Construction and Building Materials 201 (2019) 599–609

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Construction and Building Materials

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

The effect of fly ash additive on the resistance of concrete to alkali silica
reaction
Džigita Nagrockienė ⇑, Aurimas Rutkauskas
Vilnius Gediminas Technical University, Sauletekio 11, LT-10223 Vilnius, Lithuania

h i g h l i g h t s

 Fly ash are among the most promising of concrete components.

 Fly ash additives increased concrete alkali silica reaction resistance.
 Fly ash additives can be used for modification of concrete.

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

Article history: Concrete is the most widely used construction material obtained after the setting of the mix composed
Received 8 October 2018 course and fine aggregates, cement and water. The main properties of concrete are determined by the
Received in revised form 24 December 2018 quality and characteristics of aggregates, w/c ratio, and the uniformity of mix compaction. Materials
Accepted 31 December 2018
used: Portland cement CEM I 42.5 R, 0/4 fraction sand, 4/16 fraction gravel, fly ash, superplasticizer,
and water. 7 batches of specimens were made with different fly ash content: 0%, 15%, 25%, 35%, 45%,
55%, 65% (replacing cement in the mix, %). Compressive strength and flexural strength, water absorption,
Keywords:
density, ultrasonic pulse velocity, and alkali silica reaction resistance were tested in modified concretes
Fly ash
Concrete
against the expansion of the specimens. Concrete, where 65% of cement is replaced by fly ash, has higher
Compressive strength density, ultrasonic pulse velocity, and lower water absorption rate. Subsequently, the expansion of mod-
Expansion ified specimens is lower. All these characteristics improve the alkali silica reaction resistance of concrete.
Alkali silica reaction resistance The obtained relationship between the fly ash content in concrete mix, the change of ultrasonic pulse
velocity and expansion of the specimen is used to evaluate the alkali silica reaction effect on concrete.
The tests revealed that concrete modified with 65% of fly ash has better durability and alkali silica reac-
tion resistance characteristics and can be used in construction works.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
In the present day, concrete is the most widely-used construc-
tion material in the world [1]. Concrete is made of aggregates,
water and a binding material (cement or other cementitious mate-
rials). The reactions between aggregates and binding agents are
very complex [2]. Silica dioxide released from reactive aggregates
reacts with the alkali-hydroxides (sodium and/or potassium) pre-
sent in base metals to form ASR gel [3]. The alkali in concrete
mix mainly come from cementitious materials. This interaction is
widely known as alkali silica reaction [2].
Alkali silica reaction is one of the most deleterious reactions in
concrete [4]. ASR can cause destructive expansion, which is
⇑ Corresponding author.
E-mail addresses: dzigita.nagrockiene@vgtu.lt (D. Nagrockienė), aurimas.rut-
kauskas@vgtu.lt (A. Rutkauskas).
affected by many factors, such as the nature and dosage of activa-
tors, binders, reactive aggregates, testing methods. All factors
should be considered at the same time to understand the beha-
viour of the materials studied [5]. There are many ASR affected
structures around the world for which periodical repairs and pre-
ventive maintenance policies represent on going costs [6]. The
damage caused in concrete due to alkali-silica reaction (ASR) was
first recognized in the U.S. already in 1940 and since then has been
investigated in many countries. Researchers have identified three
major factors causing ASR in concrete: the alkalis contained in
the pore solution, reactive amorphous or poorly crystallized silica
present in certain aggregates, and water [7].
ASR related damage is the cracking of concrete structure result-
ing from the expansion of alkali silica reaction (ASR) product
calcium hydrosilicate gel [8]. This gel can appear as a dark border
around the aggregate or a white spot within the aggregate.
Sometimes the white area extends into the concrete matrix [9].

