Construction and Building Materials 36 (2012) 10821089

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Construction and Building Materials

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Durability of mortars of white cement against sulfate attack in

elevated temperatures
N. Patsikas a, N. Katsiotis a, P. Pipilikaki a,1, D. Papageorgiou b, E. Chaniotakis b, M. Beazi-Katsioti a,
a
b

National Technical University of Athens, School of Chemical Engineering, Athens, Greece

Titan Cement Company SA, Group R&D and Quality Department, Athens, Greece

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

" Same compressive strength class

mortars.
" 0% and 15% Limestone substitution.
" 15%s Microstructure blocks sulfate

ions.

a r t i c l e

i n f o

Article history:
Received 23 September 2011
Received in revised form 9 May 2012
Accepted 4 June 2012
Available online 11 August 2012
Keywords:
Durability
White cement mortar
Sulfate attack
Elevated temperature
Ettringite
Limestone
Same class category

a b s t r a c t
In this study, white cement CEM I-32,5 & white limestone cement CEM II-A/LL, with 15% limestone substitution, were investigated. Mortars were made from these types of cement and the durability of these
mortars against sulfate attack as well as the effect of temperature (50 C) were investigated.
During the experiment, the mortar samples were being observed visually on a regular basis using the
Heine Delta 20 LED Illuminated Loupe 10 device. After a period of 90 days, the mortar samples compressive strength was determined and the deterioration products which affected the durability were
identied. The identication of the deterioration products was made through means of X-ray Diffraction
(XRD), Scanning Electron Microscopy (SEM-EDAX), Thermogravimetry (TG), Infra-Red Spectroscopy
(FT-IR) and Mercury Porosimetry (MP).
The results of this study clearly displayed that the rate of sulfate attack to the cement with limestone
substitution was lower compared to that of pure cement. Furthermore, it was shown that this type of
cement is three times more durable than pure cement of the same category. It was also identied via different methods of analysis that the cause of the deterioration was the development of microcrystalline
ettringite which caused microcracks and degradation of the specimens.
In conclusion, it is shown that in the case of same class cement with limestone substitution, such a
microstructure is developed which does not allow the penetration by sulfate ions. This is demonstrated
through the higher resistance of this specic mortar despite the adverse conditions in which these mortars were exposed to.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Sulfate attack in cement has been attributed to be a main
deterioration agent; one of the most common and destructive
causes of deterioration of cement-based materials. The term
Corresponding author. Tel.: +30 210 772 3206; fax: +30 210 772 3188.
1

E-mail address: katsioti@central.ntua.gr (M. Beazi-Katsioti).

Dr. Chemical Engineer.

0950-0618/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.06.050

sulfate attack describes and incorporates a series of physicochemical reactions which manifest through the degradation of
the materials quality (i.e. through expansion, cracks and/or decomposition of cement hydration products, etc.). External Sulfate Attack
(ESA) induces damage which is determined by the chemical
interaction between a sulfate-rich environment (water or soil)
and the cement paste itself [1,2]. For ESA to take place, three
conditions should apply and be fullled at the same time: (a) high

N. Patsikas et al. / Construction and Building Materials 36 (2012) 10821089

permeability of the cement-based material, (b) a sulfate-rich environment and (c) the presence of water [35].
Early ettringite formation during the cements hydration is
considered benecial while Delayed Ettringite Formation (DEF)
favored by elevated temperatures-causes damage to cement.
Furthermore, delayed ettringite appears in two forms, each one
different as to its size and behavior. The rst one (Type I) is characterized by long lath-like crystals which range from 10 to
100 lm and several lm thick, formed at low hydroxyl ion concentrations (pH = 10). In the case of hydrated cement containing signicant amounts of Type I ettringite crystals, these have been
attributed to lead to high strength values and non-expansion; thus
the classication of Type I ettringite as not expansive [57].
The second type (Type II) of delayed ettringite is comprised of
rod-like crystals which range from only 1 to 2 lm long and 0.1
to 0.2 lm thick, are formed at high hydroxyl concentrations
(pH > 12) and is classied as the expansive form of ettringite [8].
The expansion mechanism has long been studied meticulously
and has yet to be fully documented; its complexity lying in the
simultaneous interactions of chemical and physical factors. It has
been found though that the initiation of this damage mechanism
is concurrent with the different ettringite modication and formation mechanism [9,10]. Furthermore, it has been shown that: heat
treatment of higher temperatures, freezing-thawing, carbonation
processes, moisture and temperature changes (such as occurring
under natural conditions) can cause ettringite formation in hardened concrete and mortars. Thus, it is important to dene and develop acceptable cure conditions in order to avoid problematic
situations [11,12]. At the same time, there is a practical interest
in delayed ettringite formation in the eld of precast concrete
[13,14].
Based on the existing bibliography concerning delayed ettringite formation conditions (excessive sulfates ions, high-temperature
curing and presence of water), the overall reactions characterizing
the process are described by Eqs. (1)(4) [1520]:

