Construction and Building Materials 36 (2012) 838844

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Construction and Building Materials

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Properties of concrete incorporating nano-silica

A.M. Said a,, M.S. Zeidan a, M.T. Bassuoni b, Y. Tian a
a
Department of Civil and Environmental Engineering, University of Nevada, Las Vegas, USA
b
Department of Civil Engineering, University of Manitoba, Winnipeg, Canada

h i g h l i g h t s

" Colloidal nano-silica was studied in concrete with and without y ash.
" Two dosage levels of nano-silica in concrete mixtures were evaluated.
" Adding nano-silica enhanced the mechanical and micro-structural properties of concrete.
" Nano-SiO2 enhanced properties through pozzolanic reaction and ller effect.

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

Article history: This study investigated the effect of colloidal nano-silica on concrete incorporating single (ordinary
Received 21 July 2011 cement) and binary (ordinary cement + Class F y ash) binders. In addition to the mechanical properties,
Received in revised form 13 May 2012 the experimental program included tests for adiabatic temperature, rapid chloride ion permeability, mer-
Accepted 4 June 2012
cury intrusion porosimetry, thermogravimetry and backscattered scanning electron microscopy in order
Available online 15 July 2012
to link macro- and micro-scale trends. Signicant improvement was observed in mixtures incorporating
nano-silica in terms of reactivity, strength development, renement of pore structure and densication of
Keywords:
interfacial transition zone. This improvement can be mainly attributed to the large surface area of nano-
Nano-silica
Fly ash
silica particles, which has pozzolanic and ller effects on the cementitious matrix. Micro-structural and
Durability thermal analyses indicated that the contribution of pozzolanic and ller effects to the pore structure
Pozzolanic effect renement depended on the dosage of nano-silica.
Filler effect 2012 Elsevier Ltd. All rights reserved.
Reactivity

1. Introduction
Nanotechnology has been dened by Drexler et al. [1] as the
control of the structure of matter based on molecule-by-molecule
control of products and by-products. Nanotechnology can be
considered as the most modern aspect in the elds of science and
technology. Because nanotechnology has great market potential
and economical impact, the need for research and exploration in
this eld and of its applications has been growing signicantly dur-
ing the last few decades. The aim of this research is to gain better
understanding of the behavior of materials on the nano-scale level
as well as determine how to improve the microstructure of cemen-
titious materials.
Concrete, which is known to be the most used manmade mate-
rial, is primarily based on the cement industry; in the last few
years, the total annual worldwide production of concrete exceeded
Corresponding author. Address: Civil and Environmental Engineering Depart-
ment, University of Nevada, Las Vegas, 4505 S. Maryland Pkwy, Las Vegas, NV
89154-4014, USA. Tel.: +1 702 895 2722; fax: +1 702 895 3936.
E-mail address: aly.said@unlv.edu (A.M. Said).
2600 million tons [2]. The cement industry is considered to be one
of the most energy consuming industries, with a high rate of car-
bon dioxide (CO2) emissions. Every year, it is responsible for
approximately 5% of the global manmade CO2 emissions [3]; 50%
of these emissions are caused by chemical manufacturing pro-
cesses and 40% are due to burning fuel. Extensive research efforts
have been directed to reducing the effect of the cement industry
on greenhouse gases either by improving the efciency of the
cement manufacturing process [4,5] or by using supplementary
cementitious materials (SCMs), which partially replace ordinary
cement [6]. Various SCMs have been investigated, including y
ash, ground granulated blast furnace slag, natural pozzolans, and
silica fume. Recent studies [7] have indicated that the use of new
technologies may lead to industrial breakthroughs for the manu-
facture of SCMs. It is believed that nanotechnology is one of the
most promising research elds that may signicantly improve
the mixture design, as well as the performance and production of
cement-based materials.
Fly ash, a by-product of coal consumption, is considered to be
one of the most used SCMs alternatives to partially replace cement
in concrete because it is cost efcient and widely available.

