Construction and Building Materials 68 (2014) 517–524

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Construction and Building Materials

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Investigation of durability of CEM II B-M mortars and concrete with

limestone powder, calcite powder and fly ash
Hüseyin Temiz a,⇑, Fatih Kantarcı b
a _
Kahramanmarasß Sütüçü Imam University, Engineering and Architectural Faculty, Civil Engineering Department, 46050-9 Kahramanmarasß, Turkey
b_
Inönü University, Engineering Faculty, Civil Engineering Department, 44280 Malatya, Turkey

h i g h l i g h t s

 We investigated the engineering properties of the new binding materials.

 The volume expansion of samples were increased with amount of stone powders.
 The strength of samples were decreased with increasing amount of stone powders.
 With addition of FA were increased the strength of samples after 28 days.
 Mass loss and damage have not been observed in any of the samples with FA addition.

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

Article history: In this study, a new binding material obtained by mixing limestone, calcite powders and fly ash in various
Received 2 January 2014 ratios were used instead of mineral admixture in CEM II/B-M. Mechanical and physical properties of the
Received in revised form 21 May 2014 samples were tested. Results showed that an increase which agreed with the standard requirements was
Accepted 30 June 2014
observed in the setting times and volume expansion of paste samples with increasing amount of
Available online 26 July 2014
limestone and calcite powder. Also, the compressive strength of mortar samples decreased with
increasing the amount of limestone and calcite powder. Compressive strength of samples with fly ash
Keywords:
had a significant increase after 28 days. When samples with limestone and calcite powder were
CEM II/B-M
Limestone and calcite powders
immersed in chemical solutions, compressive strength of samples decreased and weight loss increased.
Strength Ó 2014 Elsevier Ltd. All rights reserved.
Durability
Microstructure

1. Introduction
The cement is the main binding material of the mortar and con-
crete. In national and international cement industry studies, having
low price and high quality stands forward. That’s why, use of the
new technologies in the cement production process, investigations
of the availability of the different raw materials and the additives
have been carried on. An important consideration such as contrib-
uting to the sustainable nature has effect upon the researches of
the new materials. In this respect, the ways of benefiting from var-
ious waste and coproduct (fly ash, chalk stone dust, silica fume,
blast furnace slag, etc.) have been searched.
The addition of hydrated lime and silica fume improved the
early age compressive strength of concrete samples with fly ash.
The air permeability of concretes with fly ash containing hydrated
⇑ Corresponding author.
E-mail address: htemiz@ksu.edu.tr (H. Temiz).
lime and silica fume either decreased or remained almost the same
when compared to the concrete without them. The addition of
hydrated lime and silica fume also improved the sorptivity of fly
ash concretes. DSC/TG analyses showed that the addition of
hydrated lime increased the Ca(OH)2 content whereas the addition
of silica fume decreased the Ca(OH)2 contend in the cement pastes.
It was also found that the amount of Ca(OH)2 decreased with time
for both hydrated lime and silica fume added fly ash cement paste.
The addition of hydrated lime and silica fume reduced the total
porosity of fly ash cement paste [1].
Lime-based mortars modified with admixtures were prepared
and subjected to different environments such as outdoor and
indoor exposures, climatic chamber, SO2-chamber, and freezing–
thawing cycles. Ageing resistance and mechanical strengths
improved when additives reduced the water retention and
increased the air content. High dosages of water repellents were
necessary to enhance the durability, sodium oleate being the most
effective additive endures freezing process [2].

http://dx.doi.org/10.1016/j.conbuildmat.2014.06.078
0950-0618/Ó 2014 Elsevier Ltd. All rights reserved.
518 H. Temiz, F. Kantarcı / Construction and Building Materials 68 (2014) 517–524

