J. Mater. Sci. Technol., 2012, 28(1), 73-82.

Eects of Fe
2
O
3
Nanoparticles on Water Permeability
and Strength Assessments of High Strength
Self-Compacting Concrete
Ali Khoshakhlagh
1)
, Ali Nazari
2)
and Gholamreza Khalaj
1)
1) Department of Materials Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran
2) Department of Materials Engineering, Saveh Branch, Islamic Azad University, Saveh, Iran
[Manuscript received August 16, 2010, in revised form September 28, 2010]
In this work, compressive, exural and split tensile strength together with coecient of water absorption of
high performance self-compacting concrete containing dierent amount of Fe
2
O
3
nanoparticles have been
investigated. The strength and the water permeability of the specimens have been improved by adding Fe
2
O
3
nanoparticles in the cement paste up to 4.0 wt%. Fe
2
O
3
nanoparticle as a foreign nucleation site could
accelerate C-S-H gel formation as a result of increased crystalline Ca(OH)
2
amount especially at the early age
of hydration and hence increase the strength of the specimens. In addition, Fe
2
O
3
nanoparticles are able to
act as nanollers and recover the pore structure of the specimens by decreasing harmful pores to improve the
water permeability. Several empirical relations have been presented to predict the exural and the split tensile
strength of the specimens by means of the corresponding compressive strength at a certain age of curing.
Accelerated peak appearance in conduction calorimetry tests, more weight loss in thermogravimetric analysis
and more rapid appearance of peaks related to hydrated products in X-ray diraction results indicate that
Fe
2
O
3
nanoparticles up to 4 wt% could improve the mechanical and the physical properties of the specimens.
KEY WORDS: Water permeability; Fe
2
O
3
nanoparticles; Compressive strength; Split tensile
strength; Flexural strength
1. Introduction
Advancements in concrete technology have re-
sulted in development of a new type of concrete, which
is known as self-compacting high performance con-
crete (SCHPC). The qualities of SCHPC are based
on the concept of the self-compacting high perfor-
mance concretes. Self-compacting concrete (SCC) is
a uid concrete that spreads through congested re-
inforcement, lls every corner of the formwork, and
is consolidated under its weight
[1]
. SCC necessitates
excellent lling ability, good passing ability, and ade-
quate segregation resistance. But it does not include
high strength and good durability as signicant per-
formance criteria. On the other hand, high perfor-
mance concrete (HPC) has been dened as a con-
Corresponding author. Assis. Prof.; Tel.: +98 255 2241511;
Fax: +98 255 2241501; E-mail address: alinazari84@aut.ac.ir
(A. Nazari).
crete that is appropriately designed, mixed, placed,
consolidated, and cured to provide high strength and
low convey properties or good durability
[2]
. HPC ex-
hibits good segregation resistance, but does not pro-
vide excellent lling and passing ability, and therefore
needs external means such as rodding or vibration for
suitable consolidation. Hence, a concrete that fullls
the performance criteria of both SCC and HPC can
be referred to as SCHPC. An SCHPC is such type of
concrete, which oers excellent performance with re-
spect to lling ability, passing capability, segregation
resistance, strength, transport properties and dura-
bility.
Nearly all research has used SCC which includes
active additions to satisfy the great demand for nes
needed for this type of concrete, thereby improving
their mechanical properties in comparison with nor-
mally vibrated concrete (NVC). Koning et al.
[3]
and
Hauke
[4]
registered strength increase in SCCs made
74 A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382.
Table 1 Chemical and physical properties of Portland cement (wt%)
SiO
2
Al
2
O
3
Fe
2
O
3
CaO MgO SO
3
Na
2
O K
2
O Loss on ignition
21.89 5.3 3.34 53.27 6.45 3.67 0.18 0.98 3.21
Note: Specic gravity, 1.7 g/cm
3
Table 2 Properties of nano-Fe
2
O
3
Diameter/nm Surface volume ratio/(m
2
/g) Density/(g/cm
3
) Purity/%
152 15918 <0.15 >99.9
with dierent amount of y ash. According to Fava
et al.
