Construction and Building Materials 70 (2014) 1725

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Comparison of y ash, silica fume and metakaolin from mechanical

properties and durability performance of mortar mixtures view point
_
Sezer, Kambiz Ramyar
Ali Mardani-Aghabaglou , Gzde Inan
_
Turkey
Department of Civil Engineering, Eng. Faculty, Ege University, Bornova, Izmir,

h i g h l i g h t s
 The contribution of silica fume and metakaolin to the strength was started as early as 3 days.
 For the y ash this duration was 180 days.
 Mineral admixtures improved transport properties greater than mechanical properties.
 The presence of the mineral admixture and its type changed the ettringite morphology.

a r t i c l e

i n f o

Article history:
Received 1 May 2014
Received in revised form 13 June 2014
Accepted 23 July 2014
Available online 15 August 2014
Keywords:
Mineral admixture
Microstructure
Transport properties
Durability performance

a b s t r a c t
In this study the effect of cement replacement with y ash, silica fume and metakaolin on the compressive strength, dynamic elastic modulus, chloride-ion penetration, water absorption, water sorptivity, and
freezethaw and sulfate resistance of the mortar mixtures were comparatively investigated. In addition,
micro-structural investigation was performed on some selected mortar mixtures, and regression analysis
was applied on the sulfate resistance test results. It was observed that, the presence of the mineral admixture and its type changed the ettringite morphology. Besides, only ball-ettringite and a special type of
ettringite were observed in the silica fume- and metakaolin-bearing mixtures, respectively. The needle-like and ball-ettringite formation were found in the y ash mixtures. In the control mixture the needle-like, ball-ettringite and massive ettringite were detected. Overall test results revealed that the
performance of the mixtures was arranged in descending order as silica fume-, metakaolin-, y ash-bearing mixtures and the control one.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Some of the mineral admixtures used nowadays are industrial
by-products [1,2]. Silica fume is a by-product of the manufacture
of silicon metal and ferrosilicon alloy and it contains more than
8085% SiO2 in amorphous form. Thus, it has highly pozzolanic
properties and is suitable to use in the cement and concrete industries [36]. Metakaolin is produced by calcinations of pure or
rened kaolinitic clay at a temperature range between 650 and
850 C. It is also a processed amorphous silica material [7]. Fly
ash is obtained as a waste product upon the combustion of pulverized coal in thermal power plants [810].
Mineral admixtures are used as cement replacement material in
mortar mixtures and several special types of concrete such as selfcompacting, reactive-powder, roller compacted and lightweight
concrete. Mineral admixtures are used in order to improve
Corresponding author. Tel.: +90 232 3886026; fax: +90 232 3425629.
E-mail address: ali.mardani16@gmail.com (A. Mardani-Aghabaglou).
http://dx.doi.org/10.1016/j.conbuildmat.2014.07.089
0950-0618/ 2014 Elsevier Ltd. All rights reserved.

mechanical properties of the mixture because of its pozzolanic

and/or self cementitious nature. In addition, resistance of the mixture to freezethaw cycles [11], sulfate attack [12,13], acidic attack
[14], alkaliaggregate reaction [15] and reinforcement corrosion
[16] as well as transport properties of the mixture [17,18] were
reported to be improved with the addition of mineral admixture.
However, the improvement of the above mentioned properties of
the cementitious systems were found to be higher when ultrane
mineral admixtures such as silica fume and metakaolin were incorporated into the mixture [19,20]. Besides, mineral admixtures
cause to decrease cost of the mixture upon enhancement of workability of fresh concrete. Moreover, fresh concrete mixtures containing mineral admixtures are less prone to bleeding [1].
The effect of mineral admixtures on the properties of mortar or
concrete mixtures was investigated by many researchers. However, there is relatively little data on the microstructure of the
binders exposed to various deleterious effects. The aim of this
study was to investigate comparatively the effect of y ash, silica
fume and metakaolin on the strength, ultrasonic pulse velocity,

