at
*140 C was less in samples with opoka (1.57 %)
than in pure OPC samples (2.01 %) after 3 months of
curing in a 5 % Na2SO4 solution. It is obvious that less
ettringite formed in the samples with opoka.
The thermal effect of gypsum dehydration cannot
be seen (Fig. 5) because it is overlapped by a wide
endothermic peak of calcium silicate hydrate decomposition. The mass loss during dehydration of portlandite at 430 C was greater in pure OPC samples
than in OPC with opoka (Table 4). In OPC samples,
mass loss during decomposition of portlandite was
60
Fig. 4 X-ray diffraction (XRD) patterns of samples treated for

3 months in a 5 % Na2SO4 solution: 1pure ordinary Portland
cement (OPC); 2OPC with opoka. Abbreviations: CH
Ca(OH)2, CC CaCO3, E (CaO)3(Al2O3)(CaSO4)332H2O,
Q SiO2, CSH CSH, G CaSO42H2O
After 28 days of hydration in water and 3 months in a

saturated NaCl solution, XRD analysis (Fig. 6) of
OPC and OPC with opoka showed peaks characteristic
of portlandite, calcium silicate hydrates, chloraluminates (Friedels salt), and ettringite. In samples with
opoka, the peaks characteristic of ettringite were
similar to those of the samples hydrated for 28 days in
normal conditions. In OPC samples, no evidence of
ettringite was found after curing under normal conditions, but it formed after treatment in the saturated
1906
3CaO Al2 O3 CaCO3 11H2 O 2NaCl ! 3CaO

Al2 O3 CaCl2 10H2 O 2Na CO2
3 H2 O
1
Ca
CO2
3
! CaCO3
DSC analysis (Fig. 7) showed endothermal effects

at 130 C and 312 C and exothermal effects at
620640 C, characteristic of Friedels salt in both
samples after 3 months of treatment in a saturated
NaCl solution. The 130 C event was attributed to
removal of interlayer water, whereas at 312 C, the
remaining water was lost. The anhydrous product
CH
2
E Fr
CC
CH
CH CSH
Fr Q
CH CH
CC CC
CC
E EQ E
CC
CH
CH
CH
CH
CSH
1
E Fr
10
Fr CH Fr
E
20
30
CC
CH
CSH
CH
CC
40
50
CH
CH CH
60
70

3 months in a saturated NaCl solution: 1pure ordinary
Portland cement (OPC); 2OPC with opoka. Abbreviations:
E (CaO)3(Al2O3)(CaSO4)332H2O, CH Ca(OH)2, CC CaCO3,
Q SiO2, Fr Ca4Al2(OH)12Cl26H2O, CSH CSH
312
424
exo
638
Heat flow, a.u.
679
620
1
100
312
436
endo
NaCl solution. These patterns of the appearance of

ettringite can be explained by chloride penetration into
monosulfoaluminate. Additional ettringite forms as a
result of reaction of liberated sulfate ions with
persisted monosulfoaluminate. XRD data also showed
the formation of Friedels salt, Ca4Al2(OH)12Cl2
6H2O (d-spacing: 0.778, 0.388, 0.376 nm) in both
samples (Fig. 6). It forms as a result of aluminate
phase interaction with dissolved NaCl [6].
It should be noted that no traces of monocarboaluminate patterns were observed in samples of OPC
with opoka, whereas after 28 days of hydration in
water, monocarboaluminate was clearly seen (Fig. 1,
curve 2). It can be concluded that Friedels salt forms
from monocarboaluminate under these conditions and
that Cl ions penetrate into monocarboaluminate and
release CO32 ions in the following order:
103
0
200
400
600
800
1000
Temperature, oC

samples cured for 3 months in a saturated NaCl solution: 1
pure ordinary Portland cement (OPC); 2 OPC with opoka
recrystallized exothermically at 620640 C, yielding