https://doi.org/10.1016/j.conbuildmat.2018.12.225
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
600 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609
High-swelling gels may cause pressure exceeding the tensile
strength of concrete, which results in concrete cracking. Tempera-
ture also influence swelling pressures [10]. ASR may take from 3 to
even more than 25 years to develop significantly in concrete
structures depending on the main factors such as the nature
(reactivity level) of the aggregates used, the moisture and temper-
ature conditions, and the alkali content in concrete [11]. Two main
steps describe the mechanism [12]: The first step is the chemical
reaction between the reactive silica in the aggregate with the alkali
present in concrete to produce alkali-silica gel. The second step is
the expansion of the alkali-silica gel when it comes in contact with
water [13].
Different admixtures of concrete mixes improve the durability,
rheology of fresh concrete, and mechanical properties of hardened
concrete [14]. The use of pozzolans as a measure to prevent ASR
had been studied extensively since the 1950s [15]. Mineral admix-
tures are finely divided siliceous materials that are added to con-
crete during mixing in relatively large amounts. Industrial by-
products are the primary source of mineral admixtures [16]. The
benefits of mineral admixtures are often associated with the prop-
erties of hardened cement paste; however, mineral admixtures
may also influence the properties of wet concrete: water demand,
heat of hydration, and reactivity [17].
Fly ash (FA) is a fine-grained solid material having a particle size
range of 0.2–200 lm. The range of particle size of any given FA
depends largely on the fineness of the pulverised coal and the type
of flue gas scrubbing systems [18]. The chemical composition of FA
is determined by the type of the mineral matter present in the coal
used. More than 85% of most FA consists of silica (SiO2), alumina
(Al2O3), iron oxide (Fe2O3), lime (CaO) and magnesia (MgO). The
chemical and mineralogical compositions as well as the physical
properties of fly ashes vary depending on the source of the coal
used in the thermal power plant, method of burning, combustion
equipment, ash collection methods, etc. [18]. Lenke and Malvar
[19] report that there are three characteristics of a fly ash that
determine its efficiency in preventing ASR: fineness, chemistry,
and mineralogy.
When fly ash is mixed with Portland cement and water, it gen-
erates a product similar to that formed by cement hydration but
having a denser microstructure that is less permeable [20]. Fly
ash in concrete reduces drying shrinkage [21], thus generates
fewer cracks which ensure greater resistance to deterioration. It
is generally accepted that FA, if appropriately used, can prevent
ASR caused expansion [22]. Fly ash has been shown to be effective
in reducing AAR expansion [23]. Almost all fly ashes can be used to
prevent damaging expansion as a result of alkali-silica reaction
provided they are used in sufficient quantity [24].
The decrease in AAR comes from the fact that fly ash reacts
chemically with and absorbs alkalis in the cement, thus making
them unavailable for reaction later with the reactive aggregate
[25]. The amount of fly ash required depends on the reactivity of
the aggregate, the quantity of alkalis contributed by the Portland
cement, and the composition of the fly ash [26]. The paper by Lim-
bachiya et al. presents the results of tests into the properties of
concrete mixes made of sand, coarse aggregates and recycled con-
crete aggregate, where a certain proportion of cement was
replaced with fly-ash. Researchers found that specimens with ash
additive had better mechanical characteristics compared to the
control specimen. The specimens were tested after 3, 7, 14, 28,
56, 91, and 365 days of curing. The authors claim that specimens
containing ash additive had a lower W/C ratio than specimens
without ash. A linear relationship between the compressive
strength and the rate of carbonation was detected. Higher resis-
tance to sulphate attack and thus better durability characteristics
of concrete was also observed [27].
Porosity is a very important parameter for the durability of con-
crete. Freeze–thaw resistance of concrete mainly depends on cap-
illary porosity and entrained air. These parameters are controllable
in concrete manufacturing process. There are four types of pores in
the pore system of concrete: gel pores; capillary pores of 5–50 lm
in size; macropores resulting from entrained air and macropores
resulting from insufficient compaction. Gel pores have a negative
effect on concrete strength. Capillary pores and bigger pores
reduce the strength of concrete [28]. It is generally known that
low W/C ratio and appropriate curing conditions are the key fac-
tors for producing freeze–thaw resistant concrete products [29–
32]. Asrara claims that amorphous silica dioxide provides corrosion
protection and increases the strength of concrete by reducing
porosity and participating in the building of CSH crystals through
the reaction with calcium hydroxide. The reaction outcomes are
the reduction of Ca(OH)2 content and increase of C–S–H content,
which improves the strength and durability of concrete [33].
The object of research is enhanced ASR resistant concrete mod-
ified with fly ash. To investigate the effect of fly ash on the ASR in
concrete containing aggregates contaminated with reactive parti-
cles. The following objectives were set to reach the aim: to analyze
the effect of fly ash on the properties in concrete and determine the
dependence between their amount, the change in speed and
expansion of the ultrasound pulse with aggregates contaminated
with reactive particles; To evaluate the effect of ASR process on
the structure and properties of concrete extending the duration
of the research from 14 to 56 days. The results of the research will
be used in designing ASR resistant reinforced concrete structures
and production of concrete with enhanced resistance to ASR basing
on the tests of the effect of fly ash on ASR in concrete containing
aggregates contaminated with reactive particles.
2. Materials and research methods
CEM I 42.5 R type Portland cement complying with LST EN 197-
1:2001 requirements was used in the tests. Characteristics and
chemical composition of Portland cement are presented in Tables
1 and 2. Chemical composition of fly ash is presented in Table 3.
0/4 fraction sand complying with LST EN 12620:2003 require-
ments was used as fine aggregate. Physical characteristics of sand
are presented in Table 4.
Characteristics of water used to prepare concrete mix: clean,
without any harmful deposits, which would prevent the normal
setting of concrete, i.e. potable water complying with EN
1008:2003 requirements. Polycarboxylate resin-based plasticizer,
pH value 4.5, solution density 1060 kg/m3, was added to the mix.
Superplasticizer was used to achieve the same flowability of the
concrete mix. Superplasticizer MC-3100 PowerFlow characteristics
are presented in Table 5.
Fly ash was used as cement replacement additive. The concrete
mix was prepared in accordance with the requirements of standard
EN 196-1:2016 [34]. 7 batches of concrete mixes were mechani-
cally produced under laboratory conditions for the tests. The
Table 1
Physical–mechanical properties of the cement.
Properties Portland cement CEM I 42.5 R
Specific surface area, cm2/g 3700
Particle density, kg/m3 3200
Bulk density, kg/m3 1200
Standard consistency paste, % 25.4
Initial setting time, min 140
Final setting time, min 190
Compressive strength after 7 days, MPa 28.9
Compressive strength after 28 days, MPa 54.6
 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609 601