CaOH2 Na2 SO4 H2 O ! CaSO4  2H2 O 2NaOH

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information for the further escalation towards the study of concrete, a composite and multifactorial material.

2. Sample preparation and methods

The samples were prepared via mixing of white cement type
CEM I-32,5 and white cement type CEM II-32,5 with 15% limestone
substitution according to the ELOT EN 1961 Standard [21]. All
samples were formulated with a w/c ratio equal to 0.6 while the
specimens sizes were 4  4  16 cm. During the initial two-day
period, all samples were preserved in their respective molds inside
a wet chamber (humidity > 95%, 20 C temperature) and after that
period, were unmolded and preserved in a saturated Ca(OH)2 solution for the remaining 12 days (total of 14 days), according to EN
1961 specied maintenance.
After this initial maintenance stage, the specimens were exposed to 50 C for 90 days under two distinct conditions, each
one representing a different environment: (a) a 5% Na2SO4 solution
was applied to simulate an environment of high external sulfate
presence and increased temperature and (b) a saturated Ca(OH)2
solution, in order to evaluate the effect of increased temperature.
Consequently, the specimens compressive strength was measured
at 28, 56, 90 days according to EN 1961, while simultaneously
during this period, the specimens were regularly inspected; Their
expansion was determined by measuring their length with a
micrometer and they were visually inspected with a Heine Delta
20 LED Illuminated Loupe 10 device while at the same time
being compared to the control specimens (i.e. those not exposed
to the above environments).
Surface samples were collected from the surfaces of all mortars
and investigated using X-ray Diffraction (XRD), Scanning Electron
Microscopy (SEM-EDAX), Thermogravimetry (TG), Infra-Red Spectroscopy (FT-IR) and Mercury Porosimetry (MP). It is of high importance to make clear that the sample collection only took place from
the mortars surfaces, due to the fact that external sulfate attack
occurs through diffusion of sulfates from the solution to the specimens surface.

C3 A 3CaSO4  2H2 O 36H2 O ! 3C3 A  CaSO4

 14H2 O monosulfate

2CaSO4 C3 A  CaSO4  14H2 O ! 3CaO  Al2 O3  3CaSO4

 32H2 O

3.1. Chemical analysis

C3 A  6H2 O 3CaSO4  2H2 O 20H2 O

! C3 A  3CaSO4  32H2 O ettringite

3. Results and discussion

In this work, the effect of sulfates and temperature were studied

in white cement CEM I-32,5 and white limestone cement CEM II-A/
LL with 15% limestone substitution (both of which were especially
ground in order to belong to the same cement strength class) immersed in (a) a 5% Na2SO4 solution and (b) a saturated Ca(OH)2
solution.
As presented previously, ettringite formation on cement can be
deleterious and the ettringite formation mechanisms have yet to
become entirely clear. What is certain and has been scientically
proven is that ettringite formation is directly related to the C3A
amount available in cement-based material. Therefore, it is vital
to study ettringite formation in white cement with an essentially
high C3A amount. Furthermore, the scope of this work has expanded to include the effect of additives on the ettringite formation itself, since this has not been yet studied extensively and
even though blended cements have been used widely.
All the data presented in this work, all the experimental
results based on cement mortar samples, provide the necessary

The chemical analysis results of the samples are shown in

Table 1, where the 0% LL samples C3A amount was determined
according to Bogue equations [22] while for the 15% LL sample,
the C3A amount was determined employing XRD quantitative
analysis.
The raw materials chemical analysis shows that if the amount
of limestone is increased, then the amount of C3A is decreased by
approximately two units, which is considered signicant for
ettringite formation.
3.2. Visual inspection
The samples visual check -both macroscopically and through the
usage of a Heine Delta 20 LED Illuminated Loupe 10 deviceshowed that after the 90 days period, the mortar without limestone substitution had lost its consistency, resulting in it being
fragile and having completely peeled off. This was noted to be also
the case for the mortar with limestone substitution, yet to a significantly lesser extent. Another indication of this difference was the
existence of various vertical and horizontal cracks throughout the
specimens surface, which were more extensive on the mortar
without limestone substitution.