The results showed that the use of limestone filler instead of

quartz filler modifies the cement hydration process and was bene-
ficial for the mortar properties at 20 °C and at 5 °C. It accelerated
the early hydration of the cement, thus reduced the initial setting
time. After some days, the calcite from the lime stone filler leaded
to the formation of hemicarbonate, which tended to stabilize
ettringite and to minimize the formation of monosulphoaluminate.
It efficiently increased the strength of the mortars containing lime-
stone filler rather than quartz filler [3].
The long term endurance of the Portland limestone cement was
examined. Limestone content of samples were taken between 0%
and 35%. Produced samples were kept in 1.8% magnesium sulphate
solution at +5 °C for 5 years. At the end of 5 years, it was observed
that as the amount of limestone increased the severity of the cor-
rosive effect ascended and significant amount of damage occurred.
Sample damages can be attributed to forming of ettringite {Ca6[Al Fig. 1. PC clinker, FA, limestone and calcite powder.
(OH)6
12H2O]2 (SO4)3(H2O)2} and thaumasite {Ca6[Si(OH)6

12H2O]2 (SO4)2(CO3)2} [4].
The comparison of the features of Portland limestone cement Fig. 1 PC clinker (CL), Fly ash (FA), limestone (LS) and calcite (CT) powders are given.
The chemical analysis of fly ash and CEM II B-M is given in Table 1. Some chemical
and the other composite cement were carried out. The taken
and physical properties of the limestone and calcite used in the study are given in
proportion of clinker was 80%, chalk was 15% and plaster was 5%. Table 2. With regard to limestone CaCO3 proportion, it is suitable to EN 197-1 and
During early ages, the endurance of the samples produced with because its total organic carbon proportion is 0.5%, it is in (L) class [8]. The mixing
PC and PLC bindings was detected higher, in 28 days while it rates of the raw materials used in the research are given Table 3.
started to be equalized, later the endurance of the samples pro-
duced from Portland Puzolan cement (PPC) and Portland with high 2.2. Methods
furnace cinder (PFC) was detected higher. As a principle, although
Aggregate size distribution analysis was carried out according to EN 933-2 [9].
the hydration products of the composite cement were similar to Coarse and fine aggregates are crushed stone. The size distribution and reference
the pure Portland cement, mineral additions affected the products curves of the aggregate used in the study are shown in Fig. 2. Los Angeles abrasive
from ettringite to hydrate [5]. value of the large aggregate was found 15.8%.
In the carried out research, sulphate resistance of paste, mortar Additive content of the new mixtures was taken in equal rates with total
addition of CEM II/B-M. Normal water consistency rates and setting time were con-
and concrete samples made from CEM I 42.5R, CEM II/B-M(P-V) ducted according to EN 196-3 [10]. In the designation of the volume change sound-
42.5, CEM IV/B (P-V) 32.5R and SRPC cement was been examined. ness of the cement, Le Chatelier apparatus which made of brass was used. Scanning
In CEM II/B 10.8% trass, 14.9% fly ash, for its first group of CEM IV/B electron microscope (SEM) investigations were conducted on samples taken from
22.2% and 15.3%; for its second group 20.9% and 13.1% proportion #2 (61.5 CL + 35% LS + 3.5% G), #3 (61.5CL + 30% LS + 5% FA + 3.5% G), #5
(61.5CL + 20% LS + 15%FA + 3.5% G), #7 (61.5 CL + 35% CT + 3.5% G) and #10