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A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

dynamic elastic modulus, chloride ion penetration, water absorption, water sorptivity, sulfate resistance and freezethaw resistance of cement mortars. For this purpose, 10 w% of the cement
was replaced with y ash, silica fume and metakaolin. The 7, 28,
90, 180 and 300-day compressive strength, as well as 300-day
transport properties and freezethaw resistance of the mortar mixtures were determined. Besides, the behavior of the mixtures
exposed to sodium and magnesium sulfate solutions for 300 days
was studied. In addition micro-structural investigation and regression analysis was performed on mortar mixtures exposed to sulfate
attack.
2. Experimental study
2.1. Materials
In this study, a CEM I 42.5 R type cement conforming to EN 197-1 standard [21]
was used. A high-lime (class C according to ASTM C 618-03 [22]) y ash conforming
to EN 450-1 standard [23], a silica fume and a metakaolin were used as the cementitious material. Pozzolanic activity indices of the mineral admixtures were determined according to ASTM C311 [24]. The chemical composition, as well as some
mechanical and physical properties of the cement, y ash, silica fume and metakaolin obtained from their manufacturers, is presented in Table 1. The standard sand
conforming to EN 196-1 standard [25] with saturated surface dry bulk specic gravity of 2.72 and absorption capacity of 0.70% was used.
In all of the mixtures, water/binder (w/b) ratio and sand/binder (s/b) ratio were
kept constant as 0.485 and 2.75 (by weight), respectively. In addition to the control
mixture containing no mineral admixture; in the test mixtures, 10 wt% of portland
cement was replaced with y ash, silica fume and metakaolin. Flow values of the
fresh mortar were determined in accordance with ASTM C1437 [26]. The recorded
ow values were in the range of 170 20 mm. The lowest ow values were
obtained in the mixtures containing either silica fume or metakaolin. This was
due to the extremely high neness values of these admixtures.
2.2. Test procedures

mt
Ad

where, I = sorptivity (mm), mt = change in weight at the time t, A = exposed area of

the specimen (mm2), and d = density of the water (g/mm3).
25  25  285 mm prism specimens were prepared for sulfate resistance tests.
Sulfate resistance tests were performed according to ASTM C1012 standard [35].
The specimens were separately immersed in 5% sodium sulfate and 4.2% magnesium sulfate solution. The length changes were measured every 30 days until
300 days. Then micro-structural investigations were performed on selected specimens. After exposure to sulfate solutions, the specimens were cut and dried at
35 C and 50% relative humidity for 2 h. The micro-structure of the specimens
was studied by using JEOL JSM 6060 electron microscope. Scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) analyses were attempted to
identify the composition of these materials and their morphology. EDS results are
the average of three measurement.

3. Test results and discussion

3.1. Compressive strength

50 mm cube specimens were prepared for compressive strength and ultrasonic

pulse velocity tests. 7, 28, 90, 180 and 300-day compressive strengths and ultrasonic pulse velocities of the mortar mixtures were determined according to ASTM
C109 [27] and ASTM C597 [28] standards, respectively. Dynamic elastic moduli of
the mixtures were calculated regarding their ultrasonic pulse velocity and density
values using Eq. (1) [2,29]:

Edn qc2

resistance of the mortar mixtures cured for 300 days in water were determined
in accordance with ASTM C1202 [30], ASTM C642-97 [31], ASTM C1585 [32] and
ASTM C 666 [33] standards, respectively.
For chloride penetration test, the amount of electrical current passed through
the cylinder specimens was measured for 6 h. At the end of 6 h the total charge
passed, in coulombs, was measured. For water absorption test, saturated surface
dry specimens were weighed and then kept in an oven at 105 5 C until attaining
a constant mass. For freezethaw resistance test, the mortar specimens were frozen
in air from 5 2 C to 18 2 C within 3 h and were thawed in 5 2 C water
within 1 h in a single cycle. The changes in weight of each specimen were calculated
at every 30 freezethaw cycles until 300 cycles in accordance with TSE CEN/TS
12390-9 [34] standard. For water sorptivity test, the specimens were dried at
105 C until a constant weight, and then the side surfaces of the specimens were
sealed with an acrylic copolymer-based sealing material. Supporting rods were
placed at the bottom of a pan and the pan was lled with the tap water to provide
13 mm water level on the top of the supporting rods. At 0, 5, 10, 20, 30, 60, 120,
180, 240, 300, 360 min time intervals the specimens were weighed. The sorptivity,
I, was obtained from Eq. (2):