mainly calcium chloraluminate (11CaO7Al2O3
CaCl2) [1, 2]. The intensity of the exothermal effect
was much higher in the pure OPC samples than in
samples with opoka.
Moreover, mass loss during the thermal effect at
312 C was 2.8 % of pure OPC samples and 2.4 % of
OPC with opoka, which means that less Friedels salt
was formed in the OPC with opoka (Table 5).
The weaker formation of Friedels salt in samples
with opoka can be explained by smaller amounts of
alumina phases, which can react with chloride to form
Friedels salt. Formation of Friedels salt also consumes some of the alkaline reserve. In the samples
with opoka, portlandite reacted with amorphous SiO2
(pozzolanic reaction), and the amount of CH decrease.
It should be noted that the mass loss attributed to
decomposition of calcium carbonate was less (4.25 %)
in the samples with opoka after 3 months of treatment
in the NaCl solution than in the samples cured for
28 days in water (5.43 wt%) (Table 3). These data
show that calcium carbonate from opoka continued to
react with Portland cement hydrates, even in the
FT-IR analysis showed a similar spectrum for both
samples (Fig. 8). The main difference between them
was that the peak intensity characteristic of portlandite
(3644 cm-1) was weaker in samples of OPC with
opoka than in samples of OPC alone (Fig. 8 curve 1).
Ettringite (shoulder at 1119 cm-1) was identified in
both samples, and a higher intensity was obtained in
pure OPC.
The FT-IR spectrum (Fig. 8) characteristic of
Friedels salt consists of absorption peaks where wave
1907

in a saturated NaCl solution
Mass loss, %
100200
312
440460
700760
OPC
10.7
2.8
3.6
1.0
OPC with opoka
12.6
2.4
2.6
4.25
-1
-1
numbers are 3636 cm , 3480 cm

(mOH),
1621 cm-1 (dH2 O ), 785 cm-1, 620 cm-1, and
532 cm-1 (O and OH vibration) [3]. Only the
peak at 532 cm-1 is not covered by the absorption
ranges of other cement minerals; thus, the existence of
the absorption band at 532 cm-1 is evidence of the
formation of Friedels salt.

of treatment in a saturated NaCl solution
and 3 months in 5 % Na2SO4
After 3 months of treatment in a saturated NaCl
solution and 3 months in 5 % Na2SO4, deterioration is
visible (Fig. 9) in both samples (pure OPC had greater
cracks then OPC with opoka) was identified, but no
visible deterioration of samples was found in samples
treated only in 5 % Na2SO4. Thus, both samples of
pure OPC and samples of OPC with opoka became
less resistant to sulfate attack when treated in a

Ettringite and gypsum as a result of sulfate
corrosion were identified by XRD analysis in both
samples (Fig. 10). It is important to note that diffraction peaks characteristic of Friedels salt still
remained, meaning that Friedels salts remained stable
during the sulfate attack process during whole investigation period.
Intensive peaks characteristic of gypsum were
identified in pure OPC samples (Fig. 10, curve 1),
whereas in samples of OPC with opoka, only traces
were observed. Peaks of ettringite were obtained in
both samples.
DSC analysis (Fig. 11) showed a more intensive
endothermal effect due to dehydration of ettringite
(*146 C) in the pure OPC samples than in the OPC
with opoka. TG results (Table 6) support the trend: the
532
460
875
713
1119
1425
973
1637
3443
3643
4000
3600
3200
2800
2400
2000
Wave number , cm-1
1600
1200
800
532
461
974
873
1119
3439
1635
1480
3644
Transparency T, a.u.
Fig. 8 Fourier transform

infrared (FT-IR) spectrum
of samples treated for
3 months in a saturated
NaCl solution: 1pure
ordinary Portland cement
(OPC); 2OPC with opoka
Fig. 9 Optical photograph of samples treated for 3 months in a

saturated NaCl solution and 3 months in 5 % Na2SO4 solution:
1pure ordinary Portland cement (OPC); 2OPC with opoka
1424
Sample
400
1908

in a saturated NaCl solution and 3 months in 5 % Na2SO4
CC
CH
E Fr
Q
G E
CSH
CH
G
Sample
CH
CC
CC
CH CH
CC
100200
*145
440460
700760
CH
Fr
E G
10
G EG
CC CH
CSH
CH G
20
CH CC
CC
30
CH
CC
CH CH
40
50
60

3 months in a saturated NaCl solution and 3 months in 5 %
Na2SO4 solution: 1pure ordinary Portland cement (OPC); 2
OPC with opoka
loss of mass during the dehydration of ettringite