of fly ash were put in. Sulphate solutions were prepared taking the
(61.5CL + 20%CT + 15% FA + 3.5% G) with 0.40 w/b ratio.
binding materials in the proportion of 5% and 10%. The highest Prepared paste samples were put into plastic tubes with approximately 300 g
level of expansion in the mortar occurred in CEM I 42.5 and at and covered in a way that block water and air to penetrate inside the tubes, then;
the end of the 38 weeks it completely dispersed. A significant put into another glass container and completely immersed in water, kept in cure
decrease were seen in the amount expansion of samples containing tank till experiment age (28 days). The samples which completed their experiment
age were taken out of water. 25 g of samples from the middle part was taken. The
tras and fly ash. Among the samples treated with natural water, size of the broken part was about 5 mm. To stop hydration, it was put in to pure
while the maximum compressive strength were found in the sam- acetone and kept in it for 24 h. The samples with acetone were dried in the drying
ples produced with OPC, the minimum compressive strength were oven in 40–50 °C approximately for 24 h. After that, they were coated were
found in the samples kept in 5% Na2SO4 solution. A little reduction observed with SEM.
Mortar admixture was prepared using 3 parts of standard sand, 1 part of binder
were observed in the compressive strength of the samples kept in
and ½ part of water by weight. In order to find the characteristic compressive
sulphated solutions compared to the samples treated with natural strength of the mortar prisms, 3 samples were prepared from each age group and
water [6]. cured for 7, 28 and 90 days. The compressive strength was found by averaging 6
As reported by Abalaka and Babalaga [7] 5% NaCl concentration samples – cured in given periods – from each age group obtained by splitting the
increased at early ages (7 and 21 days) compressive strength of cured samples into two [11]. A group of samples kept in cure tank and chemical
solution are seen in Fig. 3. In order to find the durability of the mortar admixture,
concrete samples. But at the end of 28 days compressive strength the samples cured in normal cure tank for 28-day and then kept in 2000 mg/l
decreased.
In this study, as a reference, a new binding material were
obtained by using ground limestone, calcite dust and fly ash with Table 1
the proportion changing from 5% to 35%, instead of mineral addi- The chemical analysis of CEM II B-M and FA.
tive which situated in composition of CEM II B-M cement with Oxides (%) FA CEM II B-Ma
the proportion of 35%. Strength and durability features of mortar
SiO2 56.66 24.20
and concrete samples were researched. Results were compared Al2O3 22.34 7.43
to reference sample and literature. Fe2O3 7.11 3.31
SiO2 + Al2O3 + Fe2O3 86.11 34.94
CaO 5.60 51.80
2. Materials and methods MgO 2.17 2.04
K2O 1.73 0.98
2.1. Materials Na2O 0.76 0.30
SO3 0.11 2.49
In this research, CEM II/B-M (V-L) 32.5R cement, Portland cement clinkers, fly A.Z. 1.86 7.50
_
ash were obtained from ÇIMSA Mersin Cement Factory; limestone and calcite pow- Blaine, cm2/g – 3680
ders were obtained from Bahçe Facility of Barit Incorporated Company; standard
a
sand was obtained from Set Cement Industry and Commerce Incorporated Com- Raw material composition of CEM II B-M: clinker 65.07%, limestone: %15.47, FA
pany, aggregate was obtained from aggregate quarries in Kahramanmarasß. In 19.46%.
 H. Temiz, F. Kantarcı / Construction and Building Materials 68 (2014) 517–524 519