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N. Patsikas et al. / Construction and Building Materials 36 (2012) 10821089

Table 1
Chemical analysis of cement mixture (before hydration).

a/a

SiO2 (%)

Al2O3 (%)

Fe2O3 (%)

CaO (%)

MgO (%)

SO3 (%)

C3A (%)

LOI (%)

0% LL
15% LL

22.65
20.44

5.32
4.92

0.25
0.29

67.46
70.32

1.01
1.05

3.30
2.97

10.0
8.1

2.06
8.29

It is suggested through the visual check that the mortar with

limestone substitution showed better cohesion and strength, being
more resistant to sulfate attack (see Figs. 14). However, these
optical indications are not sufcient enough as to determine the
cause of the damage because different deterioration mechanisms
can manifest in a similar way, producing cracks and deeming it
not possible to distinguish them optically.

3.3. Compressive strength

The compressive strength of all mortars was measured at set,
predened periods (28, 56, 90 days) and the results are shown in
Fig. 5. It is evident that the mortars strength during the exposure
to the combination of a sulfate-rich environment and increased
temperature of 50 C, signicantly declines. More specically, the

Fig. 1. Result of optical inspection on sample with 15% Na2SO4 (90 days).

Fig. 2. Result of optical inspection on sample with 0% Na2SO4 (90 days).

Fig. 3. Result of optical inspection on sample with 15% Ca(OH)2 (90 days).

Fig. 4. Result of optical inspection on sample with 0% Ca(OH)2 (90 days).

N. Patsikas et al. / Construction and Building Materials 36 (2012) 10821089

1085

Fig. 5. Specimens compressive strength after curing.

Fig. 6. X-ray Diffraction for mortars 0% and 15% LL in Na2SO4 solution.

sample without limestone substitution exhibits the highest compressive strength loss -having deteriorated completely-, while the
sample having 15% limestone substitution exhibits the lower compressive strength loss (40%).
This behavior indicates that the mortars microstructure has become completely deteriorated, while it is clear that certain compounds have been formulated that affect the structural consistency
as manifested by the loss of compressive strength.
It has to also be noted that the deterioration rate of the mortar
with limestone is signicantly lower, as the compressive strength
decreases with a rate of approximately 1.5 MPa per 10 days of
exposure to a sulfate-rich environment and 50 C in relation to
the approximately 4 MPa per 10 days of exposure to a sulfate-rich
environment and 50 C of the mortar without limestone substitution. Comparing the two values it can be concluded that the great
difference in the evolution of the phenomenon is derived not only
from the decreased amount of C3A in cement (8.1 as opposed to
10.0) but also due to other factors concerning the microstructure
itself of the mortar made with limestone substitution (e.g. porosity
and pore size distribution).
Finally, if the equations for the total collapse of the mortar with
15% limestone substitution are applied, it can be concluded that
this will take place after approximately 260 days exposure to this
specic adverse environment. Thus, this particular type of cement
is three times more durable than the pure cement of the same
class.

Fig. 7. FT-IR spectra of samples immersed in Ca(OH)2 and Na2SO450 C (90 days
period, 50 C).

3.4. X-ray Diffraction

In order to identify the sulfate attack deterioration products
during the 90 days period, samples were collected from all the
mortars surfaces and analyzed through the usage of X-ray
Diffraction.

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N. Patsikas et al. / Construction and Building Materials 36 (2012) 10821089

Table 2
Surface samples consistency according to the Rietveld method.