Table 2
Chemical and mineral characteristics of the cement.

Chemical composition of cement, %

SiO2 Al2O3 Fe2O3 CaO K2O SO3 Na2O H2O MgO Other
20.76 6.12 3.37 63.50 1.00 0.8 0.3 – – 4.45

Table 3
Chemical and mineral characteristics of the fly ash.
28 days. After 28 days of curing in water of 20 ± 2 °C temperature,
Chemical composition Fly ash, % the density of the specimens was measured according to EN
SiO2 49.80 12390-7:2009 [35], the compressive strength was measured
Al2O3 19.10 according to EN 12390-3:2009/AC:2011 [36], the flexural strength
Fe2O3 7.03 was measured according to EN 12390-5:2009 [36], and ultrasonic
CaO 6.92
pulse velocity was measured according to EN 12504-4:2004 [37].
K2O 1.82
MgO 1.58
The total water absorption of the specimens was measured after
P2O5 1.41 soaking in water for 96 h. The specimens were soaked in water
SO3 1.02 of 20 ± 2 °C temperature and kept there until the constant mass
TiO2 1.00 was achieved. Specimens in the bath must be placed at 15 mm
Na2O 0.79
between specimens and the layer of water above the specimens
BaO 0.28
SrO 0.18 must be at least 20 mm. The constant mass was achieved when
MnO 0.06 the difference in weight every 24 h was <0.1%. Prior to weighting
ZrO2 0.05 the specimens were dried with a damp cloth to remove excessive
ZnO 0.02
water.
WO3 0.02
NiO 0.02
W/C ration in all mixes was the same, 0.47. The workability of
CuO 0.01 concrete mixes according to AAR-2 test methodology must range
Other 8.89 between 205 and 220 mm.
The particle size distribution of fly ash was measured with the
laser particle size analyzer Cilas 1090 LD. The particle size is mea-
sured in the range of 0.01–500 lm. The chemical analysis of fly ash
Table 4 was done by the X-ray fluorescence spectrometer Bruker X-ray S8
Physical properties of sand.
Tiger WD. Rh target X-ray tube was used, anode voltage up to
Aggregate Particle density, Bulk density, Water 60 kV, current I up to 130 mA. Pressed specimens were measured
kg/m3 kg/m3 absorption, % in helium atmosphere.
Sand 0/4 2631 1661 0.40 Phase analysis of fly ash was done by X-ray diffraction meter
SmartLab (Rigaku) with a rotating Cu anode X-ray generator tube.
The X-ray diffraction patterns were recorded in the angular range
Table 5 5–75° (2h), detector step 0.02°, detector movement speed 1°/min.
Superplasticizer MC-3100 PowerFlow characteristics. Database of crystal structures PDF-4+ (2016) was used for the
Characteristics Unit of Significance Notes analysis.
measurement The microstructure of concrete specimens and fly ash was
Density kg/dm3 1.06 ±0.02 kg/dm3 tested with the scanning electron microscopy (SEM) device SEM
Recommended dosage g/1 kg of cement 1–50 JEOL 7600F. Electron microscopy parameters: Power 10 kV and
Maximum chloride content % <0.10 20 kV, distance to specimen surface 7–10 mm. Characteristics of
Maximum alkali content % <2.0 the microstructure was identified by testing the specimen splitting
surface. The image was obtained by recording the signal of sec-
ondary electrons. Before testing the splitting surface was coated
with electrically conductive thin layer of gold by evaporating the
batches differed by the type of cement and fly ash content ranging gold electrode in the vacuum using the instrument QUOR-
from 0% to 65% by weight of cement (the binder was replaced by UMQ150R ES. The specimens of the tested materials were pho-
silica fume). Compositions of concrete mixes are presented in tographed by the digital camera Sony ILCE 5000.
Table 6. Concrete mixes were mechanically mixed under labora- The resistance of concrete specimens to ASR was tested in
tory conditions and 40  40  160 mm size specimens were accordance with the standardised methodology Rilem AAR-2.
formed in metal casting moulds. Specimens were removed from According to AAR-2 method the specimens (40  40  160 mm)
the moulds after 24 h of curing and soaked in 20 ± 2 °C water for cured in 80 °C water are further conditioned in 80 °C 1 M NaOH