Table 2 Table 4
Some chemical and physical properties of limestone and calcite. Concrete admixture proportions.

Attributes Limestone Calcite Material Name Quantity (kg/m3)

Clay content (g/100 g) 0.17 – Coarse aggregate 1243
Total organic carbon (%) 0.05 – Fine aggregate 556
CaCO3 (%) 93.63 99.1 Binder (cement + mineral additives) 350
Residue (%) 45 lm sieve 16.9 4.4 Water 172
Total 2321
w/b 0.49

Table 3
The mixing proportions of the binding materials.

Sample Number Material proportions (weight %) The concrete admixture prepared according to the standard and proportion
given above was put into the moulds in 15 cm diameter and 30 cm height. There
Cement LS CT FA G
was a 2 cm diameter hole in the middle of moulds. Three samples were prepared
1 (Ref.) CEM II/B-M 15 20 3.5 for each admixture and kept for 24 h in the moulds, after that the steel bar in the
2 61.5 CL 35 – – 3.5 middle was removed and the samples were put into the cure tank. The bottom
3 61.5 CL 30 – 5 3.5 and upper surfaces of the 60-day samples were coated with paraffin during the
4 61.5 CL 25 – 10 3.5 experiment and they were made impervious against water. 10 atm pressure was
5 61.5 CL 20 – 15 3.5 applied to the samples to find permeability values. Pressure increase was 1 kgf/
6 61.5 CL 5 30 3.5 cm2 (0.1 N/mm2) per minute. This process lasted for 7 days and water flow was
7 61.5 CL – 35 – 3.5 checked by doing the assessment of situation twice a day. The results were inter-
8 61.5 CL – 30 5 3.5 preted according to the quantity of flowing water and its depth penetrating into
9 61.5 CL – 25 10 3.5 the concrete.
10 61.5 CL – 20 15 3.5 To find surface wear of hardened concrete samples, 15  15  15 cm cube sam-
11 61.5 CL – 5 30 3.5 ples were produced with mixture proportions indicated in Table 4. After reaching
90 days age, samples were cut about 71  71  71 mm size. Cube samples in
CL: clinker, LS: limestone powder, CT: calcite powder, G: gypsum, FA: fly ash. 71 mm size were done oven-dried after controlling curvature and parallelism.
The unit weight and the sample mass was weighed to an accuracy of 0.001 g. The
surfaces to be abraded were numbered from 1 to 4 and measured with a microm-
eter. 22 spin of the rotary disk was accepted as one period and 16-period abrasion
was applied to each sample. After the operation completed, their measurement was
done with a micrometer and abrasion loss was calculated by DIN 52108 method
[14].

3. Results and discussion

3.1. Setting times and volume expansion

Setting times and soundness values of paste samples are given

in Table 5. Begin and final setting times determined for all samples
were compatible with the values expressed in EN 197-1 for 32.5 N
Fig. 2. Aggregate size distribution and reference curves.
and 32.5 R cements [8]. As seen, minimum begin setting time was
in #1 sample with 138 min; the maximum begin setting time was
in #7 example with 250 min. The minimum final setting time was
obtained in #2 sample with 195 min, the maximum setting time
was also obtained in #7 sample with 320 min. According to these
results, the addition of calcite powder caused a significant increase
in both begin and final setting times compared to limestone pow-
der. FA addition did not cause a significant change in setting times
of the samples. Soundness of samples are also seen in Table 5 and
these values were shorter than 10 mm value which is given in EN
197-1 [8]. However, the calcite powder addition had a higher
increase in expansion compared to the other samples. The maxi-
mum expansion was in #7 with 1.85 mm, the smallest expansion
was in #1 sample with 1.10 mm.

Fig. 3. Mortar samples cured in tank and chemical solutions.

3.2. The microstructure of the paste samples

The microstructures of hardened 28-day paste samples were

and 5000 mg/l Na2SO4 and MgSO4, 50 mg/l and 90 mg/l NH4Cl and 10,000 mg/l
NaCl2 solution for 15 months. Essential chemical materials for the solutions and
their rates were taken according to Ref. [12]. Also in order to make a comparison;
three samples from each admixture were kept in saturated cure tank for 15 months.
During their curing period, the weight loss of the samples were found in 3, 5, 7, 9,
11, 13, 15 month periods and their deformation in form was examined. At the end
of 15 months, their compressive strength was also found.
The water permeabilities of concrete samples were examined in accordance
with EN 12390-8 test method [13]. The admixture design of the concrete samples
is given in Table 4. The permeability test device and a group of sample are seen
in Fig. 4.
investigated with SEM. These images are seen in Fig. 5–8. When
the figures are examined, it is seen that main hydration products
of cement (calcium silicate hydrate, calcium hydroxide and cal-
cium sulfoaluminate) appear and the substances used as additives
have been also partially hydrated.
SEM pictures of #2 and #7 samples cured for 28 days are seen in
Figs. 5 and 6 respectively. When Figs. 5 and 6 are examined, it is
seen that their microstructures are similar. C–S–H, CH, ettringite,
monosulphate and gaps are formed in both admixtures. #8 and
#10 microstructures of the samples produced from admixtures
520 H. Temiz, F. Kantarcı / Construction and Building Materials 68 (2014) 517–524

Fig. 4. Permeability test process and a group of tested samples.