[5]
, in SCCs with granulated blast furnace slag,
this increase is also evident. On the other hand, when
limestone ller is used, Fava et al.
[5]
and Daoud et
al.
[6]
achieved a tensile strength in SCC lower than
other normal types of concrete.
Permeability of concrete is dened as the move-
ment of liquid and gas or both through a mass of con-
crete under a constant pressure gradient. It is an in-
herent property of concrete that chiey depends upon
the geometric arrangement and characteristics of the
constituent materials. The permeability of concrete
is mainly controlled by the solidity and porosity of
the hydrated paste present in bulk paste matrix and
interfacial transition zone. In the hydrated paste, the
capillary and gel pores can be distinguished. The gel
pores are very small. Although they constitute a net-
work of open pores, the permeability of this network
is very low. Conversely, the capillary pores are rela-
tively large spaces existing between the cement grains.
It is the capillary porosity that greatly aects the per-
meability of concrete
[7]
. The permeability of SCHPC
is typically lower than that of ordinary concrete. The
previous research showed that SCHPC results in very
low water and gas permeability
[8,9]
. This is mostly
attributed to the superior ow properties, dense mi-
crostructure and rened pore. Good ow properties
result in superb packing condition due to better con-
solidation, and thus contribute to reduce the perme-
ability of concrete.
As authors

knowledge, there are few works on

incorporating nanoparticles about SCCs to achieve
improved physical and mechanical properties. Only,
there are several reports on integration of nanoparti-
cles in NVCs, most of which have focused on using
SiO
2
[1019]
and TiO
[20,21]
2
nanoparticles. There are
a few studies on incorporating nano-Fe
2
O
[22]
3
, nano-
Al
2
O
[23]
3
, and nanoclay particles
[24,25]
. Additionally,
a limited number of investigations are dealing with
the manufacture of nanosized cement particles and
the development of nanobinders
[26]
. Previously, a se-
ries of works
[2734]
have been conducted on cemen-
titious composites by adding dierent nanoparticles
evaluating the mechanical properties of the compos-
ites. Nanoparticles can act as heterogeneous nu-
clei for cement pastes, further accelerating cement
hydration because of their high reactivity, as nano-
reinforcement, and as nano-ller, densifying the mi-
crostructure, thereby, leading to a reduced porosity.
Fig. 1 Particles distribution pattern of ordinary Port-
land cement
The most signicant issue for all nanoparticles is that
of eective dispersion.
Incorporating of other nanoparticles is rarely re-
ported. Therefore, introducing some other nanopar-
ticles which probably could improve the mechanical
and physical properties of cementitious composites
is inherent. The aim of this study is incorporating
Fe
2
O
3
nanoparticles into SCCs to study compressive
strength and water permeability of self-compacting
high strength concrete. In addition, pore structure,
thermal properties and microstructure of the concrete
specimens have been evaluated. Several specimens
with a constant amount of polycarboxylate super-
plasticizer (PC) have been prepared and their phys-
ical and mechanical properties have been considered
when, instead of cement, Fe
2
O
3
nanoparticles were
partially added to the cement paste.
2. Materials and Methods
Ordinary Portland cement (OPC) conforming to
ASTM C150
[35]
standard was used as received. The
chemical and physical properties of the cement are
shown in Table 1. The nanoparticle size distribution
pattern of the used OPC has been illustrated in Fig. 1.
Fe
2
O
3
nanoparticles with average particle size of
15 nm and 45 m
2
/g Blaine neness producing from
Suzhou Fuer Import & Export Trade Co., Ltd was
used as received. The properties of Fe
2
O
3
nanoparti-
cles are shown in Table 2. Scanning electron micro-
graphs (SEM) and powder X-ray diraction (XRD)
diagrams of Fe
2
O
3
nanoparticles are shown in Figs. 2
and 3.