1 m1  2m
1  m

where, Edn = dynamic elastic modulus of the mortar (MPa), q = hardened density
(kg/m3), c = ultrasonic pulse velocity (km/s) and m = Poissons ratio. Poissons ratio
was assumed as 0.2 for all of the mixtures.
The 100  50 mm cylinder specimens were prepared for chloride-ion penetration, water absorption and freezethaw resistance tests. In addition,
40  40  160 mm prism specimens were prepared for water sorptivity test. The
chloride-ion penetration, water absorption, water sorptivity and freezethaw

Compressive strength values of the mortar mixtures are shown

in Fig. 1. The silica fume-bearing mortars showed the highest compressive strength values compared to those of the other mortar
mixtures. However, the y ash mortars presented the lowest compressive strength values up to 180 days. Beyond this age, compressive strength values of the y ash-bearing mixtures were higher
than that of the control mixture. The compressive strength of the
mortar mixtures containing metakaolin and silica fume were
higher than that of the plain mixtures at all ages. As it is well
known, the pozzolanic materials form additional calcium silicate
hydrate (CSH) upon the reaction of reactive silica of pozzolan
and calcium hydroxide (CH) produced by the cement hydration.
This provides additional strength particularly at later ages. Since,

Table 1
Some physical, chemical and mechanical properties of using materials.
Chemical Composition (%)

Physical Properties of Cement

*

Cement
FA
SiO2
23.84
32.80
Al2O3
4.2
13.77
Fe2O3
3.4
4.78
CaO
61.0
39.69
MgO
1.8
2.05
Na2O
0.20
0.40
K2O
0.46
1.18
SO3
2.93
4.22
Cl
0.0064

LOI
1.74
1.34
IR
0.30

Compressive Strength of Cement (MPa)

3-day
7-day
28-day
*

FA = Fly ash, SF = Silica fume and MK = Metakaolin.

SF
87.29
0.47
0.63
0.81
4.47
1.25
1.28
0.22

2.70

MK
63.53
32.36
0.54
0.29
0.18
0.33
1.08
0.01

1.00

25
37.2
44.6

Initial setting time (min)

Final setting time (min)
Volume expansion (mm)
Specic gravity

Specic surface area (cm2/g)

Cement (Blaine method)
Fly ash (Blaine method)
Silica fume (BET method)
Metakaolin (BET method)
Pozzolanic activity index (%)
Fly ash
Silica fume
Metakaolin

Cement
Fly ash
Silica fume
Metakaolin

110
166
1
3.11
2.29
2.10
2.20

7-Day
69
101
102

3360
4040
18000
11768
28-Day
79
132
110

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A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

Compressive Strength (MPa)

70

Control
10% Metakaolin

60
55
50

Control

45

10% Fly Ash

40

10% Metakaolin

35

10% Silica Fume

30
25
0

50

100

150

200

250

300

Age (Days)

Dynamic elastic modulus (GPa)

65

10% Fly Ash

10% Silica Fume

50
40
30
20
10
0

Fig. 1. Compressive strength of mortar mixtures.

28

90

180

300

Age of concrete (Day)

sufcient amount of CH is not available at early ages of hydration
of cement, the early strength of pozzolanic mortars can be lower
than that of control mortars. However, pozzolanic activity index
and specic surface of silica fume and metakaolin were extremely
higher than y ash. So, even seven-day compressive strength of the
mortars containing these pozzolans was also higher than that of
the control mixture. It was found that, the 300-day compressive
strengths of silica fume-, metakaolin- and y ash-bearing mixtures
were 5%, 10% and 20% greater than that of the control mixture,
respectively.
3.2. Dynamic elastic modulus determined by ultrasonic pulse velocity
(UPV)
The ultrasonic pulse velocity and dynamic elastic modulus of
the mortar mixtures are shown in Figs. 2 and 3, respectively. As
it can be seen from Fig. 2, except for 7 days, the UPV values of
the control mixture and mixtures containing silica fume and
metakaolin were higher than 4.5 km/s, the limit specied for
strong concrete by Whitehurst [36]. However, y ash mixtures
reach this limit after 28 days. As it is well known, the mix proportion, materials properties, pore structure and interfacial transition
zone (ITZ) characteristics are highly effective on UPV values of the
mortar mixtures. It seems that the pozzolanic materials, depending
on their neness and activity, caused renement of the pores in the
ITZ and in the matrix. The fact is reported to be both due to the
physical pore-lling effect and to the pore renement upon formation of additional CSH through pozzolanic reaction [1,2]. Since,
silica fume has the highest specic surface and activity the highest
UPV values belong to silica fume mixtures at all ages.
Dynamic elastic moduli of the pozzolanic mortars were less
than that of the control mixture at 7 days. Beyond this age,

Whitehurst [36] : UPV

> 4.5 Strong,
3.5 - 4.5 Good,
3 - 3.5 Intermediate,
< 2 Weak.