(*146 C) was 3.35 % of the pure OPC samples and
2.64 % of the samples of OPC with opoka. Thus, more
ettringite formed in pure OPC samples. Moreover,
thermal effects characteristic of Friedels salt at
312 C were also identified in both samples.
The main difference in the FT-IR spectrum
(Fig. 12) between OPC and OPC with opoka was the
intensity of the absorption bands characteristic of
sulfate components. An intensive absorption band
characteristic of ettringite at 1119 cm-1 was identified
in pure OPC samples (Fig. 12 curve 1), whereas only a
weak shoulder was found at 1114 cm-1 in the samples
of OPC with opoka (Fig. 12 curve 2). It is obvious that
145
109
312
112 146
312
691
431
717
endo
exo
Heat flow, a.u.
Mass loss, %
200
443
400
600
800
1000
Temperature, oC

samples cured for 3 months in a saturated NaCl and 5 %
Na2SO4 solution: 1pure ordinary Portland cement (OPC); 2
OPC with opoka
OPC
10.2
3.35
3.4
OPC with opoka
10.5
2.64
1.5
5.4
this peak slid to the longer wavelength side, where

1110 cm-1 is characteristic of monosulfoaluminate.
Moreover, absorption bands attributed to gypsum at
16701685, 1622, and 669 cm-1 were identified only
in the pure OPC samples.
It was found that the sulfate attack process after
treatment of samples in the NaCl solution differed
from simple sulfate attack. When samples are held in a
NaCl solution, Cl- ions penetrate to monosulfoaluminate, form Friedels salt, and release SO42- ions,
which react with unaffected monosulfoaluminate and
form extra ettringite. Later, after immersion of samples into a 5 % Na2SO4 solution, the ettringite that has
already been formed acts as nucleation sites for the
formation of a greater quantity of new ettringite,
because mass loss during dehydration of ettringite
increases after treatment for 3 months in a saturated
NaCl solution and 3 months in a 5 % Na2SO4
solution: from 2.01 % to 3.35 % for pure OPC and
from 1.57 to 2.64 % for OPC with opoka.
In practice, it has been noticed that lifetime of many
cement-based products used as road elements (curbs,
sidewalks, etc.) is quite short. Cracks, gaps, and splits
have been observed after only a couple years of use.
This could be the result of the use of saturated NaCl
salt used as a deicer in wintertime. However, the
influence of the NaCl solution on cement stone has no
severe deterioration effect; moreover, it lasts for a long
time. Presumably, cement products are less resistant to
the effects of other aggressive environments, such as
attack by sulfates formed because of acid rain,
groundwater, car emission gases, and moisture interaction. One way of preventing this deterioration could
be the use of opoka as an additive in cement.
Opoka plays a simultaneous role in the hydration
process of Portland cement under aggressive conditions: first, the replacement of part of the cement with a
pozzolanic material entails a reduction in the content
530
456
875
713
1114
973
1431
1647
3440
3644
4000
3600
3200
2800
2400
2000
1600
1200
800
669
603
536
455
972
874
1119
3409
1684
1622
1488
1425
3645
Transparency T, a.u.
Fig. 12 Fourier transforminfrared (FT-IR) spectrum

of samples treated for
3 months in a saturated
NaCl and 5 % Na2SO4
solution: 1pure ordinary
Portland cement (OPC); 2
OPC with opoka
1909
400
Wave number , cm-1
of the aluminate-bearing phase. Second, the consumption of portlandite reduces the formation of Friedels
salt and gypsum, whereas the ettringite may become
less expansive [13]. Third, the formation of secondary
CSH (as a result of the pozzolanic reaction) also
results in the densification of the hardened cement
paste (opoka decreases the threshold pore diameter);
therefore, the chloride and sulfate ions cannot easily
penetrate through the hardened cement paste, as in the
case of OPC.
4 Conclusions
1.
2.
3.
It was estimated that under normal conditions,

pozzolana additive accelerates the hydration of
calcium silicates and initiates the formation of
CO32-AFm, and opoka decreases the threshold
pore diameter of hardened Portland cement paste.
The sulfate attack process after treatment of
samples in a NaCl solution differs from simple
sulfate attack: Cl- ions penetrate into hardened
cement paste, forming Friedels salt and extra
ettringite; later, the ettringite that is already
formed acts as nucleation sites for the formation
of a greater quantity of new ettringite.
It was found that during the hydration process of
Portland cement under aggressive conditions in
samples with opoka, less Friedels salt and
secondary ettringite are formed; that is, pozzolana
additive reduces the penetration of chloride and

sulfate ions into the structure of Portland cement
hydrates and inhibits sulfate attack of cement
stone treated in a saturated NaCl solution.
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Influence of Pozzolana On Sulfate Attack of Cement Stone Affected by Chloride Ions

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Materials and Structures (2014) 47:19011910