Table 5
Some physical properties of powder materials.

Sample No Normal water consistency ratio (%) Setting time (min) Soundness (mm)
Initial Final
1 (CEM II/B-M) 28.0 138 203 1.10
2 (61.5% PC CL + 35% LS + 3.5% G) 29.5 150 195 1.35
4 (61.5% PC CL + 25% LS + 10% FA + 3.5% G) 28.5 147 200 1.30
7 (61.5% PC CL + 35% CT + 3.5% G) 28.5 250 320 1.85
9 (61.5% PC CL + 25% CT 10% FA + 3.5 % G) 29.0 235 290 1.80
12 (61.5% PC CL + 15% CT + 20% FA + 3.5% G) 29.0 215 285 1.70

Fig. 7. The microstructure of sample 8.

Fig. 5. The microstructure of sample 2.

Fig. 8. The microstructure of sample 10.

Fig. 6. The microstructure of sample 7.

and cured for 28 days are seen in Figs. 7 and 8 respectively. In
Figs. 7 and 8 CSH gels form are more intensively compared to Figs. 5
and 6.
3.3. Compressive strengths of mortar prisms
Compressive strengths of mortar prisms for 7, 28 and 90-day
were obtained as average of 6 samples and results are given in
Fig. 9. The maximum 7-day compressive strength of the samples
was obtained from #7 with 27.5 MPa. The minimum compressive
strength was also obtained from #11 with 22.7 MPa. The maxi-
mum 28-day compressive strength of the samples was obtained
from #6 with 55.1 MPa. This value is higher than reference sample
about 9%. The minimum compressive strength was also obtained
from #2 with 36.6 MPa. The compressive strength of #2 is 27% less
than strength of the reference sample. Of the 90-day compressive
strength of samples, #11 had the maximum compressive strength
with 58.2 MPa. In this age group, #2 had the minimum
 H. Temiz, F. Kantarcı / Construction and Building Materials 68 (2014) 517–524
70
7 day 28 day 90 day
60
Compressive strength (Mpa)
50
40
30
20
10
0 Fig. 11. Water permeability of concrete samples.
1 2 3 4 5 6 7 8
Sample numbers
Fig. 9. Compressive strength of the samples.
compressive strength with 40.7 MPa. These findings show that
additives react depending on their percentages. Of the 7-day
samples, 35% limestone and calcite powder additives (#2 and #7)
samples gave higher strength. Of the 28 and 90-day samples, the
maximum strength value was found in #11 with 30% FA + 5% CT
powder additives and in #6 with 30% FA + 5% LS powder additives.
In later ages, substances remaining unreacted causes lower
compressive strength of mortar samples containing high rate of
limestone and calcite powder (#2 and #7). In later ages, FA addi-
tion causes higher compressive strength because of FA pozzolanic
reactions. These findings based on experimental study result are
confirmed by several studies [15,16].
3.4. Mechanical abrasion
The abrasion losses of limestone and calcite powder additive
concrete samples and reference samples are given in Fig. 10. When
abrasion losses are analyzed, it is seen that very low values of abra-
sion losses are obtained. It is understood that there is a contrast
relation between the compressive strengths and abrasion losses
of the admixtures as expected. Namely, admixtures having high
compressive strength have low abrasion loss. While the maximum
abrasion loss is in #2, the minimum is found in #6 sample. As lime-
stone and calcite stone powder content increased, abrasion losses
also increased. The abrasion losses obtained from all samples is
lower than the predicted maximum value of 18 cm3/50 cm2 given
in EN 1338 for inter locking paving stone. These findings are in
agreement with the literature [17].
3.5. Water permeability
Water permeability results conducted on concrete samples are
shown in Fig. 11. Acquired values show that high rate of calcite
Fig. 10. Abrasion loss of the concrete samples.
521
10
Depth of water penetration into
9
8
concrete (mm)
6
5
4
3
2
1
0
Sample numbers
9 10 11
and limestone additives causes a slight increase in the depth of
penetration of water into concrete but penetration depth of water
decreases with FA addition. High rate of calcite and limestone pow-
der additives causes an increase in the depth of penetration of
water into the samples and makes the unreacted substance