7-Days
90-Days
300-Days

28-Days
180-Days

UPV (Km/s)

5
4
3
2
1
0

Control

10% FA

10% MK

10% SF

Fig. 2. Ultrasonic pulse velocity values of mortar mixtures.

Fig. 3. Dynamic elastic modulus of mortar mixtures.

dynamic elastic modulus values of the control mixture were below

silica fume- and metakaolin-bearing mixtures. As it was expected,
the unit weight of the mortar mixtures decreased with the using of
mineral admixtures due to their lower specic gravity values compared to that of the cement. Since y ash had the lowest specic
gravity among the mineral admixtures used in this study, it
resulted in a mixture having the lowest unit weight. As it is shown
in Eq. (1), dynamic elastic modulus depends on the unit weight and
UPV values of the mixture. In spite of having higher UPV values, y
ash mixtures showed the lowest dynamic elastic modulus beyond
28 days. This fact arises from the unit weight of the y ash mixture
which is the lowest among the unit weights of the mixtures.
The relationship between compressive strength and UPV values
of the mortar mixtures are plotted in Fig. 4, indicating that there is
a strong relationship between UPV values and compressive
strength values of the mortar mixtures. The coefcient of correlation (r) values are found to be close to 1.
3.3. Transport properties
The chloride ion penetration, water absorption and water sorptivity as well as the relationship between water absorption and
sorptivity values of the mortar mixtures are shown in Figs. 58.
As it can be seen from Fig. 5, chloride ion penetration values of
the control mixture and mixtures containing y ash or metakaolin
were in the range of 20004000 and 10002000 coulombs, respectively, the limits specied for moderate and low chloride ion penetration resistance of the mixtures in accordance with ASTMC 1202
standard [30]. However, chloride ion penetration value of silica
fume-bearing mixture was lower than 1000 coulombs, the limit
specied for very good chloride ion penetration resistance of the
mixtures in accordance with the relevant standard. From the
results of the chloride ion penetration test, it becomes evident that
the use of silica fume, metakaolin and y ash reduces the charge
passed through the mortar by 75%, 65% and 45%, respectively. As
it can be seen from Fig. 6, the water absorption values of the control and y ash mortar mixtures were in the range of 35%, the
limit specied as average in accordance with CEB-FIP [37]. However, water absorption of the mortar mixtures incorporated
metakaolin or silica fume were lower than 3%, the limit specied
as good in accordance with the given standard. The maximum
and minimum absorption values were obtained in the control
and silica fume mortar mixtures as 4.2% and 1.8%, respectively.
The water absorption value of the control mixture was decreased
by 60% upon silica fume incorporation. As it can be seen from
Fig. 7, water sorptivity of the mortars were decreased by the

A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

Compressive strength (MPa)

Control

70
65
60
55
50
45
40
35
30
25
3.8

y = 29.22x - 85.419
r = 0.9925

4.3

70

4.8

UPV (Km/s)

(a)

(b)

10% Metakaolin

65
60
55

y = 28.312x - 81.228
r = 09881

50
45
40
35
30
25
3.8

70
10% Fly Ash
65
60
55
y = 33.42x - 104.92
50
r = 0.9948
45
40
35
30
25
3.8
4
4.2 4.4 4.6

UPV (Km/s)

Compressive strength (MPa)

Compressive strength (MPa)

Compressive strength (MPa)

20

4.2

4.4

4.6

4.8

5.2

70

4.8

5.2

4.8

5.2

10 % Silica Fume

65
60

y = 32.565x - 101.35
r = 0.9951

55
50
45
40
35
30
25
3.8

UPV (Km/s)

4.2

4.4

4.6

UPV (Km/s)

(c)

(d)

Fig. 4. Relationship between compressive strength and UPV values of mortar mixtures: (a): control mixture, (b) 10% y ash, (c) 10% metakaolin, (d) 10% silica fume.