Table 6
Concrete mix compositions, %.

Fly ash, % Cement, % Sand, % Water, % Fly ash, % W/C Plasticizer, % Consistency, mm
0 26.88 60.48 12.63 0.00 0.47 – 205
15 22.85 60.48 12.63 4.03 0.47 – 210
25 20.16 60.48 12.63 6.72 0.47 0.05 213
35 17.47 60.48 12.63 9.41 0.47 0.10 217
45 14.79 60.48 12.63 12.10 0.47 0.10 208
55 12.1 60.48 12.63 14.79 0.47 0.10 210
65 9.41 60.48 12.63 17.47 0.47 0.15 218
602 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609
solution for 56 days and afterwards their expansion is measured.
According to ASTM C 441 test method, the critical expansion limit
is 0.1%.
3. Analysis of test results
The X-ray structural analysis of fly ash (Fig. 1) revealed that
quartz (SiO2) Q was the prevailing mineral (55%). Mullite (Al2.34-
Si0.66) M was the second mineral by content (29%) present in fly
ash. Traces of calcium carbonates (CaCO3) C, calcium oxide (CaO)
L and diopside (CaMgSi2O6) D were also found at 3.7%, 4.9% and
7.4% respectively.
SEM images of the microstructure of fly ash powder are pre-
sented in Fig. 2. Regular spherical particles prevail in the image
of fly ash magnified 500 times (Fig. 2a). The average particle size
is 13 lm. The image magnified 3000 times (Fig. 2b) reveals the
same: the finest particles have the regular shape of small balls.
Fig. 3 illustrates the analysis results of the effect of fly ash on the
density of modified concrete. The tests carried out with modified
specimens revealed that replacement of cement with up to 55%
of fly ash increases the density, which is 2183 kg/m3 or 61 kg/m3
(2.79%) higher compared to the density of the control specimen.
However, the density reduces to 2179 kg/m3 in concrete specimens
modified with 65% of fly ash. The density become 4 kg/m3 lower
compared to specimens modified with 55% of fly ash.
Fig. 4 illustrates the results of compressive strength of concrete
modified with fly ash after 7 and 28 days of curing. The compres-
sive strength increases (2.35 MPa) compared to control specimen
and reaches 49.13 MPa in specimens modified with 15% of fly
ash. A similar growth of compressive strength is observed in spec-
imens modified with 25% of fly ash. After 7 days of curing the com-
pressive strength of these specimens was 51.98 MPa. The highest
compressive strength of 54.16 MPa was observed in specimens
modified with 35% of fly ash. It is a 15.78% increase compared to
the control specimen. Further increase of fly ash content in con-
crete mix up to 45% resulted in a slight drop of density down to
54.01 MPa. When cement is replaced with 55% and 65% of fly
ash, the compressive strength values go down to 52.99 MPa and
50.75 MPa respectively.
After 28 days of curing the compressive strength of control
specimens not modified with fly ash was 52.08 MPa. The highest
compressive strength value of 57.46 MPa was recorded in speci-
mens containing 35% of fly ash; the compressive strength of these
specimens was 10.33% higher compared to control specimens. The
12000
Relative intensity, a.u.
10000
8000
M
6000
4000
2000
15
Fig. 1. X-ray diffraction pattern of fly ash: Q – quartz (SiO2); M – mullite (Al2.34Si0.66); C – calcium carbonate (CaCO3); L – calcium oxide (CaO); D – diopside (CaMgSi2O6).
compressive strength of specimens containing 45% of fly ash was
56.92 MPa or 0.54 MPa lower compared to specimens containing
35% of fly ash. The tests revealed that with the increase of fly ash
content up to 55% and the highest tested content of 65%, after
28 days of curing the compressive strength reduced to 55.01 and
53.99 MPa respectively.
Fig. 5 illustrates the results of flexural strength of concrete mod-
ified with fly ash after 7 and 28 days of curing. The highest flexural
strength of 6.39 MPa was observed in specimens modified with
35% of fly ash. It is a 7.39% increase compared to the control spec-
imen. Further increase of fly ash content in concrete mix up to 45%
resulted in a slight drop of flexural strength down to 6.33 MPa.
When cement is replaced with 55% and 65% of fly ash, the flexural
strength values go down to 52.99 MPa and 50.75 MPa respectively.
The test results revealed that after 28 days of curing specimens
modified with 35% of fly ash had the highest flexural strength of
7.35 MPa and that value was 6.37% compared to the flexural
strength of control specimens. The flexural strength of specimens
containing 45% of fly ash was 7.34 MPa or 0.44 MPa lower com-
pared to specimens containing 35% of fly ash. The increase of fly
ash content up to 55% and the highest tested content of 65%, after
28 days of curing the flexural strength reduced to 7.31 and
7.28 MPa respectively.
Fig. 6 illustrates the change of ultrasonic pulse velocity in con-
crete modified with fly ash after 7 and 28 days of curing. In speci-
mens modified with 15% and 25% of fly ash, the ultrasonic pulse
velocity (UPV) after 7 days of curing increases 0.27% and 0.61%
up to 4108 and 4122 m/s respectively. When the binder is replaced
with 35% of fly ash, UPV increases up to 4137 m/s, and this value is
0.98% higher compared to UPV in control specimens. When fly ash
content is increased to 45%, UPV increases up to 4145 m/s or 1.17%
more. The highest UPV of 4151 m/s was recorded in specimens
containing 55% of fly ash, and this value is 1.32% higher compared
to UPV in control specimens. When fly ash content is increased to
65%, UPV drops down to 4147 m/s.
Ultrasonic pulse velocity tests were done with concrete speci-
mens modified with fly ash and cured for 28. Control specimens
not modified with mineral additives had the UPV 4244 m/s. When
15% and 25% of fly ash is added into concrete mix, the ultrasonic
pulse velocity (UPV) increases 0.21% and 0.57% up to 4253 and
4268 m/s respectively. When the binder is replaced with 35% of
fly ash, UPV increases up to 4277 m/s, and this value is 0.78%
higher compared to UPV in control specimens. The highest UPV
of 4291 m/s was recorded in specimens containing 45% of fly ash,
and this value is 1.11% higher compared to UPV in control speci-
Q
M
Q
M
M M
C D M L M
Q L Q Q
20 25 30 35 40 45
Diffraction angle 2 θ, degrees
 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609 603