0950-0618/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.06.044
 A.M. Said et al. / Construction and Building Materials 36 (2012) 838844
Furthermore, y ash is much more environmentally friendly than
cement [8]. Therefore, US Green Building Council (USGBC) consid-
ers using y ash in concrete as a contributing factor to earn points
in the Leadership in Energy and Environmental Design (LEED)
program. In addition to its economical and environmental benets,
cement blended with y ash improves durability properties of con-
crete [9]. For example, Alasali and Malhotra [10] showed that bin-
ary binders (ordinary cement and y ash) signicantly reduce the
expansion in mortar/concrete due to alkali silica reactivity (ASR).
Hence, several transportation agencies include in its specication
for concrete mixtures a minimum amount of y ash to prevent/
mitigate the effect of ASR [11]. The main concern about y ash con-
crete, particularly that containing Class F y ash, has been its slow
rate of strength development compared to normal concrete
[12,13]. Numerous studies have been conducted to explore differ-
ent solutions for this issue, but until this stage, concrete compris-
ing Class F y ash is not suitable for many applications where
early strength is required, such as repairs and rapid construction.
Experimental results [14,15] indicated that the performance of
concrete is generally improved by adding nano-silica. At rst, it
was believed that the improvement in concrete performance due
to the addition of nano-silica is attributed to its ller effect and its
pozzolanic reaction. Recently, however, it has been reported that
the small particle size of nano-silica provides a larger surface area,
which speeds up the rate of cement hydration and pozzolanic reac-
tions [16]. This may be supported by the fact that other nano-mate-
rials, such as titanium oxide (TiO2), accelerate the hydration reaction
of the main clinker phases, such as tricalcium silicate (C3S) [17].
Nano-silica is available in two main forms: compacted dry
grains and colloidal suspension. Dry nano-silica requires a special
preparation procedure before mixing in order to insure the thor-
ough dispersion of the nano-particles in the mixing water, or other
liquid admixtures, so that it can be well distributed in the concrete
mixture. On the other hand, colloidal nano-silica, which is manu-
factured as a suspension stabilized by a dispersive agent, is a
ready-to-use form of nano-silica. Previous work [18] indicated that
better behavior was achieved when colloidal nano-silica was
added to mortar mixtures, compared to dry grained nano-silica.
This was attributed to the better dispersion of colloidal nano-silica
with highly reduced agglomeration, in contrast to the dry form. In
this study, the effect of incorporating colloidal nano-silica in con-
crete prepared with single (OPC) and binary (OPC + Class F y
ash) binders is investigated. The inuence of the nano-silica dosage
on the mechanical and durability properties of concrete was eval-
uated in the light of micro-structural and thermal analyses.
2. Experimental program
2.1. Materials
The cement used was Type II/VI Portland cement, which meets ASTM C 150
(Standard Specication for Portland Cement). The main composition and properties
of the cement used are presented in Table 1. Six mixtures were prepared and Class F
y ash, whose composition and properties are also shown in Table 1, was used in
three mixtures. The nano-silica used was in a colloidal form of an aqueous solution
with 50% SiO2 content. The mean particle size of the nano-silica was 35 nm, and the
specic gravity and pH were 1.36 and 9.5, respectively. In order to achieve a con-
stant workability level, a high-range water reducing admixture (HRWRA), based
on polycarboxylic acid and complying with ASTM C 494 (Standard Specication
for Chemical Admixtures for Concrete) Type F, was used at different dosages for
all mixtures. Well-graded natural gravel was used as coarse aggregate. The specic
gravity, absorption, and dry rodded unit weight were 2.79%, 0.60% and 1634 kg/m3,
respectively. The ne aggregate was natural sand with a specic gravity, absorption,
and neness modulus of 2.78%, 0.80% and 3.0%, respectively.
2.2. Procedures
Constituent materials were mixed in a mechanical mixer according to ASTM C
192 (Standard Practice for Making and Curing Concrete Test Specimens in the Lab-
oratory). In this study, three mixtures included only Type II/V cement as a binder
839
Table 1
Properties of cement and y ash.
Type II/VI Portland Cement Class F y ash
SiO2 (%) 20.64 58.25
Al2O3 (%) 3.40 16.60
Fe2O3 (%) 3.40 4.63
CaO (%) 63.5 10.23
MgO (%) 4.70
SO3 (%) 2.40 0.84
Na2O (%) 0.46
Loss on ignition 1.20 1.52
Specic gravity 3.15 2.35
Fineness (m2/kg) 376 290
