Construction and Building Materials 52 (2014) 189–193

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Construction and Building Materials

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

Effects of nano-Al2O3 on early-age microstructural properties

of cement paste
Salim Barbhuiya a,⇑, Shaswata Mukherjee b, Hamid Nikraz a
a
Curtin University of Technology, Australia
b
Jadavpur University, Kolkata, India

h i g h l i g h t s

 Early-age microstructural properties of cement paste containing nano-Al2O3.

 No changes noticed in the early-age compressive strength with nano-Al2O3 addition.
 No new crystalline phase was developed with nano-Al2O3 addition.
 Formation of much denser microstructure with nano-Al2O3 addition.

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

Article history: The effects of nano-Al2O3 addition on the early-age microstructural properties of cement paste is
Received 24 September 2013 reported in this paper. The study was limited to evaluation of properties of cement paste hydrated up
Received in revised form 17 October 2013 to an age of 7 days. Ordinary Portland cement was replaced by nano-Al2O3 powder at 2% and 4% by
Accepted 2 November 2013
weight. The water–binder ratio was fixed at 0.4. No changes were noticed in the early-age compressive
Available online 5 December 2013
strength with nano-Al2O3 addition. XRD analysis confirmed that no new phase developed due to the addi-
tion of nano-Al2O3 powder. However, FTIR analysis shows a shift in water associated band to lower fre-
Keywords:
quency mostly with 4% nano-Al2O3 addition. Scanning electron microscopy reveals the formation of
Nano-Al2O3
Cement
much dense microstructure with larger crystals of portlandite within the cement matrix.
XRD Ó 2013 Elsevier Ltd. All rights reserved.
FTIR
SEM
Compressive strength

1. Introduction Al2O3 during cement hydration was found to responsible for

Concrete is one of the common and widely used building mate-
rials in the world and it is a nano-structured, multi-phase, compos-
ite material that ages over time [1]. The concept of incorporating
nanomaterials in cement matrix is a new and promising research
field. Various nano-materials such as nano-SiO2, nano-TiO2, nano-
Al2O3, nano-Fe2O3, carbon nano-tubes, carbon nano-fibres and
nano-clay have recently being used in cement and concrete to im-
prove their mechanical, physical, durability and several others no-
vel properties [2]. Recent research by Li et al. [3] has found that the
use of nano-Al2O3 has no change in compressive strength, but its
use can increase the elastic modulus of cement mortar by 143%
at 28 days with 5% nano-Al2O3. Densification of the ITZ by nano-
⇑ Corresponding author. Address: Department of Civil Engineering, Curtin Uni-
versity of Technology, GPO Box U1987, Perth, WA 6845, Australia. Tel.: +61 8 9266
2392; fax: +61 8 9266 2681.
E-mail addresses: Salim.Barbhuiya@curtin.edu.au (S. Barbhuiya), shaswataa@
gmail.com (S. Mukherjee), Hamid.Nikraz@Curtin.edu.au (H. Nikraz).
increment of the elastic modulus. If the replacement level was in-
creased more than 5%, agglomerations of nano-Al2O3 particles de-
creased the elastic modulus by ineffective densification.
Achieving a high-quality concrete may not be possible if ade-
quate attention is not paid to its early-age properties. For instance,
the mechanical performance and long-term durability of concrete
can be seriously affected due to inadequate curing or insufficient
compaction during placement. Moreover, accelerated construction
schedules aiming at economic gains have led to tragic failures dur-
ing construction due to inadequate knowledge of the concrete
behavior at the early age. Therefore, a fundamental understanding
of the behavior of concrete at early age is essential to ensure safety
during construction, as well as adequate durability and long-term
properties.
Ali and Shadi [4] studied the heat of hydration, up to 70 h, by
partially replacing the binder materials (Portland cement + slag)
with nano-Al2O3 at levels of 0%, 1%, 2%, 3% and 4%, by weight. Addi-
tion of nano-Al2O3 in cement pastes was found to accelerate the
peak times and drop the heat release. The highest drop in the heat

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.11.010
190 S. Barbhuiya et al. / Construction and Building Materials 52 (2014) 189–193

release was more prominent for 3% nano-Al2O3 content mix. Ali
et al. [5] reported a decrease in workability and reduction in set-
ting time with nano-Al2O3 addition. However, a detailed study on
the effects of nano-Al2O3 on the microstructure and changes in
quality and quantity of hydration product is missing in the litera-
ture. This experimental study focuses on the microstructural prop-
erties of cement pastes with nano-Al2O3 addition. This is needed
for better understanding the effects of nano-Al2O3 addition in
cement.
2. Materials and methods
2.1. Materials
3. Results and discussion
3.1. Compressive strength
Compressive strength of cement paste containing 2% and 4%
nano-Al2O3 was found to increase slightly at 1 and 7 day. The
changes in compressive strength at 1, 3 and 7 day is very small
and it was found that addition of nano-Al2O3 in cement paste does
not have any direct effect on the compressive strength of paste
samples. However, the long-term compressive strength of cement
paste containing nano-Al2O3 may be more than the control. There-
fore, there is a need to investigate the long-term compressive
strength (see Fig. 3).