Crushed limestone aggregates were used to pro-
duce self-compacting concretes, with gravel 4/12 and
two types of sand: one coarse 0/4, for ne aggregates
and the other ne 0/2, with a very high nes content
(particle size <0.063 mm) of 19.2 wt%, the main
A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382. 75
Table 3 Physical and chemical characteristics of the polycarboxylate admixture
Appearance Solid residue pH Specic gravity Rotational C Na
+
K
+
/(kg/L) viscosity/(MPas) /% /10
6
/10
6
Yellow-brown liquid Approximately 36% 5.25.3 Approximately 1.06 79.30 52.25 9150 158
Table 4 Mixture proportion of nano-Fe
2
O
3
particles blended self-compacting concretes
Sample designation Fe
2
O
3
nanoparticles/% PC content/%
Quantities/(kg/m
3
)
Cement Fe
2
O
3
nanoparticles
C0SCC1 0 1.0 450 0
N1SCC1 1 1.0 445.5 4.5
N2SCC1 2 1.0 441.0 9.0
N3SCC1 3 1.0 437.5 13.5
N4SCC1 4 1.0 432.0 18.0
N5SCC1 5 1.0 427.5 22.5
Note: Water to binder (cement + nano-Fe
2
O
3
) ratio of 0.40
Fig. 2 SEM micrograph of Fe
2
O
3
nanoparticles
Fig. 3 XRD analysis of Fe
2
O
3
nanoparticles
function of which was to provide a greater volume
of ne materials to improve the stability of the fresh
concrete.
A polycarboxylate with a polyethylene condensate
defoamed based admixture (Glenium C303 SCC) was
used. Table 3 shows some of the physical and chem-
ical properties of polycarboxylate admixture used in
this study.
Totally, two series of mixtures were prepared in
the laboratory trials. C0SCC series mixtures were
prepared by cement, ne and ultra-ne crushed lime-
stone aggregates with 19.2 wt% ultra-ne ones and
1.0 wt% polycarboxylate admixture replaced by wa-
ter. NSCC series were prepared with dierent con-
tents of Fe
2
O
3
nanoparticles with the average particle
size of 15 nm. The mixtures were prepared with the
cement replacement by Fe
2
O
3
nanoparticles from 1.0
to 5.0 wt% and 1.0 wt% polycarboxylate admixture.
The superplasticizer was dissolved in water, and then
the nano-Fe
2
O
3
was added and stirred at a high speed
for 3 min. Though nano-Fe
2
O
3
cannot be dissolved
in water, a smaller amount of nano-Fe
2
O
3
can be dis-
persed evenly by the superplasticizer
[11]
. The water
to binder ratio for all mixtures was set at 0.40
[36]
. The
binder content of all mixtures was 450 kg/m
3
. The
proportions of the mixtures are presented in Table 4.
The mixing sequence for SCCs consisted of ho-
mogenizing the sand and cementitious materials for
1 min in the mixer and then approximately 75% of
the mixing water were added. The coarse aggregate
was introduced and then the superplasticizer was pre-
dissolved in the remaining water and was added at the
end of the mixing sequence. The total mixing time in-
cluding homogenizing was 5 min.
Several types of tests were carried out on the pre-
pared specimens:
Strength evaluation tests: Cubic specimens with
100 mm edge length for compressive tests. Cylin-
drical specimens with the diameter of 150 mm and
the height of 300 mm for split tensile tests and cu-
bic specimens with 200 mm50 mm50 mm edges
length for exural tests were made. The moulds were
covered with polyethylene sheets and moistened for
24 h. Then the specimens were demoulded and cured
in water at a temperature of 20

C in the room con-
dition prior to test days. The strength tests of the
samples were determined at 2, 7 and 28 days of cur-
ing. Compressive tests were carried out according to
the ASTM C 39
[37]
standard, split tensile tests were
done in accordance to the ASTM C 496
[38]
standard
and exural tests were performed conforming to the
ASTM C 293
[39]
standard. The tests were carried
out triplicately and average strength values were ob-
tained.