remain. Although stone powder materials that cannot connect with
concrete contribute to fill the spaces, they lead a rise in permeabil-
ity because of not to be able to make a solidified structure. How-
ever, the free flow of water did not occur from any of the
samples. When penetration of water into concrete under the pres-
sure of 10 atm is taken as reference, it is seen that 35% limestone or
calcite powder addition does not cause any problems in terms of
permeability. Results show that the maximum water penetration
depth is obtained from #2 with 9.3 mm, the minimum one is in
#1 sample with 6.1 mm. It is also seen that limestone and calcite
powder contents have similar effects on permeability.
3.6. Durability of mortar prisms in chemical solutions
Weight changes of mortar prisms are given in Figs. 12–15 after
being immersed in 2000 mg/l Na2SO4, 5000 mg/l Na2SO4, 2000 mg/
l MgSO4, 5000 mg/l MgSO4, 50 mg/l NH4Cl, 90 mg/l NH4Cl and
10,000 mg/l NaCl solutions for 15 months. In Fig. 12, weight loss
of mortar prisms immersed in 2000 mg/l Na2SO4 and 5000 mg/l
Na2SO4 solutions is seen. As seen in Fig. 12, there was a slight
increase in weight of the samples immersed in 2000 mg/l Na2SO4
solution. When samples are observed in external appearance, it is
seen that there is no damage and deformity on any of the samples.
On the other hand, on corners of #2 and #7 samples immersed in
the 5000 mg/l Na2SO4 solution, slight erosion appears to occur. In
the weight change of the samples kept in this solution, it is
observed that there are some differences according to the values
obtained from 2000 mg/l Na2SO4 solution. For instance, while the
Fig. 12. Mass changes of the mortar prisms in Na2SO4 solution.
522 H. Temiz, F. Kantarcı / Construction and Building Materials 68 (2014) 517–524
Fig. 13. Weight change of mortar prisms in MgSO4 solutions.
Fig. 14. Mass change in mortar prisms in NH4Cl solutions.
Fig. 15. Weight change of mortar prisms in 10,000 mg/l NaCl2 solution.
weight of #2 and #7 samples increased up to 11 months, after that
moment decrease began. For the reason of increase in weight, fill-
ing the blank with gypsum can be said; for the decrease in weight,
deterioration of the bond providing the strength can be shown
because of sulphate. Results also showed that the solution had fur-
ther negative effects on the admixtures containing high rate of
limestone and calcite stone powder.
Weight loss of the mortar prisms immersed in 2000 mg/l
MgSO4 and 5000 mg/l MgSO4 solutions are seen in Fig. 13. There
was no damage and deformity on samples immersed in 2000 mg/
l MgSO4 solution. Yet, it was seen that there was a little rise in
weight of all admixtures during the testing process. It was also
observed that the least weight increase was in #1 and the maxi-
mum increase was in #7 sample. For the samples analyzed in
5000 mg/l MgSO4 solution, slight erosion appeared to occur in
the corners of #2, 3, 7, and 8 samples including high rate of lime-
stone and calcite stone powder. When the percentages of weight
change analyzed, it was seen that there was no decrease in #1, 5
and 10 samples and the change was approximately fixed at the
end of 15 months. In #2 and 7 samples, containing high amount
of stone powders additives; weight change tends to decrease after
11 months. It is thought that the reasons of increase and decrease
are similar to the effect of Na2SO4 solution. In other words, MgSO4
solution forms gypsum in the space of sample and this causes
weight increase. The least weight increase was obtained from #1
and the maximum weight increase was also obtained from #7.
These results showed that there was no significant amount of
increase in weight change during testing process (15 months).
In Fig. 14 Weight change in mortar prisms immersed 50 mg/l
and 90 mg/l NH4Cl solution is given. When the values are examined,
it is seen that solution are more effective on admixtures containing
high level of stones powder. The reason why the solutions are more