Cement used was ordinary Portland cement. Nano-Al2O3 powder was supplied
by Nanostructured & Amorphous Material Inc., USA. The chemical composition of
cement is presented in Table 1, and the properties of nano-Al2O3 powder are given
in Table 2. Fig. 1 represents the XRD analysis of cement and nano-Al2O3. It can be
seen that corundum is the major mineral present in nano-Al2O3 powder whereas
alite and belite are the major minerals in cement. The absolute spectra of nano-
Al2O3 powder and dry Portland cement are shown in Fig. 2. Possible assignment
to some of the peaks of dry cement at different wavenumber (cm 1) are: 2100–
2300 due to CaCO3, 1400–1500 due to CO3, 1100–1200 due to v3 of SO4, 1011–
1080 due to polymerized silica, 877–878 due to v2 of CO3, 847–848 due to Al–O,
Al–OH and 656–658 due to v4 of SiO4. The infrared spectrum which characterizes
nano-Al2O3 powder is in the wave number range from 400 to 1000 cm l.

2.2. Sample preparation

Portland cement was replaced by nano-Al2O3 powder at 0.2% and 4% by weight.

The nano-Al2O3 powder was mixed with cement in dry condition and the dry mix
was sieved several times for proper dispersion of the nano-Al2O3 powder. The
water-binder ratio (W/B) used was 0.4. Cement paste cubes of 50 mm size were cast
and vibrated in table vibrator. Specimens were then demoulded and cured in nor- 20 30 40 50 60 70 80
mal tap water until required for testing. Microstructural properties of hydrated
2 Theta (deg.)
cubes were evaluated at the age of 1, 3 and 7 day.

Fig. 1. XRD analysis of nano-Al2O3 and cements.

2.3. Test methods

The compressive strength was measured for 50 mm cube specimens. At each

test date, after crushing the specimens, they were ground manually and sieved
through 150 lm sieve for XRD analysis. For this, XRD machine, using Cu Ka radia-
tion (Wavelength = 1.5405 Å) was used. Spectra were collected on a FTIR machine
fitted with a single-bounce diamond ATR. Sixty-four background and 64 sample
spectra were co-averaged and ratioed to generate the transmission spectrum.
Two levels of zero filling (3 additional data point between each pair of data points
in the interferogram), Norton-Beer strong apodization (to minimize side-lobes), and
Mertz phase correction were employed. The spectral resolution was 4 wavenum- Cement
bers. Specimens were broken with a hammer into small pieces for SEM. The micro-
scope used was operated with high vacuum and accelerated voltages of 5 kV. Nano Alumina
Specimens were coated with platinum with a thickness of 10 lm. Several regions
were examined and finally the reported figures are selected at 30,000
magnification.
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wave Number (cm-1)

Table 1 Fig. 2. FTIR analysis of nano-Al2O3 and cement.

Chemical composition of cement.

Oxides (%)
SiO2 20.4 60
Al2O3 4.3
Compressive strength (MPa)

0% nano alumina
Fe2O3 2.5 50
CaO 62.6 2% nano alumina
MgO 2.4 40 4 % nano alumina
SO3 2.2
LOI 1.0
30

20

Table 2 10
Properties of nano-Al2O3 powder.
0
Constituents Crystal phase Purity Average particle size 1 day 3 day 7 day
Nano-Al2O3 a 99.5% 27–43 nm
Fig. 3. Compressive strength of cement replaced with 0%, 2% and 4% nano-Al2O3.
 S. Barbhuiya et al. / Construction and Building Materials 52 (2014) 189–193 191

3.2. X-ray diffraction
Figs. 4–6 illustrate the XRD analysis of cement paste replaced
with 0, 2% and 4% nano-Al2O3 at 1, 3 and 7 day respectively.
Ettringite, portlandite, Alite, Belite and Gypsum were found to be
major phases for all the mixes. Changes in peak height and forma-
tion of new peaks were found at 7 day. Intensity of Alite and Belite
phase decreased and new peak of portlandite (2 theta deg. 34, 47,
51, etc.) were found at 7 day. A new peak of Gypsum was found
after 7 day curing (2 theta deg. 11) and is more prominent for
4% nano-Al2O3 content mix. However, no other new crystalline
phase was found with nano-Al2O3 addition.
3.3. Fourier transform infrared spectroscopy
Vibrational frequencies of 0%, 2% and 4% nano-Al2O3 content
mix at 1, 3 and 7 day measured by FTIR (Figs. 7–9) generally give
an indication of changes in silicate, sulfate, hydroxide and
carbonate phases. The silicate condensation reaction can be
studied by silicate infrared bands. Out of plane Si–O bending
4 4
(V4 SiO4 ), Asymmetric Si–-O stretching (V 3 SiO4 ) and in plane
4
Si–O bending (V 2 SiO4 ) typically centred at around wavenumber
508, 941 and 440 cm 1. The % transmittance was found to be
decrease at 1 and 3 day for 4% nano-Al2O3 content mix. Some

0% Alumina, Day 1
2% Alumina, Day 1
5 10 15 20 25 30 35 40 45 50 55 60 65 4% Alumina, Day 1
2 Theta (deg.)