3000
3211

2500
2000
1500

1824

1000
1089

500

759

Control

10% FA

10% MK

10% SF

Fig. 5. Chloride ion penetration test results of all mortar mixtures.

Initial rate of sorptivity

3500

(mm/s1/2)

ASTMC1202[30]: Charge passed is

>4000 High,
2000-4000 Moderate,
1000-2000 Low,
100-1000 Very Low,
<100 Negligible.

1x10-3

Charge passed (Coulomb)

4000

6
5

5.9

4.8

4
3

3.4
2.9

2
1
0

Control
CEP [37] : Water absorption ratio is
< 3% Good,
3-5% Average,
>5% Poor.

Water absorption (%)

4
4.2

3
3.1
2.8

1.8

10% FA

10% MK

10% SF

Fig. 7. Water sorptivity of mortar mixtures.

inclusion of mineral admixture. The sorptivity values of the control, y ash-, metakaolin- and silica fume-bearing mixtures were
5.9, 4.8, 3.4 and 2.9 mm, respectively. Silica fume showed the most
superior result compared to the other pozzolans. The reason for
improvement of the transport properties of the mixtures are similar to those given for the strength and UPV test results.
Fig. 8 indicates that, there is a strong relationship between
water absorption and chloride ion penetration of the mortar
mixtures.
3.4. Sulfate resistance

Control

10% FA

10% MK

Fig. 6. Water absorption of mortar mixtures.

10% SF

Expansion values of the mortar mixtures immersed in Na2SO4

and MgSO4 sulfate solutions are presented in Fig. 9. Not surprisingly,

A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

Charge passed (Coulomb)

3500
3000

y = 333.37x2 - 955.96x + 1370.3

r = 0.9866

2500
2000
1500
1000
500
0
1.5

2.5

3.5

4.5

Water absorption (%)

Fig. 8. Relationship between water absorption and chloride ion penetration of
mortar mixtures.

the control mortar had the highest length change values at all ages
compared to those of the pozzolanic mortars. However, the difference between expansion values of the control and the pozzolanic
mixtures increased by increasing the pozzolanic activity index of
the mineral admixture incorporated to the mortar. The expansion
values of the mortar mixtures immersed in sodium sulfate solution
were lower than the expansion of these immersed in the magnesium
sulfate solution. The more destructive effect of magnesium sulfate
compared to that of sodium sulfate is attributed to the destruction
of CSH upon magnesium sulfate attack [1,2].

0.3

Control
10% Fly Ash
10% Metakaolin
10% Silica Fume

Expansion (%)

0.25
0.2
0.15
0.1
0.05
0
0

30

60

90

120

150

180

210

240

270

300

Holding time in sulfate solution (Days)

(a)
0.35

Control
10%Fly Ash
10% Metakaolin
10% Silica Fume

Expansion (%)