(single binder, Group A), while the other three mixtures had 30% of the cement re-
placed by Class F y ash (binary binder, Group B). The cementitious materials con-
tent (390 kg/m3) and the water-to-cementitious material ratio (0.40) were kept
constant for all the mixtures. Variable dosages of nano-silica were used (0%, 3%,
and 6% by total mass of cementitious materials) in each of the two groups of mix-
tures (A and B). The amount of mixing water was adjusted for each mixture to ac-
count for the water content of the nano-silica solution. Also, different amounts of
HRWRA were used for different ratios of nano-silica in order to maintain a slump
between 50 and 100 mm. Higher amounts of HRWRA were needed with the larger
dosages of nano-silica. Table 2 shows the different proportions for the six mixtures.
2.3. Testing methods
Immediately after mixing, 100  200 mm concrete cylinders were prepared and
thermocouples were inserted at mid-height of the cylinders in order to measure the
temperature of the mixtures during hardening according to ASTM C 1064 (Standard
Test Method for Temperature of Freshly Mixed Portland Cement Concrete). For each
mixture, two cylinders were used to measure the change in temperature and their
average temperature was recorded. The molds were covered and sealed to prevent
moisture loss during the test, and were kept in room temperature (23 2 C). The
adiabatic temperature of concrete was recorded every 2 min using a data logger
for 30 h after mixing.
The compressive strength at different curing ages (3, 7, 28, 90, and 365 days)
and the splitting tensile strength at 28 days were evaluated for the six mixtures
using 100  200 mm cylinders according to ASTM C 39 (Standard Test Method for
Compressive Strength of Cylindrical Concrete Specimens) and ASTM C 496 (Stan-
dard Test Method for Splitting Tensile Strength of Cylindrical Concrete Specimens),
respectively. After 24 h of mixing, the cylinders were unmolded and placed in a
standard curing room (maintained at a temperature of 23 2 C and with a relative
humidity of more than 95%) until they were ready for testing.
At 28 days, the rapid chloride ion permeability test (RCPT) was conducted for all
the mixtures to evaluate the resistance of the mixtures to the penetrability of
aggressive ions. The test procedures were conducted according to ASTM C 1202
(Standard Test Method for Electrical Indication of Concretes Ability to Resist Chlo-
ride Ion Penetration). In order to measure the physical penetration depth of chloride
ions, the specimens were axially split immediately after testing. Then, the inner face
of each half specimen was sprayed with a silver nitrate solution, which forms a
white precipitate of silver chloride in approximately 15 min. The average depth
of the white precipitation was determined by measuring the depth at ve different
positions along the diameter of each half specimen. This average depth is consid-
ered to be an indication of the physical ingress of the chloride ions [19].
The mercury intrusion porosimetry (MIP) technique was used to assess pore
size distribution and the total porosity of the mixtures. After 28 days, small pea-
sized chunks taken from at least two concrete cylinders were used as test samples
for MIP [20]. These chunks were around 310 mm in size, and were carefully se-
lected so that large aggregates were not included. The samples were oven dried
for 72 h at a temperature of 60 2 C; then, until the time of testing, they were kept
in a desiccator containing silica gel. This method of drying using a lower temper-
ature for a longer period was adopted to avoid the formation of micro-cracks,
which may occur at high temperatures. In this study, the contact angle and the sur-
face tension of mercury were taken as 130 and 485 dynes/cm, respectively [21,22].
The effect of nano-silica on the hydration and pozzolanic reactions was assessed
by determining the quantity of portlandite (calcium hydroxide) in the matrix after
28 days. Thermogravimetry (TG) at a heating rate of 10 C/min was used for this
purpose. After 28 days, chunks were obtained from crushed concrete cylinders.
For the TG tests, the chunks were ground to powder, passing a #200 sieve
(75 lm). The content of portlandite was calculated by determining the drop in
the percentage mass of TG curves at a temperature range of 420450 C (chemically
bound water in portlandite) and multiplying it by 4.11 (ratio of the molecular mass
of portlandite to that of water). To complement the ndings of the MIP and TG tests,
backscattered scanning electron microscopy (BSEM) was used on polished thin sec-
tions, which were prepared by cutting 25  50 mm specimens from the concrete
 840 A.M. Said et al. / Construction and Building Materials 36 (2012) 838844