effective in this samples; (i) the dissolution of NH4Cl in water and
decomposition ammonium and chloride ions (NH4Cl ? NH+4 + Cl ,
NH+4 M NH3 + H+) and NH3 which is moving fast effects concrete
adversely, (ii) samples which are containing high proportions lime-
stone and calcite powder have lower compressive strength so NH4-
Cl can effect samples easily. However, it is seen that the weight loss
of all the samples are very little. According to the test results which
were carried out for observational investigation; no damage
occurred in any samples. Weight increases of the samples
immersed in both solutions did not show much difference.
Weight change of mortar prisms immersed in 10,000 mg/l
NaCl2 solution is given in Fig. 15. Salts consist of tightly bound ions.
These bounds weaken in the water and ions become active. This
reaction is NaCl ? Na1+ + Cl1 . Solution of salt is generally electro-
lyte. Due to these properties, salt solutions penetrate into concrete
and can cause to form of 2NaOH vs H2CO3 in concrete. Salt solution
also can cause erosion on the surface of concrete. Likewise, there
was very little weight increase in the samples immersed in this
solution. Additionally, it should be expressed that 15 months is
not enough time for some durability investigations.
Compressive strength of prism samples immersed in solutions
and in normal water are given Figs. 16–19. In Fig. 16; 2000 mg/l
Na2SO4 and 5000 mg/l Na2SO4, in Fig. 17; 2000 mg/l MgSO4 and
5000 mg/l MgSO4, in Fig. 18; 50 mg/l NH4Cl and 90 mg/l NH4Cl,
in Fig. 19; 10,000 mg/l NaCl2 solutions are given. According to com-
pressive strength results given in Fig. 16, negative effect of Na2SO4
solution in both rates on #1 sample was not seen (64.8, 63.6 MPa).
Compressive strength of #1 sample in both solutions was a little
higher than the strength of the sample immersed in normal water.
The minimum compressive strength values in both rates of solu-
tion were obtained from #2 (41.0, 38.9 MPa). These compressive
strength values were less than reference samples in rates of 58%,
63% respectively. According to the examined strength values, com-
pressive strength of the samples containing high rate of limestone
and calcite powder and kept in Na2SO4 solution was lower than
sample immersed in normal water. The reason why Na2SO4
solutions have more negative effects on the samples containing
Fig. 16. Compressive strength of mortar prisms in Na2SO4 solution.
 H. Temiz, F. Kantarcı / Construction and Building Materials 68 (2014) 517–524
Fig. 17. Compressive strength of mortar prisms in MgSO4 solution.
Fig. 18. Compressive strength of mortar prisms in NH4Cl solution.
Fig. 19. Compressive strength of mortar prisms in NaCl2 solution.
high rate of limestone and calcite powder is that Ca(OH)2, unreac-
tive product; comes out in samples produced with these admix-
tures. Ca(OH)2 forms ettringite and monosulphate compounds by
reacting with magnesium and sodium sulphates. Another result
that can be derived from Fig. 16 is that negative effect of Na2SO4
solution could not occur on the samples having high rate of fly
ash. This result is clearly seen in #5 sample.
According to the compressive strength presented in Fig. 17, neg-
ative effect of 2000 and 5000 mg/l MgSO4 solutions on #1 sample
was not seen and the maximum compressive strength was
obtained from this samples (65.2, 63.1 MPa). The minimum com-
pressive strength in both solutions is obtained from #7 (41.6,
39.5). Respectively, these values are 56%, 59% lower than reference
sample strength and also 7%, 13% lower than sample kept in nor-
mal water. Compressive strength of samples which are immersed
in MgSO4 solutions show similar features with samples immersed
in Na2SO4 solutions. As compressive strength values seen in Fig. 17,
it is understood that there are no negative effects of MgSO4 solu-
tions on the samples containing high rate of fly ash.
523
According to the values in Fig. 18, there are no negative effects