Water permeability tests: The water permeability
tests are performed with several methods such as per-
centage of water absorption, rate of water absorption
and coecient of water absorption. In this work,
76 A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382.
Table 5 Compressive strength of C0SCC and NSCC specimens
Compressive strength/MPa
Sample designation Fe
2
O
3
nanoparticles/%
2 days 7 days 28 days
C0SCC1 0 14.0 20.6 31.6
N1SCC1 1 16.1 26.1 38.1
N2SCC1 2 17.5 31.3 41.5
N3SCC1 3 19.3 35.2 48.2
N4SCC1 4 20.5 40.7 54.3
N5SCC1 5 22.0 38.4 52.8
to evaluate the water permeability of the specimens,
percentage of water absorption is an evaluation of the
pore volume or porosity of concrete after hardening,
which is occupied by water in saturated state. Water
absorption values of Fe
2
O
3
nanoparticle blended con-
crete samples were measured as per ASTM C 642
[40]
after 7, 28 and 90 days of moisture curing.
Mercury intrusion porosimetry: There are several
methods generally used to measure the pore structure,
such as optics method, mercury intrusion porosime-
try (MIP), helium ow and gas adsorption
[41]
. MIP
technique is extensively used to characterize the pore
structure in porous material as a result of its sim-
plicity, quickness and wide measuring range of pore
diameter
[41,42]
. MIP provides the information about
the connectivity of pores
[41]
.
In this study, the pore structure of concrete is eval-
uated by using MIP. To prepare the samples for MIP
measurement, the concrete specimens after 28 days of
curing were rst broken into smaller pieces, and then
the cement paste fragments selected from the center
of prisms were used to measure pore structure. The
samples were immersed in acetone to stop hydration
as fast as possible. Before mercury intrusion test, the
samples were dried in an oven at about 110

C until
constant weight to remove moisture in the pores. MIP
is based on the assumption that the non-wetting liq-
uid mercury (the contact angle between mercury and
solid is greater than 90 deg.) will only intrude in the
pores of porous material under pressure
[41,42]
. Each
pore size is quantitatively determined from the rela-
tionship between the volume of intruded mercury and
the applied pressure
[42]
. The relationship between the
pore diameter and applied pressure is generally de-
scribed by Washburn equation as follows
[41,42]
:
D = 4 cos /P (1)
where D is the pore diameter (nm), is the surface
tension of mercury (10
5
N/cm), is the contact an-
gle between mercury and solid (deg.) and P is the
applied pressure (MPa).
The test apparatus used for pore structure mea-
surement is Auto Pore III mercury porosimeter. Mer-
cury density is 13.5335 g/ml. The surface tension of
mercury is taken as 48510
5
N/cm (485 dyne/cm),
and the contact angle selected is 130 deg. The
maximum measuring pressure applied is 200 MPa
(30000 psi), which means that the smallest pore di-
ameter that can be measured reaches about 6 nm (on
the assumption that all pores have cylindrical shape).
Conduction calorimetry: The test was run out
on a Wexham Developments JAF model isothermal
calorimeter, using IBM program AWCAL-4, at 22

C
for a maximum of 70 h. 15 g of cement was mixed
with water and saturated limewater and admixture
before introducing it into the calorimeter cell.
Thermogravimetric analysis (TGA): A Netzsch
model STA 409 simultaneous thermal analyzer
equipped with a Data Acquisition System 414/1 pro-
grammer was used for the tests. Specimens which
were cured for 28 days were heated from 110 to
650

C, at a heating rate of 4

C/min and in an inert
N
2
atmosphere.
Scanning electron microscopy (SEM): SEM inves-
tigations were conducted on a Hitachi Model S-9260
CD-SEM apparatus. Backscattered electron (BSE)
and secondary electron (SE) imaging was used to
study the samples, which were prepared under con-
ditions that ensured their subsequent viability for an-
alytical purposes.
X-ray diraction (XRD): A Philips PW-1730 unit
was used for XRD analysis which was taken from 4 to
70 deg.