Table 2
Proportions of mixtures per cubic meter of concrete.

Mixture Cement (kg) Fly ash (kg) Colloidal nano-SiO2 (kg) Water* (kg) HRWRA (mL/100 kg of binder) Coarse aggregate (kg) Fine aggregate (kg)
A-0 390 156 326 1184 789
A-1 390 23.4 144.3 457 1175 783
A-2 390 46.8 132.6 914 1162 774
B-0 273 117 156 261 1163 775
B-1 273 117 23.4 144.3 326 1154 769
B-2 273 117 46.8 132.6 653 1143 762
*
The content of mixing water was adjusted by the amount of water in the nano-silica solution.

29 140
A-0 (0% N.S.)
28 120
A-1 (3% N.S.)

Compressive Strength (MPa)

27
100
A-2 (6% N.S.)
Temperature (C)

26
80
25
60
24 A-0 (0% N.S.)
A-1 (3% N.S.)
40
23 A-2 (6% N.S.)
B-0 (0% N.S.)
20 B-1 (3% N.S.)
22
B-2 (6% N.S.)
0
21 0 50 100 150 200 250 300 350
0 5 10 15 20 25 30 35
* Note N.S.: Nano Silica Age (Days)
Time (hrs)
Fig. 3. Compressive strength versus curing time.
Fig. 1. Adiabatic temperature test results for Group A mixtures.

29 either for Group A (without y ash) or for Group B (with 30% y

B-0 (0% N.S.) ash) with the exception of mixture A-2. For example, comparing
28
mixtures B-1 and B-2 to mixture B-0 (Fig. 2), the peak tempera-
B-1 (3% N.S.)
27 tures were about 20% higher and were reached in a shorter time
B-2 (6% N.S.) period (4 h earlier).
Temperature (C)

26
This increase in the peak temperature, within 15 h after mixing,
25
indicates acceleration in the rate of hydration due the presence of
nano-silica. This increase cannot be ascribed to the pozzolanic
24 effect of nano-silica, as the pozzolanic reaction usually takes place
later after adequate formation of portlandite [23]. Hence, it may be
23
attributed to the very high surface area of nano-silica particles
22
(average particle size of 35 nm and a specic surface of 80 m2/g),
which act as nucleation sites for the hydration reactions. These re-
21 sults indicate that the role of nano-silica is not limited to pozzola-
0 5 10 15 20 25 30 35
nic or ller effects, but it also speeds up the kinetics of hydration
Time (hrs)
due to its ultrane nature.
Fig. 2. Adiabatic temperature test results for Group B mixtures.
3.2. Mechanical properties

The average compressive strength of the specimens at different

cylinders after 28 days. Subsequently, they were impregnated by a low-viscosity curing ages and the average splitting tensile strength at 28 days are
epoxy resin under pressure and polished by using diamond surface-grinding
equipment.
8
7
Tensile Strength (MPa)

3. Results and discussion

6

3.1. Adiabatic temperature 5

4

The temperature recorded over 30 h was plotted against time, 3

as shown in Figs. 1 and 2. For all mixtures, the temperature in- 2

creased just after mixing within the acceleration period and the 1

setting period until a peak was reached. The increase in tempera- 0

A-0 A-1 A-2 B-0 B-1 B-2
ture was followed by a decrease during the deceleration period un-
Mixture
til a relatively constant temperature was recorded. Generally, the
peak temperature was higher for mixtures containing nano-silica Fig. 4. Splitting tensile strength of all the mixtures at 28 days.
 A.M. Said et al. / Construction and Building Materials 36 (2012) 838844 841

Table 3
Early age compressive strength of concrete mixtures.