Fig. 2. Microstructure (SEM) of fly ash: (a) magnification 500, (b) magnification 3000.

2250

y = -0.0382x2 + 4.7948x + 2029.1

2200 R² = 0.9775; R = 0.9887 2183 2179

2152 2156
Density, kg/m3

2150 2138

2100 2083

2050 2031

2000
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Amount of fly ash mineral additive, %

Fig. 3. Relationship between density and fly ash content in concrete.

Compressive strength after 7 days curing, MPa

Compressive strength after 28 days curing, MPa
60
y = -0.0033x2 + 0.2507x + 51.552 57.5
58 56.9
Compressive strength, MPa

R² = 0.8212; R = 0.9062
56 54.9 55.0
53.8 54.0
54
52.1 54.2 54.0
52 53.0
52.0
50 y= -0.0043x2 + 0.3596x + 46.056
50.8
R² = 0.9181; R = 0.9582
48 49.1
46.8
46
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Amount of fly ash mineral additive, %
Fig. 4. Relationship between the compressive strength and fly ash content after 7 and 28 days of curing.
604 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609

Flexural strength after 7 days curing, MPa Flexural strength after 28 days curing, MPa

8
y = -0.0002x2 + 0.018x + 6.8643
R² = 0.8984; R = 0.9478 7.4 7.3
7.5 7.3 7.3
7.2
Flexural strength, MPa 7.0
6.9
7

6.4 6.3
6.5 6.3 6.3 6.3
6.2
6.0
6
y = -0.0002x2 + 0.0189x + 5.9434
5.5 R² = 0.9552; R = 0.9773

5
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Amount of fly ash mineral additive, %

Fig. 5. Relationship between the flexural strength of concrete and fly ash content after 7 and 28 days of curing.