Fig. 4. XRD analysis of cement replaced with 0%, 2% and 4% nano-Al2O3 at 1 day. 4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wavenumber (cm-1)

Fig. 7. FTIR analysis of cement replaced with 0%, 2% and 4% nano-Al2O3 at 1 day.

0% Alumina, Day 3
2% Alumina, Day 3
4% Alumina, Day 3
5 10 15 20 25 30 35 40 45 50 55 60 65
2 Theta (deg.)
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Fig. 5. XRD analysis of cement replaced with 0%, 2% and 4% nano-Al2O3 at 3 day. Wavenumber (cm-1)

Fig. 8. FTIR analysis of cement replaced with 0%, 2% and 4% nano-Al2O3 at 3 day.

0% Alumina, Day 7
2% Alumina, Day 7
4% Alumina, Day 7

5 10 15 20 25 30 35 40 45 50 55 60 65 4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
2 Theta (deg.) Wavenumber (cm )

Fig. 6. XRD analysis of cement replaced with 0%, 2% and 4% nano-Al2O3 at 7 day. Fig. 9. FTIR analysis of cement replaced with 0%, 2% and 4% nano-Al2O3 at 7 day.
192 S. Barbhuiya et al. / Construction and Building Materials 52 (2014) 189–193
Fig. 10. 1 Day SEM of 0% nano-Al2O3.
Fig. 11. 1 Day SEM of 2% nano-Al2O3.
Fig. 12. 1 Day SEM of 4% nano alumina.
Fig. 13. 3 Day SEM of 0% nano alumina.
Fig. 14. 3 Day SEM of 2% nano alumina.
Fig. 15. 3 Day SEM of 4% nano alumina.
Fig. 16. 7 Day SEM of 0% nano alumina.
possible assignments of peaks are given by Ylmen et al. mostly
matches for our samples and are taken as Ref. [6]. The bands at
3640 cm 1 is due to the presence of calcium hydroxide and the
band at 3397 cm 1 is because of v3H2O and capillary water. Other
major bands at wavenumber 1655 cm 1 is due to v2H2O,
1414 cm 1 is due to CO3, 1109 cm 1 is due to v3SO4, 872 cm 1 is
due to v2CO3 and 621 cm 1 is due to v4SiO4. With the increment
of nano-Al2O3 content in the mix, water associate bands have
shifted slightly to lower frequencies. No such changes were noticed
for sulfate, silicate and hydroxide associated bands with nano-
Al2O3 addition.
3.4. Scanning electron microscopy
Figs. 10–18 represents the scanning electron microscope images
of 0%, 2% and 4% nano-Al2O3 content mix cured up to 1, 3 and
 S. Barbhuiya et al. / Construction and Building Materials 52 (2014) 189–193
Fig. 17. 7 Day SEM of 2% nano alumina.
Fig. 18. 7 Day SEM of 4% nano alumina.
7 days. Formation of C–S–H and ettringite is found for 1 day cured
specimens for 0%, 2% and 4% nano-Al2O3 content mix specimens.
The structure was found to be with fewer voids with 4% than 0%
and 2% nano-Al2O3 content specimens. Formation of larger crystal
of portlandite was found for 2% and 4% at 7 day compared to 0%
193
nano-Al2O3 content specimens. Agglomerations of nano-Al2O3 par-
ticles were also noticed with 2% and 4% nano-Al2O3 content spec-
imens that are represented by the white circles in the SEM
images. SEM analysis reveals formation of much denser micro-
structure with nano-Al2O3 addition.
4. Conclusions
From the experimental results obtained, the following conclu-
sions are drawn:
i. Addition of nano-Al2O3 does not improve the compressive
strength of cement paste at early age.
ii. XRD analysis confirms that no new crystalline phase was
developed with nano-Al2O3 addition within 7 days of curing.
iii. From FTIR analysis water associated bands were found to be
shifted to lower frequency with nano-Al2O3 addition and no
such major changes in sulfate, carbonate or silica associated
band were noticed. The % of transmittance was found to be
decreased with 4% nano-Al2O3 addition.
iv. SEM confirms the formation of much denser microstructure
with nano-Al2O3 addition and agglomeration of nano-Al2O3
particles.
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