Mixture Compressive strength (MPa)

3-days 7-days
A-0 33 49
A-1 36 51
A-2 39 58
B-0 27 39
B-1 28 40
B-2 31 44

shown in Figs. 3 and 4, respectively (three replicates were used for

each test). For concrete with or without y ash, the results gener-
ally indicate that the compressive and tensile strengths markedly
increased with the addition of nano-silica. This was statistically
supported by analysis of variance (ANOVA), at a signicance level
a = 0.05. For example, ANOVA for the compressive strength results
at 7 and 28 days showed that the increase in the dosage of nano-
silica from 0% to 6% had F values of 32.38 and 18.54, respectively
which are larger than the corresponding critical F value of 3.89.
According to Montgomery [24], exceeding the critical value of an
F-distribution density function reects that the tested variable sig- Fig. 5. Physical penetration (white line) of chloride ions for Specimens B-0 and B-2.
nicantly affects the mean of the results.
For specimens from Groups A and B, the average early age (3
and 7 days) strength increased by about 18% and 14%, respectively
with nano-silica additions (Table 3). At 28 days, the increase in 0.05

strength was further improved up to 36%. It was also observed that 0.045 A-0 (0% N.S.)
Cumulative Intrusion (ml/g)

the addition of 3% and 6% nano-silica to mixtures containing 30% 0.04

y ash (Mixtures B-1 and B-2, respectively) led to compressive 0.035
A-1 (3% N.S.)

strength that matched or exceeded the strength of the control mix- 0.03 A-2 (6% N.S.)
ture without y ash (A-0) at or before 28 days (Fig. 3). Compara- 0.025
tively, the mixture containing y ash without nano-silica (B-0)
0.02
matched the compressive strength of the control mixture (A-0) at
0.015
approximately 90 days. This suggests that the low rate of strength
0.01
development for concrete incorporating Class F y ash can be con-
0.005
trolled by the addition of nano-silica. For long-term strength, the
mixtures containing nano-silica continued to gain strength with 0
0.001 0.01 0.1 1 10 100 1000
a relatively high rate after 28 days. In general, the improvement
Pore Size (m)
in the mechanical properties for the mixtures incorporating
nano-silica can be ascribed to the pozzolanic and ller effects of Fig. 6. Pore size distribution for Group A mixtures.
nano-silica, as shown by the thermal and micro-structural
analyses, which are discussed later in the text.

3.3. Rapid chloride permeability test (RCPT)

are listed in Table 4, which also shows qualitative evaluation for the
In the rapid chloride ion permeability test (ASTM C 1202), penetrability of the chloride ions, as specied by ASTM C 1202. Con-
charges passing through concrete disc specimens within 6 h were siderable improvement was noted with the addition of nano-silica.
recorded, and the depth of chloride penetration was physically mea- ANOVA, at a signicance level a = 0.05, for the results of passing
sured after testing by the colorimetric method [19]. The average charges and penetration depths showed that the variation of the
passing charges and penetration depths for two replicate specimens nano-silica dosage from 0% to 6% had F values of 189.50 and
108.23, respectively, which are more than the critical F value of
3.89. This means that the tested variable signicantly affects the
mean of the results.
Table 4 For Group A mixtures, the penetrability class changed from
Rapid chloride ion permeability test (RCPT) results. low to very low with the addition of nano-silica (Table 4).
Fig. 5 shows an example of the physical penetration of chloride
Mixture Passing charge Penetrability class Average penetration
(Coulombs) (ASTM C 1202) depth (mm) ions in two specimens from Group B, with the penetration depth
indicated by the white line. In this gure, marked reduction of
A-0 1837 Low 10.2
A-1 939 Very low 3.1 the penetration depth can be visually observed for the specimen
A-2 294 Very low 4.6 with 6% nano-silica (B-2), compared to the specimen without
B-0 958 Very low 8.1 nano-silica (B-0). In most cases, as the dosage of nano-silica in-
B-1 491 Very low 4.1 creased, the passing charge and the physical penetration depth de-
B-2 357 Very low 3.3
creased. This indicates that adding small dosages of nano-silica had
 842 A.M. Said et al. / Construction and Building Materials 36 (2012) 838844

0.065
0.06 B-0 (0% N.S.)

0.055 B-1 (3% N.S.)

Cumulative Intrusion (ml/g)

0.05
B-2 (6% N.S.)
0.045
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
0.001 0.01 0.1 1 10 100 1000
m)
Pore Size (

Fig. 7. Pore size distribution for Group B mixtures.

Table 5
Mercury intrusion porosimetry (MIP) test results.