Ultrasonic pulse propagation velocity after 7 days curing, m/s

Ultrasonic pulse propagation velocity after 28 days curing, m/s
Ultrasonic pulse propagation velocity, m/s

4350
y = -0.012x2 + 1.4946x + 4240
R² = 0.924; R = 0.9612 4291 4287 4283
4300 4277
4268
4253
4244
4250

4200

4145 4151 4147

4150
4137
4122
4108
4097
4100 y = -0.0098x2 + 1.5289x + 4093
R² = 0.9628; R = 0.9812
4050
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Amount of fly ash mineral additive, %

Fig. 6. Relationship between the ultrasonic pulse propagation velocity and fly ash content after 7 and 28 days of curing.

mens. Further increase in fly ash content in concrete mix leads to explained by overdose of fly ash. Reduced cement content does
UPV decrease. When fly ash content is increased to 55% and 65% not provide a strong connection between the aggregate and the
by weight of cement, the ultrasonic pulse velocity drops to 4287 cement matrix.
and 4283 m/s respectively. The findings of testing the expansion of concrete modified with
Specimens of concrete modified with fly ash have a lower water fly ash are presented in Fig. 8. Expansion results were obtained
absorption rate. The test findings are presented in Fig. 7. Water after testing concrete specimens modified with fly ash additive
absorption rate decreased to 3.93% in specimens modified with after 56 days of curing. The test results revealed that the critical
15% of fly ash. Further increase of fly ash content by 10% incre- expansion limit of 0.1% was exceeded only when 15% of fly ash
ments up to 55% resulted in a stable decrease of water absorption was used. The recorded expansion value was 0.105%. The expan-
rate to 3.85%, 3.81%, 3.75% and 3.71% respectively. When the min- sion of specimens containing 25% of fly ash was 0.097%, and in
eral additive content is increased to the maximum 65%, water specimens modified with up to 35% and 45% of fly ash the expan-
absorption rate increases (3.73%), which means that fly ash content sion values were 0.091% and 0.086% respectively. Another increase
is excessive in terms of water absorption. of fly ash content by 10% up to the 55% reduces the expansion even
Physical and mechanical properties increase with increasing more down to 0.08%. When the concrete mix is modified with the
fly ash amount. The fly ash particles, due to their fineness, fill maximum amount of fly ash added at 65% by weight of cement, the
the smallest gaps in the concrete structure. Increasing the specimen expansion values remain almost the same since day 35 of
amount of fly ash in concrete density, ultrasonic pulse velocity, the test (0.067% expansion) till the end of the test (0.069%
compressive and flexural strength begin to deteriorate, which is expansion).
 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609 605

4.10

4.05
4.0
4.00

Water absorption, %
3.95
3.9

3.90
3.9
3.85 3.8
3.80
3.8
3.75
3.7
3.7
3.70

3.65
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Amount of fly ash mineral additive, %

Fig. 7. Relationship between water absorption rate and fly ash content in concrete.

0% 15% 25% 35% 45% 55% 65%

0.120

0.100

0.080
Expansion, %

0.060

0.040

0.020

0.000
0 7 14 21 28 35 42 49 56
Days

Fig. 8. Relationship between the expansion of with fly ash modified concrete specimens conditioned in 1 M NaOH solution of 80 °C for 56 days and the amount of mineral
additives.

Experimental modification of concrete mix with different
amounts of fly ash revealed that the limit content of fly ash addi-
tion is 45% because after 56 days of testing the average expansion
of concrete was 0.086%. This value did not exceed the permissible
expansion limits after conditioning the specimens in 1 M NaOH
solution at 80 °C temperature for 56 days.
X-ray diffraction analysis was done to more precise evaluation
of the effect of fly ash on ASR resistance of concrete. The mineral
structure of unmodified control specimen and a specimen
modified with the maximum 65% amount of fly ash was
investigated.
Fig. 9 illustrates the structure of unmodified concrete (control
specimen). Concrete without mineral additives is made of quartz
(SiO2) present at 47.3%, calcium carbonate (CaCO3) present at
38%, and anorthite (CaAl2Si2O8) present at 9.8%. The remaining con-
tent is made of the following minerals: microcline (K(AlSi3)O8), albite
(Na0.986(Al1.005Si2.995O8)), dolomite (CaMg(CO3)2), illite ((K,H3O)
Al2Si3AlO10(OH)2), clinochlore ((Mg, Al, Fe)6(Si,Al)4O10(OH)8).
Fig. 10 illustrates the structure of concrete without mineral
admixtures examined by the scanning electron microscope (SEM).
Layers of alkaline gel are visible around the aggregate in in ASR
affected concrete without mineral additives. These layers of gel
absorbed water and started expanding thus causing the develop-
ment of cracks in the cement matrix. A gap is also visible between
the aggregate and the gel, a product of alkaline silicate reaction.
The alkaline gel image magnified 5000 and 10,000 times reveals
the microstructure of the gel very similar to that shown in Fig. 2.
ASR caused changes in concrete microstructure deteriorate physi-
cal and mechanical properties of hardened cement paste due to
cracks, damage and scaling developing on the surface of concrete
products during their use.
Tests with specimens of concrete modified with 65% of fly ash
were done to evaluate the effect of the maximum of mineral addi-
tive. Fig. 11 illustrates the results of X-ray diffraction analysis.
X-ray diffraction images of specimens containing 65% of fly ash
and cured in 80 °C 1 M NaOH solution for 56 days are very similar
to the images of specimens modified with 45% of fly ash. The inten-
sity of peaks and the presence of elements is very similar, but
quantitative distribution of the elements differs: quartz (SiO2) –
50.4%, calcium carbonate (CaCO3) – 25.1%, anorthite (CaAl2Si2O8)
– 13.5%, dolomite (CaMg(CO3)2) – 10.2%. The remaining content
is made of the following minerals: albite (Na0.986(Al1.005Si2.995O8)),
microcline (K(AlSi3)O8), illite ((K,H3O)Al2Si3AlO10(OH)2), and clino-
chlore ((Mg,Al,Fe)6(S,Al)4O10(OH)8).
606 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609