3. Results and Discussion
Table 5 shows the compressive strength of C0
SCC and NSCC specimens at 2, 7 and 28 days
of curing. The results show that the compressive
strength increases by adding Fe
2
O
3
nanoparticles up
to 4.0 wt% replacements (N4SCC series) and then it
decreases, although adding 5.0 wt% Fe
2
O
3
nanopar-
ticles produces specimens with much higher compres-
sive strength with respect to C0SCC and NSCC
specimens with 1.0, 2.0 and 3.0 wt% Fe
2
O
3
nanopar-
ticles. The reduced compressive strength by adding
more than 4 wt% Fe
2
O
3
nanoparticles may be due
to this fact that the quantity of Fe
2
O
3
nanoparticles
present in the mix is higher than the amount required
to combine with the liberated lime during the process
of hydration thus leading to excess silica leaching out
and causing a deciency in strength as it replaces part
of the cementitious material but does not contribute
to strength. Also, it may be due to the defects gener-
ated in dispersion of nanoparticles that causes weak
zones. The higher compressive strength in the N
A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382. 77
Table 6 Split tensile strength of C0SCC and NSCC specimens
Split tensile strength/MPa
Sample designation Fe
2
O
3
nanoparticles/%
2 days 7 days 28 days
C0SCC1 1.0 0.4 1.2 1.6
N1SCC1 1 0.8 1.4 1.7
N2SCC1 2 1.4 1.7 2.1
N3SCC1 3 1.7 2.1 2.7
N4SCC1 4 2.0 2.6 3.1
N5SCC1 5 1.8 2.3 2.8
Table 7 Flexural strength of C0SCC and NSCC specimens
Flexural strength/MPa
Sample designation Fe
2
O
3
nanoparticles/%
2 days 7 days 28 days
C0SCC1 0 2.8 3.7 4.2
N1SCC1 1 3.2 4.3 4.7
N2SCC1 2 3.5 4.6 5.8
N3SCC1 3 3.6 5.0 6.7
N4SCC1 4 3.9 5.7 7.4
N5SCC1 5 3.7 5.4 7.1
Fig. 4 Relationship between split tensile strength and
compressive strength of the specimens cured at
2 days (a), 7 days (b) and 28 days (c). C denotes
compressive strength and S denotes split tensile
strength
SCC series mixtures with respect to C0SCC series is
due to the rapid consumption of crystalline Ca(OH)
2
which quickly are formed during hydration of Port-
land cement specially at early ages as a result of high
reactivity of Fe
2
O
3
nanoparticles. As a consequence,
the hydration of cement is accelerated and larger vol-
umes of reaction products are formed. Also Fe
2
O
3
nanoparticles recover the particle packing density of
the blended cement, directing to a reduced volume of
larger pores in the cement paste.