Mixture Apparent total Threshold pore Percentage of small

porosity (%) diameter (lm) pores (<0.1 lm) (%)
A-0 10.13 0.10 69.31
A-1 6.91 0.075 75.39
A-2 6.44 0.060 72.16
B-0 12.56 0.144 73.41
B-1 9.30 0.092 79.69
B-2 8.21 0.075 77.34

6%

5%

4%
Fig. 9. Image from back scattered electron microscopy (BSEM) for: (a) Specimen
Mass (%)

3% A-0 and (b) Specimen A-2.

2%

1% addition of nano-silica (Table 5). Furthermore, the threshold pore

0%
A-0 A-1 A-2 B-0
Mixture
Fig. 8. Thermogravimetry (TG) results for portlandite (CH) peaks at about 450 C.
a pronounced effect on decreasing the conductivity of concrete and
rening the pore structure, which discounted the physical penetra-
tion of chloride ions into the cementitious matrix.
3.4. Micro-structural and thermal analyses
The trends from the mercury intrusion porosimetry (MIP) for
Group A and B mixtures are shown in Figs. 6 and 7, respectively.
Also, the apparent total porosities, threshold pore diameters and
proportion of micro pores (less than 0.1 lm) for the mixtures are
shown in Table 5. It should be noted that the MIP tests were done
on at least four small chunks extracted from two replicate cylin-
ders for each mixture, which were put in the same test compart-
ment (porosimeter). Thus, the results shown in Figs. 6 and 7 and
Table 5 can be reasonably considered the averages from represen-
tative populations.
In compliance to the mechanical and durability properties, it
can be noted that the total porosity markedly decreased with the
diameters of mixtures containing nano-silica were less than those
B-1 B-2 of the control mixtures without nano-silica (A-0 and B-0). More
pore structure renement was achieved by increasing the dosage
of nano-silica (Figs. 6 and 7 and Table 5). For example, the decrease
in the threshold pore diameters for Mixtures B-1 (3% nano-silica)
and B-2 (6% nano-silica) was 36% and 48%, respectively relative
to that of Mixture B-0 (0% nano-silica). Correspondingly, the in-
crease in the percentage of micro pores for those mixtures was
8.5% and 5.4%, respectively relative to that of Mixture B-0. Again,
this trend is ascribed to the pozzolanic and ller effects of nano-sil-
ica; however, the contribution of each effect to rening the pore
structure could not be readily differentiated by the MIP results.
The thermogravimetry (TG) results are shown in Fig. 8. Com-
pared to the control mixtures without nano-silica, the addition of
nano-silica in Mixtures A-1, A-2, B-1 and B-2 led to considerable
consumption of portlandite (CH) in the cementitious matrix. This
can be attributed to the effect of the pozzolanic reaction, which
partially led to the pore structure renement observed in the
MIP results (Table 5). However, increasing the nano-silica dosage
from 3% to 6% did not seem to have a pronounced effect on the
depletion of CH (Fig. 8). For example, Mixtures B-1 (3% nano-silica)
and B-2 (6% nano-silica) had comparable CH contents of 2.69% and
2.66%, respectively. These mixtures had threshold diameters of
0.092 and 0.075 lm, respectively (Table 5). This may suggest that
the general improvement in the mechanical and durability proper-
 A.M. Said et al. / Construction and Building Materials 36 (2012) 838844
Fig. 10. BSEM Image for: (a) Specimen B-0 and (b) Specimen B-2.
ties and also in pore structure renement associated with the
increase in the nano-silica addition from 3% to 6% may be mainly
attributed to the physical ller effect of incorporating a larger
volume of ultrane particles in the cementitious matrix. This
statement may be substantiated by further testing in future re-
search by combining nano-silica with other types of inert nano-
particles.
Back-scattered electron microscopy (BSEM) was conducted on
thin sections to complement the trends observed in the MIP and
TG tests. In general, BSEM observations conformed to the results
for strength, durability, MIP, and TG tests. It should be mentioned
that some of the observed cracks in the micrographs are artifacts
due to the sample preparation procedures. However, the BSEM
analysis can still be considered as a reasonable indication for the
microstructure in the light of the trends observed from the other
tests.
For Group A mixtures (without y ash), signicant densication
was observed in the matrix at the interfacial transition zone (ITZ)
for specimens containing nano-silica. For instance, Figs. 9a-b show
the ITZ as indicated by the arrows for Specimens A-0 (0% nano-sil-
ica) and A-2 (6% nano-silica), respectively. It can be observed that