0% LL-56D
0%LL-90D
15% LL-56D
15% LL-90D

Calcite (%)

Portlandite (%)

Ettringite (%)

Gypsum (%)

24.13
24.08
56.69
49.23

28.14
24.95
13.54
18.20

47.73
50.97
29.78
32.57

6.16
6.28
7.33
4.88

The mineralogical study showed that the damaged and without

consistency samples surfaces were characterized by calcite and
portlantide, both of which are the detectable crystal phases of
the hydrated cement primary material [quartz originating from
the silica sand, ettringite and semihydrate (CaSO40.5H2O)], probably
having derived from the gypsum dehydration during the sample
preparation for analysis.
Furthermore, the last two compounds detected are the phases
that were formed during exposure. The larger ettringite peak is located at 2h = 9.2, while denite identication was attributed also
to the peaks at 2h = 15.78 and 22.9 (see Fig. 6).
In addition to the above, the peaks were quantied using the software DIFFRACplus Topas according to the Rietveld method and the
results are presented in Table 2 [23]. It is clear that ettringite
formation was found to be lower in the case of the sample with

limestone substitution. This justies the fact that more cracks were
created in the case of the sample without limestone substitution, as
mentioned in the literature [18]. Numerous conditions must be incheck in order to observe and study expansion and cracks; such conditions include: (a) the amount of ettringite produced, which must
exceed a specic limit in order to put pressure on neighboring compounds and (b) the ettringite must be formed by a topochemical procedure which leads to an oriented development of the ettringites
crystals. In the case of the pure mortar, the amount of ettringite
was found to be capable of creating expansion, cracks and ultimately, the collapse of the specimen.
A small amount of gypsum formed in the mortars indicates that
the portlantide reacted with sulfate ions. Even though this is
known from the literature to possibly cause expansion, nevertheless, the large amount of ettringite identied advocates that
ettringite was the main cause of deterioration [24].
3.5. FT-IR
The presence of ettringite was conrmed with FT-IR carried on
the deteriorated surfaces. Thus, ettringite was identied from the
peak at 850 cm1 attributed to AlO6 and the peak at 1100 cm1
attributed to SO
4 2 (see Fig. 7).
3.6. Thermogravimetry
In order to validate the formation of ettringite Differential Gravimetry Analysis was carried on the samples. The Differential Gravimetry Analysis (DTG) curves of the damaged surfaces of the
mortars are presented in Fig. 8.
The DTG results are in accordance with the mineral analysis.
The peak around 130 C is attributed to the dehydration (water
loss) of ettringite for the samples with 0% and 15% limestone, while
the peak at 450 C is attributed to the consumption of Ca(OH)2,
which appears to be decreased in the mortar with 0% limestone
substitution in 5% Na2SO4 solution; Thus, meaning that more portlandite is consumed to produce ettringite. Finally, the peak around
700 C indicates the loss of CaCO3 and is connected to the existence
of calcite.
3.7. Scanning Electron Microscopy (SEM)

Fig. 8. DTG results of samples immersed in Ca(OH)2 and 5% Na2SO450 C (90 days
period, 50 C).

To complete the investigation, the samples 0% LL and 15% LL immersed in 5% Na2SO4 at 50 C were studied using Scanning Electron

Fig. 9. Sample 0% LL immersed in 5% Na2SO4 solution (90 days period, 50 C).

N. Patsikas et al. / Construction and Building Materials 36 (2012) 10821089

1087

Fig. 10. Sample 15% LL immersed in 5% Na2SO4 solution (90 days period, 50 C).

Fig. 11. Sample 0% LL immersed in Ca(OH)2 solution (90 days period, 50 C).

Fig. 12. Sample 15% LL immersed in Ca(OH)2 solution (90 days period-50 C).

Microscopy and X-ray microanalysis (see Figs. 912). Observing

the microphotographs of the samples, it is evident that needle-like
crystals have been formed while X-ray microanalysis clearly indicates that they are similar to the composition of ettringite. In the
case of samples with 0% and 15% limestone substitution, the crystals have 5 lm size and they are located across the surface of the
specimen.