45000
Q
40000
35000

Realative intensity, a.u

30000
25000
20000
C
15000 Q

10000 A Q
Q Q Q
C
Q C Q C C
5000 C C

0
20 25 30 35 40 45 50
Diffraction angle 2 θ, degrees

Fig. 9. X-ray diffraction image of concrete without mineral admixtures conditioned in 1 M NaOH solution of 80 °C for 56 days: Q – quartz (SiO2), C – calcium carbonate
(CaCO3), A – anorthite (CaAl2Si2O8).

Fig. 10. Microstructure of concrete without mineral admixtures conditioned in 1 M NaOH solution of 80 °C for 56 days.

The following difference were observed from the comparison of
concrete modified with 65% of fly ash and concrete without min-
eral additives: modified concrete has a 3.1% higher content of
quartz (SiO2), 12.9% lower content of calcite (CaCO3), 3.7% higher
content of anorthite (CaAl2Si2O8), and also contains 10.2% of dolo-
mite (CaMg(CO3)2), which is present in very small amount in con-
crete without mineral additives.
Fig. 12 illustrates the SEM images of the microstructure of spec-
imens containing the maximum amount of fly ash and conditioned
in 1 M NaOH solution at 80 °C for 56 days.
The contact zone between the aggregate and the binding mate-
rial looks strong in the microstructure of concrete modified with
65% of fly ash: there are no gaps or signs of splitting; the cement
matrix does not have any cracks or damages, which are character-
istic of ASR affected surfaces. The image presented in Fig. 13 shows
spherical particles of fly ash visible in hardened cement paste.
The analysis of concrete microstructure revealed that fly ash
particles are covered with amorphous SiO2 and alkali reaction
product. Fly ash contains 49.8% of amorphous SiO2, which reacts
with NaOH and KOH present in the cement much faster that active
silica present in the aggregates. This reaction restricts the forma-
tion of alkali-silica gel in the contact zone between the aggregates
and the binding material and such concrete becomes ASR resistant.
Coarse aggregate affected by ASR causes a much bigger expan-
sion, i.e. it creates stronger internal stresses compared to the fine
aggregate. It is apparent that very fine fly ash particles, the particle
size of which is similar to that of cement, create very weak local
expansion during the formation of alkaline gel. Relatively low
 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609 607

70000 Q

Relative intensity, a.u

60000

50000

40000

30000

20000 Q
C
D Q
10000 A Q C
AC C Q D Q C Q C C D
0
20 25 30 35 40 45 50
Diffraction angle 2 θ, degrees
Fig. 11. X-ray image of concrete modified with 65% of fly ash conditioned in 1 M NaOH solution of 80 °C for 56 days: Q – quartz (SiO2), C – calcium carbonate (CaCO3), A –
anorthite (CaAl2Si2O8).

Fig. 12. Microstructure of concrete modified with 65% fly ash conditioned in 1 M NaOH solution of 80 °C for 56 days.