Tables 6 and 7 show the split tensile strength and
the exural strength of C0SCC and NSCC series
concretes, respectively. Similar to the compressive
strength, the split tensile strength and the exural
strength of all NSCC specimens are more than those
Fig. 5 Relationship between exural strength and com-
pressive strength of the specimens cured at 2 days
(a), 7 days (b) and 28 days (c). C denotes com-
pressive strength and F denotes exural strength
of C0SCC specimens. In addition, the split ten-
sile strength and the exural strength of NSCC se-
ries are increased by adding Fe
2
O
3
nanoparticles up
to 4.0 wt% and then they are decreased, similar to
the compressive strength results. Since evaluations
of strength with dierent tests are not aordable,
here, the relationship between compressive strength
and split tensile strength, and the relationship be-
tween compressive strength and exural strength is
presented. Fig. 4(a)(c) show the relationship be-
tween the splitting tensile strength and compressive
strength of all mixes cured for 2, 7 and 28 days, re-
spectively. In addition, Fig. 5(a)(c) show the rela-
tionship between the exural strength and compres-
sive strength of all mixes cured for 2, 7 and 28 days,
respectively. In all curves, a logarithmic relation has
78 A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382.
Table 8 Percentage of water absorption of C0SCC and NSCC specimens
Percentage of water absorption/%
Sample designation Fe
2
O
3
nanoparticles/%
2 days 7 days 28 days
C0SCC1 0 2.30 4.28 3.89
N1SCC1 1 3.62 1.85 1.70
N2SCC1 2 3.90 1.77 1.49
N3SCC1 3 4.22 1.65 1.23
N4SCC1 4 4.58 1.39 1.02
N5SCC1 5 4.39 1.48 1.13
Table 9 Total specic pore volumes and most probable pore diameters of C0SCC and NSCC
specimens
Sample designation Total specic pore volume/(mL/g) Most probable pore diameter/nm
C0SCC1 0.0304 14.0
N1SCC1 0.0341 14.1
N2SCC1 0.0314 14.1
N3SCC1 0.0293 13.0
N4SCC1 0.0272 11.9
N5SCC1 0.0285 13.0
Table 10 Porosities, average diameters and median diameters (volume) of C0SCC and NSCC
specimens
Sample designation Porosity/% Average diameter/nm Median diameter (volume)/nm
C0SCC1 7.17 10.2 22.2
N1SCC1 8.30 11.9 25.3
N2SCC1 7.92 10.8 23.6
N3SCC1 7.67 10.6 19.7
N4SCC1 7.42 9.87 14.5
N5SCC1 7.52 10.3 17.4
been adopted to show this relationship. The R-
squared values are also given in the gures and show
a good compatibility between two specied strength.
As shown in the gures, at every age of curing, one
may predict a specied strength by knowing at least
one of the specimens

strength.
Table 8 shows the percentage of water absorption
of the specimens. The percentage of water absorption
in C0SCC specimens at 2 days of curing is lower than
that of NSCC series while at 7 and 28 days of curing,
this value is lower for NSCC series concrete. This
may be due to more formation of hydrated products
in NSCC series at the early ages of curing. As men-
tioned above, Fe
2
O
3
nanoparticles accelerate the for-
mation of cement hydrates and hence the specimens
need more water to produce these products. There-
fore, at 2 days of curing, the consumption of water
in NSCC series is more than that in C0SCC series
concrete. At 7 and 28 days of curing, the pore struc-
ture of NSCC series concrete is improved and water
permeability of these series is decreased with respect
to the C0SCC series concrete.
Table 8 also shows that the percentage of water
absorption in NSCC series at 7 and 28 days of cur-
ing is decreased by increasing the Fe
2
O
3
nanoparti-
cles content up to 4.0 wt% and then it is increased.
Once again, this may be due to unsuitable dispersion
of the nanoparticles in the cement paste when the
content of the nanoparticles goes beyond 4 wt%. On
the other hand, at 2 days of curing, more water re-
quirement by increasing nanoparticles content up to
4.0 wt% results in the decrease of the coecient of
water absorption. Therefore, it can be suggested that
with prolonged curing, increasing the ages and per-
centages of Fe
2
O
3
nanoparticles can lead to reduction
in permeable voids. This is due to the pozzolanic ac-
tion and ller eects of Fe
2
O
3
nanoparticles. Another
nding is that the interfacial transition zone in con-
crete has been improved due to pozzolanic reaction as
well as ller eect of the Fe
2
O
3
nanoparticles. This
nding is partially in conrmation of the results of
the study by Bui et al
[43]
.
Table 9 shows that by increasing Fe
2
O
3
nanopar-
ticles up to 4 wt%, the total specic pore volumes of
concretes are decreased, and the most probable pore
diameters of concretes shift to smaller pores and fall in
the range of few-harm pore, which indicates that the
addition of PC renes the pore structure of concretes.
Again, adding nanoparticles improves an important
property of self-compacting concrete.
Table 10 gives the porosities, average diameters
and median diameters (volume) of various concretes.
The regularity of porosity is similar to that of total
specic pore volume. The regularity of average diam-
eter and median diameter (volume) is similar to that
of most probable pore diameter.