0.3
0.25
0.2
0.15
0.1
0.05

21

As it can be seen from Fig. 10, no signs of deterioration were

found in silica fume- and metakaolin-containing mixtures upon
300 days sulfate exposure. However, the y ash mixture and the
control mixture were seriously damaged. The effect was more pronounced in the control mixture.
Ettringite formation in the mixtures exposed to sulfate solutions up to 300 days, detected by SEMEDS analysis, are shown
in Figs. 1115. EDS analysis results were used to interpret the sulfate resistance test results. As it can be seen from Figs. 1115,
ettringite formed in all of the mixtures exposed to sulfate attack.
Ettringite formation and its morphology are the most important
factors affecting expansion upon sulfate attack [38]. It was found
that the presence of the mineral admixture and its type affect
the morphology of the ettringite. All ettringite formations such as
ball, needle-like and massive as well as gypsum crystals were
observed in the control mixture. As it can be seen from Fig. 11,
the ettringite formed nearby the gypsum crystals. Needle-like
and ball-ettringite formations were observed in the y ash mixtures (Fig. 12). However, only ball-ettringite formation was
observed in silica fume mixtures (Fig. 14). It is reported that the
ball-ettringite formation has non-expansive character; however,
the needle-like ettringite formation has an expansive character
[39]. A special type of ettringite formed in the mixtures containing
metakaolin was also found to have no expansive effect (Fig. 13).
Due to the absence of the needlelike ettringite in the silica fumebearing mixture, the expansion values of these mortars were lower
than the other mixtures. As it can be seen from Figs. 13 and 14, in
mortar mixtures containing silica fume and metakaolin, ettringite
was only formed inside the pores. However, in the control and
y ash mixtures, ettringite was formed both inside and outside
of the pores. As it is known, the ball-ettringite formed inside the
pores can be converted to needle-like form after a sufcient time.
So, microcracks in the matrix and ITZ may be increased by transforming the ball-ettringite into needle-like one. Thus, the ingression of sulfate ions into the mixture becomes easier. Finally,
needle-like ettringite formations are nested together and convert
to the massive ettringite formation [39]. The massive ettringite formation is an indicator of the severe sulfate attack accompanying a
large expansion. This may be due to the presence of more sulfates
in the structure of the massive ettringite [38].
The performance of the mixtures against sulfate attack can be
arranged in descending order as silica fume, metakaolin, y ash
and control mortars. The higher performance of the pozzolanic
mortars compared to that of control mixture is attributed to the
reduction in cement portion of the mortars upon replacement of
cement with the mineral admixture. As a result, C3A content of
the binder reduces, consequently, the ettringite formation
decreases. Besides, CH formation in the hydrated binder decreases
due to reduction of C3S and C2S content of the binder. Besides, CH
content of the hydrated binder reduces further due to the consumption of CH upon pozzolanic reaction. The CSH thus produced renes the ITZ and the matrix pores by causing lower
permeability [13]. As a result of these, transport properties are
expected to be improved. The similar improvements were obtained
in the present study. Another reason for higher sulfate resistance of
the mineral admixture-bearing mixtures is their lower permeability, which in turn, makes the ingress of the sulfate solutions
difcult.
3.5. Prediction of sodium sulfate expansion using regression analysis

0
0

30

60

90

120

150

180

210

240

270

300

Holding time in sulfate solution (Days)

(b)
Fig. 9. Expansion values of mortars mixtures (a) Na2SO4 and (b) MgSO4.

A multiple regression analysis was applied to obtain the following relationship between sodium sulfate expansion, exposure period and pozzolanic activity index the of mineral admixture.

E 94:707  1:011D  P 1:973

22

A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

Silica fume
mixture

Metakaolin
mixture

Fly ash
mixture

Control
mixture

Control
Mixture
(Before
the
damage)
Control
mixture
(After
the
damage)

Fig. 10. Images of mortar mixture at the end of 300-day sulfate attack.

XX
X

Fig. 11. SEM images of the control mortar mixtures (E: Ettringite, G: Gypsum).

where, E: expansion values of the mortars in sodium sulfate solution (%), D: sodium sulfate solution exposure period (days) and P:
28-day pozzolanic activity index of the mineral admixture (%).
The estimated values are in a good agreement with the experimental values obtained in this study. The coefcient of correlation
between estimated and experimental values is 0.89. In the other

words, the differences between the calculated and experimentally

obtained values are within the range of 0.181%. The proposed
equation is independent of the type of mineral admixture. Once,
the pozzolanic activity index of the mineral admixture and
exposure time in sodium sulfate solution is known, the expansion
values, as specied by ASTM C1012 [35] test method, can be

A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

23

Fig. 12. SEM images of the y ash mortar mixtures (E: Ettringite, CH: calcium hydroxide).

Fig. 13. SEM images of the metakaolin mortar mixtures (E: Ettringite).