3.8. Mercury porosimetry

Mercury intrusion porosimetry (MIP) was performed on a
Fisons Porosimeter 2000 in order to accurately measure the porosity of the surface samples (each samples volume was approximately 1 cm3). The total porous for the sample without
limestone substitution was found to be signicantly increased

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N. Patsikas et al. / Construction and Building Materials 36 (2012) 10821089

Table 3
Results for Hg porosimetry (28 days).
Mortar

Bulk density
(g/m)

Specic surface area

(m2/g)

Porosity
(%)

0% LL Ca(OH)2
15% LL Ca(OH)2
0% LL Na2SO4
15% LL Na2SO4

2.26
2.18
2.32
1.95

4.63
5.16
5.46
7.10

8.38
12.31
21.29
17.81

Cumulative Pore Volume

120

15% LL Ca(OH)2
100

0% LL Ca(OH)2

Pore Volume (mm3)

15% LL Na2SO4
0% LL Na2SO4

80

60

4. Conclusions

40

Analyzing the experimental results acquired from the samples

having withstood this external sulfate attack accelerating technique and cured at 50 C, it can be concluded that:

20

0
1

10

100

1000

10000

Pore Radius (nm)

Fig. 13. Cumulative Pore Volume of mortar.

(21.29%), as compared to the porous of the sample with limestone

substitution (17.81%), both samples having been immersed in 5%
Na2SO4 solution and 50 C temperature for a duration of 90 days.
Correspondingly, the porosity values for the samples immersed
in Ca(OH)2 were 8.38% for the sample without limestone substitution and 12.31% for the sample with limestone substitution (see
Table 3). Thus, these are consistent with the compressive strength
results, where the cement made with limestone substitution was
more resistant to the external sulfate attack.
It is obvious, based on the pore size distribution results that cement made with limestone substitution has smaller size capillary
porous which justies the greater resistance against sulfates than

Differential Pore Volume

15% LL Ca(OH)2

80

dV/dr (mm3/g) / log(r,nm)

the sample made without limestone substitution (see Figs. 13

and 14). Furthermore, it is also evident and noteworthy that the
sample without limestone substitution displays a wider distribution in the area of 10200 nm while the sample with limestone
substitution displays a distributional center of weight around the
value of 10 nm.
This preliminary study of durability of white cement mortars
under sulfate environment in an elevated temperature aims to
provide a better understanding of the phenomenon of ettringite
formation. It was shown that addition of limestone can lead to
an improved pore size distribution that will provide higher sulfate
resistance. In addition, substitution of cement with limestone results in reduction of the C3A amount, which is primarily responsible for ettringite formation.
The results of this study are the basis for the continuation of this
research, which aims to provide insightful knowledge on ettringite
formation and in a future stage, direct correlation with fracture and
deterioration properties.

0% LL Ca(OH)2
15% LL Na2SO4
0% LL Na2SO4

60

40

20

 Mortars made without limestone substitution and

immersed in 5% Na2SO4 solution for 90 days exhibit greater
compressive strength loss than the mortars made with 15%
limestone substitution (42% correspondingly). The sulfate
attack rate was 1.5 MPa per 10 days curing in 5% Na2SO4
solution and 50 C for mortars made with limestone substitution in relation to 4 MPa per 10 days curing in 5% Na2SO4
solution and 50 C for mortars made without limestone substitution. If the total collapse equations for the mortars with
limestone substitution are used, it is projected that total collapse will happen after 260 days of curing to this specic
environment against 90 days for mortars without limestone
substitution. Thus, the particular type of cement is three
times more durable compared to pure cement.
 Growth of microcrystalline ettringite (DEF) was identied
by different analytical methods and DEF was found to be
the main cause of deterioration and damage, having created
cracks and caused signicant degradation to the specimens.
 Despite the fact that C3A decrease in cement, due to limestone substitution, is only 19% -while corresponding
decrease of ettringite formation is 55%-, it is evident that
the protection provided to the mortar sample with limestone substitution is not only attributed to the C3A decrease
(agent responsible for ettringite formation) but also attributed
to the better microstructure of these mortars.
 Mercury porosimetry results further support the above conclusion, showing that mortars have different porous distributions while the mortar with 15% limestone substitution
has smaller capillary pores.
 In conclusion, having compared cements of the same compressive strength class, it is found that cement with 15%
limestone substitution develops such a microstructure
which blocks the sulfate ions penetration as manifested
via the greater compressive strength of this particular mortar despite the adverse conditions.

10

100

1000

Pore Radius (nm)

Fig. 14. Differential distribution curve.

10000

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