A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382. 79
Table 11 Pore size distribution of C0SCC and NSCC specimens
Sample designation
Pore size distribution Total specic pore
Harmless pores Few-harm pores Harmful pores Multi-harm pores volume /(mL/g)
(<20 nm) (2050 nm) (50200 nm) (>200 nm)
C0SCC1 0.0039 0.0090 0.0100 0.0038 0.0304
N1SCC1 0.0035 0.0096 0.0103 0.0032 0.0341
N2SCC1 0.0033 0.0091 0.0096 0.0028 0.0314
N3SCC1 0.0029 0.0081 0.0077 0.0021 0.0292
N4SCC1 0.0025 0.0073 0.0055 0.0015 0.0272
N5SCC1 0.0027 0.0077 0.0070 0.0019 0.0285
Table 12 Calorimetric results of C0SCC and NSCC specimens
Sample designation Total heat/(kJ/kg)
First peak Second peak
Time/h Rate/(W/kg) Time/h Rate/(W/kg)
C0SCC1 371.7 2.4 0.71 20.6 3.41
N1SCC1 352.0 2.3 0.70 18.9 3.08
N2SCC1 321.7 2.0 0.66 17.6 2.72
N3SCC1 305.1 1.7 0.62 15.8 2.41
N4SCC1 281.8 1.3 0.57 13.9 2.18
N5SCC1 297.9 1.5 0.59 14.9 2.33
The pore size distribution of concretes is shown in
Table 11. It is observed that by adding nanoparti-
cles, the amount of pores is decreased, which shows
that the density of concretes is increased and the pore
structure is improved.
The eectiveness of nano-Fe
2
O
3
in improving
the pore structure of concretes increases in the
order: C0SCC<N1SCC<N2SCC<N3SCC<N5
SCC<N4SCC. With increasing content of nanopar-
ticles, the reduced extent of pores in concretes is all
decreased, and the improvement on the pore structure
of concretes is weakening.
The mechanism that the nanoparticles improve
the pore structure of concrete can be interpreted as
follows
[44]
: Suppose that nanoparticles are uniformly
dispersed in concrete and each particle is contained
in a cube pattern, therefore the distance between
nanoparticles can be determined. After the hydration
begins, hydrate products diuse and envelop nanopar-
ticles as kernel
[45]
. If the content of nanoparticles and
the distance between them are appropriate, the crys-
tallization will be controlled to be a suitable state
through restricting the growth of Ca(OH)
2
crystal by
nanoparticles. Moreover, the nanoparticles located in
cement paste as kernel can further promote cement
hydration due to their high activity. This makes the
cement matrix more homogeneous and compact. Con-
sequently, the pore structure of concrete is improved
evidently such as the concrete containing nano-Fe
2
O
3
in the amount of 1 wt% binder
[45]
.
With increasing content of Fe
2
O
3
nanoparticles
more than 4 wt%, the improvement on the pore
structure of concrete is weakened. This can be at-
tributed to that the distance between nanoparticles
decreases with increasing content of nanoparticles,
and Ca(OH)
2
crystal cannot grow up enough due to
limited space and the crystal quantity is decreased,
which leads to the decrease in the ratio of crystal to
strengthening gel and the increase in the shrinkage
and creep of cement matrix
[46]
, thus the pore struc-
ture of cement matrix is looser relatively.
On the whole, the addition of nanoparticles im-
proves the pore structure of concrete. On the one
hand, nanoparticles can act as a ller to enhance the
density of concrete, which leads to the signicantly
reduced porosity of concrete. On the other hand,
nanoparticles cannot only act as an activator to ac-
celerate cement hydration due to their high activity,
but also act as a kernel in cement paste which makes
the size of Ca(OH)
2
crystal smaller and the tropism
more stochastic.
The heat release rate values in Table 12 show that
increasing the percentage of Fe
2
O
3
nanoparticles up
to 4 wt% in the pastes accelerates peak times and
drops heat release rate values. This is an indicative of
acceleration in initial cement hydration due to higher
content of Fe
2
O
3
nanoparticles. Fe
2
O
3
nanoparticles
can accelerate the cement hydration and hence in-
crease the heat release rate. As it is stated above,
the appearance of the peaks in conduction calorimetry
tests are due to CH and C
3
H compounds formation
in the cement paste. When Fe
2
O
3
nanoparticles were
partially added to cement paste, the acceleration in
formation of CH and C
3
H would result in more rapid
appearance of the related peaks.