Fig. 14. SEM images of the silica fume mortar mixtures (E: Ettringite).

estimated by using the proposed equation. However, for the mixtures exposed to the magnesium sulfate solution, there was not a
strong relationship between expansion and the other parameters.
The coefcient of correlation in the case of MgSO4 exposure was
found to be 0.43. This may be due to the fact that magnesium sulfate attack in addition to ettringite and gypsum formation expansion causes a loss of mass due to CSH destruction. It should be
emphasized that the equation is valid for the materials and the
mixtures used as well as the test conditions applied in this study.
3.6. Freezingthaw resistance
The weight change (at every 30 freezethaw cycles), the compressive strength reduction and relationship between weight loss
and water absorption of the mortar mixtures after 300 cycles of
freezingthawing are shown in Figs. 1618, respectively. At the
end of 300 cycles, the reduction in compressive strength of the
control, y ash, metakaolin and silica fume mixtures were 26%,

18%, 11% and 7%, respectively. The weight loss for these mixtures
was 1.36%, 1.05%, 0.7% and 0.48%, respectively. The weight loss of
the specimen increased with increasing of the microcracks and
scaling due to freezethaw cycles. Test results demonstrated that
the mixture containing silica fume had the best performance
against frost action. It should be mentioned that no air entraining
agent was used in the mixtures.
It is known that the degree of saturation of the material plays an
important role in the freezingthawing behavior. Thus, the transport properties can be a good measure of the freezingthawing
resistance of the material [40]. Transport properties test results
indicated that the permeability of the mortar mixtures decreased
by using of the mineral admixtures. Moreover, the mixture containing silica fume had the best transport properties compared to
the other pozzolanic mortars. As it was mentioned earlier, cement
replacement by silica fume resulted in a 75% reduction in the chloride ion penetration of the mortar. As it can be seen from Fig. 18,
the weight loss of the mortar mixtures exposed to 300 freezethaw

24

A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

Gypsum (X)

Ettringite (XX)

1.4

Control

Weight loss (%)

1.2

10% Fly Ash

10% Metakaoline

10% Silica Fume

0.8
0.6
0.4
0.2
0
0

50

100

150

200

250

300

Compressive strength reduction (%)

Fig. 16. Weight loss percentage of all mixtures during freezingthawing cycles.

26

18

11
7

10% FA

10% MK

y = 2.4657x + 0.762
r = 0.9672

1
0.3

0.5

0.7

0.9

1.1

1.3

1.5

Water absorption (%)

Number of freeze-thaw cycles

Control

Weight loss at the end of 300 freeze-thaw

cycles (%)

Fig. 15. EDS analysis of ettringite and gypsum.

10% SF

Fig. 17. Compressive strength reduction percentage of mortar mixtures after 300
freezethaw cycles.

cycles, increased linearly with increasing its water absorption

capacity.
4. Conclusion
For the materials used and the results obtained the following
conclusions may be drawn;

Fig. 18. Relationship between weight change after 300 cycles of freezing and
thawing and water absorption of mortar mixtures.

 The compressive strength, dynamic elastic modulus, ultrasonic

pulse velocity, transport properties, sulfate resistance and freezingthawing resistance of the mortar mixtures was arranged in
descending order as silica fume, metakaolin, y ash and control
mortars.
 The transport properties of the mortar mixtures were improved
upon inclusion of the mineral admixtures. Relative chloride ion
penetration values of silica fume-, metakaolin- and y ash-bearing mixtures compared to that of the control mixture were 25%,
35% and 55%, respectively. The corresponding values for the relative water absorption were 42%, 67% and 74%, for silica fumemetakaolin and y ash-containing mixtures, respectively.
 As it was expected; expansion values of the mortar mixtures
immersed in sodium sulfate solution were lower than those
obtained upon magnesium sulfate exposure.
 In the mortar mixtures containing silica fume and metakaolin,
ettringite was only formed inside the pores; however, in the
control and y ash mixtures, it was formed both inside and outside of the pores.
 The ettringite morphology was found to be affected by the type
of thee mineral admixture. Ball-ettringite formation and a special type of ettringite were observed in the silica fume- and
metakaolin-bearing mixtures, respectively. The needle-like
and ball-ettringite formations were found in the y ash mixture.

A. Mardani-Aghabaglou et al. / Construction and Building Materials 70 (2014) 1725

However, in the control mixture, in addition to the needle-like

and ball-ettringite formations, the massive ettringite was also
detected. It seems that massive ettringite causes greater
expansion.
 A good correlation was found between the predicted and measured expansion values upon sodium sulfate attack. This was
not the case for magnesium sulfate expansion.

Acknowledgement
The authors would like to thank Izmir Baticim cement plant
authorities for their kind assistance in providing the cement as
well as determining the chemical composition of the cement.
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