of NH4Cl solutions on #1 sample which is reference sample. #7 and
2 samples are the most effected samples by NH4Cl solution. In both
rates of solution, the minimum compressive strength values were
obtained from #7 sample (38.6, 34.2 MPa). Respectively, these val-
ues are around 65%, 81% lower than reference sample strength, and
also 16%, 30% lower sample kept in normal water. Results show
that the effect of solutions on the samples containing high rate of
stone powders is higher. Chlorides interact with calcium silicate
hydrates (C3S2H3) at three different levels as either chemisorbed
layer on C3S2H3, in the C3S2H3 inter layer spaces or be intimately
bound in the C3S2H3 lattice [18]. Chlorides are also known to pro-
mote the leaching of calcium hydroxide and promote the forma-
tion of porous C3S2H3 involving complex reactions [19].
Compressive strength of samples immersed in NaCl solution
was a little lower than samples cured in city drinking water. In
NaCl2 solution, maximum compressive strength was obtained from
#1 sample with 60.6 MPa; minimum compressive strength was
also obtained from #7 sample with 38.4 MPa. The compressive
strength of #7 sample immersed in salt solution is 16% lower than
the one cured in drinking water; and also 57% lower than #1 sam-
ple immersed in the salt solution. Detected compressive strengths
show that NaCl solution has more negative effect on the samples
containing high rate of stone powders as seen in other solutions.
4. Conclusion
In this study, the effect of limestone, calcite powders and fly ash
in various ratios instead of mineral admixture in CEM II/B-M were
investigated by measuring mechanical, physical and durability
properties of samples. The experimental studies led to the follow-
ing conclusions:
1. Limestone and calcite powders did not cause an important
increase in water involvement of the admixtures. There was
not any difficulty in process ability.
2. There was some increase in the setting time and soundness of
the samples containing high rate of limestone and calcite pow-
ders. However, increase in setting time and the amount of
soundness remained under the values given in standard.
3. While limestone and calcite powder increased the early age
strength, they partially caused decrease in strength in later ages.
The decrease in strength values became clear as the rate of these
additives increased. Samples containing 30% FA additive had
higher compressive strengths. Limestone and calcite powder also
caused decrease in compressive strengths. There was a little
amount of abrasion in samples having high compressive strength.
4. Limestone and calcite powder increased the permeability of the
samples a little. However, no water leak occurred in any of the
samples. It was understood that the concretes did not have per-
meability by measuring the parts moisted with water.
5. There was not a significant damage in any of mortar prisms
during being immersed in Na2SO4, MgSO4, NH4Cl and NaCl solu-
tions for 15 months. While no damage was observed in samples
with CEM II/B-M binder in any of the environments, especially
slight damage was observed on the corners of samples contain-
ing high rate of limestone and calcite powder in Na2SO4, MgSO4,
NH4Cl solutions. Little amount of weight loss and compressive
strength loss occurred.
6. Weight loss, damage and compressive strength loss were not
observed in any of the samples containing FA after exposed to
Na2SO4, MgSO4, NH4Cl and NaCl solutions. UK addition also
decreased the permeability value of the concrete samples.
7. Consequently, it can be said that CEM II B-M cement containing
limestone and calcite powder up to 35% rate can be used in the
structure which are not exposed to the effect of sulphate and
524 H. Temiz, F. Kantarcı / Construction and Building Materials 68 (2014) 517–524
chloride. Additionally, it also should be expressed that
15 months is not enough time for some durability
investigations.
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