Table 13 shows the thermogravimetric analysis re-
sults of C0SCC and NSCC specimens measured
in the 110650

C in which dehydration of the hy-
drated products occurred. The results show that af-
ter 28 days of curing, the loss in weight of the spec-
imens is increased by increasing Fe
2
O
3
nanoparticles
in concretes up to 4 wt%. Again, such as the results
obtained for conduction calorimetry, the increase in
loss weight is due to more formation of CH and C
3
H
compounds in the cement paste.
Fig. 6 shows the XRD analysis of C0SCC and
80 A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382.
Table 13 Weight loss (%) of the pastes in the range
of 110650

C at 28 days of curing of C0
SCC and NSCC specimens
Sample designation Weight loss/%
C0SCC1 10.6
N1SCC1 12.1
N2SCC1 11.9
N3SCC1 11.7
N4SCC1 11.6
N5SCC1 11.3
Fig. 6 XRD results indicating the formation of hydrated
products for dierent NSCC specimens: (a) C0
SCC1, (b) N1SCC1, (c) N2SCC1, (d) N3
SCC1, (e) N4SCC1, (f) N5SCC1
Fig. 7 SEM micrographs of C0SCC1 specimen at 2 days (a), 7 days (c), 28 days (e) of curing and NSCC4
specimen at 2 days (b), 7 days (d) and 28 days (f) of curing
A. Khoshakhlagh et al.: J. Mater. Sci. Technol., 2012, 28(1), 7382. 81
NSCC specimens at dierent time after curing. The
peak related to formation of the hydrated products
shifts to appear in earlier times indicating the positive
impact of PC on formation of Ca(OH)
2
and C-S-H gel
at early age of cement hydration.
Finally, Fig. 7 shows the SEM micrographs of
C0SCC specimen and NSCC specimen contain-
ing 4 wt% Fe
2
O
3
nanoparticles. The morphological
analysis evinces no substantial dierences in either
the form or the texture of the dierent reaction prod-
ucts in pastes with admixtures (C0SCC series). The
micrographs corresponding to paste cured for 2 and
7 days show anhydrous cement that has not yet re-
acted, along with a relatively porous mass analogous
to the reaction products. This region is more compact
and less porous in the paste with admixture. After 28
days, the reaction is observed to progress, with a con-
siderable decrease in the amount of anhydrous cement
particles. Fig. 7 shows a more compact mixture after
all days of curing which indicates rapid formation of
C-S-H gel in the presence of Fe
2
O
3
nanoparticles.
4. Conclusions
(1) As the content of Fe
2
O
3
nanoparticles is in-
creased up to 4 wt%, the compressive strength, split
tensile strength and exural strength of SCC speci-
mens are increased. This is due to more formation of
hydrated products in the presence of Fe
2
O
3
nanopar-
ticles.
(2) Fe
2
O
3
nanoparticles could act as nanollers
and improve the resistance to water permeability of
concrete at 7 and 28 days of curing. At 2 days of cur-
ing, the coecient of water absorption is increased by
increasing the nanoparticles content up to 4.0 wt%
since the specimens require more water for rapid for-
mation of hydrated products.
(3) Fe
2
O
3
nanoparticles up to 4 wt% could accel-
erate the appearance of the rst peak in conduction
calorimetry tests which is related to the acceleration
in formation of hydrated cement products.
(4) Thermogravimetric analysis shows that Fe
2
O
3
nanoparticles could increase the weight loss of the
specimens when they were partially added to cement
paste up to 4 wt%. More rapid formation of hydrated
products in the presence of Fe
2
O
3
nanoparticles which
was conrmed by XRD results could be the reason of
more weight loss.
(5) The pore structure of self-compacting concrete
containing Fe
2
O
3
nanoparticles is improved and the
content of all mesopores and macropores is increased.
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