the ITZ for Specimen A-0 (Fig. 9a) is full of voids and micro-cracks
due to the wall effect between aggregates and the cementitious
matrix. On the other hand, the ITZ in the section prepared from
Mixture A-2 (Fig. 9b) appears to be densied and rened, owing
to the chemical (pozzolanic reaction) and physical (ller action)
843
effects induced by nano-silica particles. This conforms to the re-
sults from the strength, durability, MIP, and TG tests.
For Group B specimens containing 30% Class F y ash, a more por-
ous structure was observed in the control Specimen (B-0) at 28 days.
For example, Figs. 10ab shows the BSEM images for Specimen B-0
and B-2, respectively. For Specimen B-0, without nano-silica, the
micrograph in Fig. 10a shows a coarse microstructure of the cemen-
titious matrix incorporating 30% y ash. Considering that Class F y
ash was used, the microstructure reects an insufcient degree of
hydration of the matrix at this age (28 days), which links to the lower
strength results shown in Fig. 3 and Table 3. Also, this observation
conforms to the MIP pore size distribution curve of this mixture
(Fig. 7), which had the highest total porosity and threshold pore
diameter at this age (Table 5). Conversely, for Specimen B-2, which
incorporated 6% nano-silica with 30% y ash, the BSEM micrographs,
shown in Fig. 10b, showed higher degree of hydration, as depicted by
the rened and denser microstructure and ITZ. Hence, it appears that
the addition of a small dosage of well-dispersed colloidal nano-silica
efciently catalyzed the kinetics of Class F y ash reaction in the
cementitious matrix. This suggests that the delay in strength gain,
microstructure development and durability improvement of con-
crete comprising Class F y ash can be mitigated by the addition of
small dosages of nano-silica.
4. Conclusions
With the advent of nano-size materials to the concrete industry,
rigorous research data should be provided to gain better under-
standing on the effects of such materials on the macro- and mi-
cro-scale properties of concrete. Considering the materials,
mixture designs, and testing methods implemented in the present
study, the following conclusions can be drawn:
 The overall performance of concrete, with or without y ash,
was signicantly improved with the addition of variable dos-
ages of nano-silica.
 For mixtures incorporating nano-silica, the increase in the peak
temperature recorded within 15 h after mixing indicated that
the ultrane nature of nano-silica was responsible for speeding
up the kinetics of hydration reactions.
 At all curing ages, the strength generally increased with the
addition of nano-silica up to 6%. In particular, at 28 days, the
compressive strength was considerably improved for mixtures
incorporating 30% Class F y ash and nano-silica, which indi-
cates that the inherently slower rate of strength development
of concrete containing Class F y ash can be controlled by the
addition of small dosages of nano-silica.
 The RCPT results showed that the passing charges and physical
penetration depths signicantly decreased with the addition of
nano-silica. This suggested that the incorporation of small dos-
ages of nano-silica has a pronounced effect on reducing the con-
ductivity and rening the pore structure of the cementitious
matrix.
 MIP results showed that the total porosity and the threshold
pore diameter were signicantly lower for mixtures containing
nano-silica. More renement of the pore structure was achieved
with increasing the nano-silica dosage up to 6%.
 TG results indicated that the addition of nano-silica led to sig-
nicant consumption of portlandite (CH) in the pozzolanic reac-
tion. However, increasing the dosage of nano-silica from 3% to
6% did not increase the consumption of CH, which suggests that
the general improvement in performance associated with the
increase of the nano-silica addition from 3% to 6% may be
mainly attributed to the physical ller effect in the cementitious
matrix.
844 A.M. Said et al. / Construction and Building Materials 36 (2012) 838844

 BSEM analysis showed notable densication in the ITZ for spec-
imens containing nano-silica. Also, for specimens containing
Class F y ash and nano-silica, BSEM showed higher degree of
hydration at 28 days relative the control mixture containing
only Class F y ash. This suggests that the delay in
microstructure development and durability improvement of
concrete comprising Class F y ash can be mitigated by the
addition of small dosages of nano-silica.
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