Fig. 13. Particles of fly ash in hardened cement paste after expansion tests of conditioning in 1 M NaOH solution of 80 °C for 56 days.

internal stresses do not exceed the strength of concrete and do not
cause concrete damages.
Fig. 14 illustrates the change of UPV in concrete modified with
fly ash admixture after 28 days curing and conditioning the speci-
mens in 1 M NaOH solution at 80 °C temperature for 56 days.
Ultrasonic pulse velocity decreased in concrete tested for ASR
effects, however the change differs depending on the fly ash con-
tent. The change in specimens without mineral admixtures was
8.3%, whereas in specimens modified with 45% of fly ash the
change of UPV dropped to 3.1%. In specimens with the maximum
65% content of fly ash the change was only 2%. The change of
UPV in specimens cured in water for 28 days and conditioned in
1 M NaOH solution at 80 °C for 56 days for ASR tests is directly
related to the amount of the mineral additive in concrete mix.
The change in UPV reduces with higher additive content.
To evaluate the effect of fly ash on the expansion of concrete, a
relationship between fly ash content, the change of ultrasonic
pulse velocity after 28 days of curing in water and after ASR
testing (DVUIG), and the expansion rate after conditioning the
specimens in 1 M NaOH solution at 80 °C for 56 days was deter-
mined (Fig. 15).
The relationship between fly ash content in concrete mix and
the change in ultrasonic pulse velocity in hardened cement paste
specimens cured in water for 28 days and conditioned in 1 M
608 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609

Fig. 14. Relationship between the change of ultrasonic pulse velocity and fly ash content.

Fig. 15. Relationships between the expansion of concrete after conditioning in 1 M NaOH solution of 80 °C for 56 days, the amount of fly ash and the change in ultrasonic
pulse velocity.

NaOH solution at 80 °C for 56 days for expansion tests was 4. Conclusions

obtained. The expected expansion of specimens made of concrete
mix containing 60% of fly ash and conditioned in 1 M NaOH solu-
tion at 80 °C for 56 days is 0.08–0.085% at the change of UPV of
5%. This expansion rate does not exceed the permissible expansion
limit value of 0.1% after conditioning in 1 M NaOH solution at 80 °C
for 56 days and such concrete is ASR resistant.
1. It was found that particles of fly ash mainly have a regular
spherical shape, the average particle size is 13 lm. X-ray
diffraction microscopy analysis revealed that fly ash mainly
consists of quartz (SiO2) amounting to 55%, and mullite (Al2.34-
Si0.66) amounting to 29%.
 D. Nagrockienė, A. Rutkauskas / Construction and Building Materials 201 (2019) 599–609
2. The results of compressive strength tests with modified con-
crete mixtures revealed that in specimens where up to 65% of
cement was replaced with fly ash the compressive strength
increased by 7.83% after 7 days of curing and 3.54% after
28 days of curing. The best effect in compressive strength
increase is observed when 35% of cement in concrete mixture
is replaced with fly ash. The compressive strength of concrete
increased 13.6% after 7 days of curing and 9.37% after 28 days
of curing.
3. Fly ash added to concrete mix at 65% reduces the expansion of
concrete specimens and such concrete has better ASR resistance
properties. Control specimens containing 0% of fly ash had the
highest expansion of 0.113. The lowest expansion of 0.069
was observed in specimens containing 65% of fly ash.
4. Concrete, where 65% of cement is replaced by fly ash, was found
to have higher density, ultrasonic pulse velocity, compressive
and flexural strength, lower water absorption rate and expan-
sion. Subsequently, ASR resistance of such concrete is improved.
5. The analysis of concrete microstructure revealed that fly ash
particles are covered with amorphous SiO2 and alkali reaction
product. Fly ash contains 49.8% of amorphous SiO2, which reacts
with NaOH and KOH present in the cement much faster that
active silica present in the aggregates. This reaction restricts
the formation of alkali-silica gel in the contact zone between
the aggregates and the binding material and such concrete
becomes ASR resistant.
6. The obtained relationship between the fly ash content in con-
crete mix, the change of ultrasonic pulse velocity and expansion
of the specimen is used to evaluate the ASR effect on concrete.
7. The tests revealed that concrete modified with fly ash has better
durability and ASR resistance characteristics and can be used in
construction works.
Conflict of interest
None.
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Džigita Nagrockienė Prof. at the Department of Building Materials and Fire Safety,
Vilnius Gediminas Technical University (VGTU). PhD (2003). Research interests:
concrete durability, concretes with superplasticizers, frost resistance of concrete,
concrete with additives, materials science, concrete technology, natural zeolites and
fly ash in concrete.
Aurimas Rutkauskas PhD at the Department of Building Materials and Fire Safety,
Vilnius Gediminas Technical University (VGTU). Research interests: concrete alka-
line corrosion, concrete with additives, mineral additives, concrete properties,
reactive concrete aggregate.