International Conference on Advances in Structural and Geotechnical Engineering ICASGE’15

6-9 April 2015, Hurghada, Egypt

MODIFIED PROPERTIES OF CEMENTITIOUS

MATERIALS WITH Cr2O3 AND AL2O3 NANOPARTICLES

E.E. Etman1, A.M. Atta1, M.H. Taman1, N.A.Ali2, A. M. Wahba2

1
Department of Structural Engineering, Tanta University, Egypt.
E-mail: emadetman@gmail.com
E-mail: Drahmedatta2003@yahoo.com
E-mail: mohamed.taman@f-eng.tanta.edu.eg
2
Department of Engineering Physics and Mathematics, Tanta University, Egypt.
E-mail: nehalzr@gmail.com
E-mail: a_m_wahba@yahoo.co.uk

In this study, the effect of nano-Cr2O3 and different-phase Al2O3 nanoparticles addition on the
fresh and hardened properties of cement mortar has been investigated. Ordinary Portland cement
was replaced by nano powder at 0.5%, 1.25% and 2.5%wt percent. Nano Cr 2O3 and
Al2O3 nanoparticles were prepared via citrate-precursor autocombustion method. The structure
of the prepared nanoparticles was characterized using X-ray diffraction (XRD). The results
illustrate that the obtained powders have a single phase structure. The morphology and the size
of the synthesized nano-particles were analyzed using Transmission Electron Microscope
(TEM). Photographs confirmed nanoscale crystallized structure. Properties of fresh density and
flow percentage were evaluated in fresh state. The compressive strength along age of the cement
paste was the evaluated property in hardened state. Different mixing methods to uniformly
disperse the nanoparticles within the cement matrix were explored and a suitable mixing
technique was suggested. Scanning electron microscope (SEM) revealed that the microstructure
of the composites with -phase Al2O3 nanoparticles were more compact and dense than that of
plain composite.
Keywords: Nano-Cr2O3, Nano-Al2O3, cementitious materials.

1 Introduction
In the field of nanotechnology, tailored nano-composites have the prime focus as one of the most
major and significant areas of research. There is a particular interest in developing
nanotechnology for cement and concrete. Not only the chemistry that forms cement hydration
products but also the physical behaviour of those products are acceptable for manipulation
through nanotechnology. The mechanical properties of nanoparticles depict their immense
potential for use as reinforcements in composite materials.
Most of the published studies on the use of nano-particles in cement and concrete have
utilized nano-oxides, especially SiO2 and Fe2O3 (Li 2004, Li et al. 2004, Korpa et al. 2005, Lin
et al. 2008, Abbas 2009, Qing et al. 2009). The early work of Li (Li 2004) showed that nano-

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SiO2 could significantly increase the early compressive strength of concrete containing large
amounts of fly ash (Kopra et al. 2005), and improve pore size distribution by filling the pores
between large fly ash and cement particles at the nano-scale. Also, the slurry of amorphous
nano-silica was used to improve the segregation resistance of self-compacting concrete. Another
nano-sized oxide of interest in construction is titanium oxide (TiO2) (Han et al. 2004, Xiong et
al. 2006).
To our knowledge, there are few works on incorporating nanoparticles into cementitious
materials to achieve improved physical and mechanical properties. There are several reports on
incorporation of nanoparticles in normally vibrated concretes, most of which have focused on
using SiO2 nanoparticles (Bjornstorm et al. 2004). In addition, some of the works have
utilizednano-Al2O3 (Li et al. 2006, Campillo et al. 2007), and zinc–iron oxide nanoparticles
(Flores-Velez and Dominguez 2002). Previously, the effects of ZnO2 (Nazari and Riahi 2010e,
Nazari and Riahi 2010d) nanoparticles on different properties of self-compacting concrete have
been studied.
In addition, the works investigating the effects of several types of nanoparticles on properties
of concrete specimens (Nazari 2010, Nazari and Riahi 2010a, Nazari and Riahi 2010b, Nazari
and Riahi 2010c) which are cured in different curing media have been reported. Incorporation of
other nanoparticles is rarely reported. Therefore, introducing some other lab-made nanoparticles,
which probably could improve the mechanical and physical properties of cementitious
composites, taking into considerations the low cost of the additives would be interesting.
The use of different-phase Al2O3 nanoparticles had not been examined in previous work. So
the main aim of this study is preparing -phase Al2O3, -phase Al2O3, in addition to Cr2O3
nanoparticles by laboratory method and incorporating them into cement matrix as a replacement
to study its impact to the fresh and hardened properties of cementitious materials. Several
specimens with fixed amounts of superplasticizer have been prepared and their physical and
mechanical properties have been considered.

2 Materials and Methods

2.1 Preparation of the nanoparticles
Aluminium nitrate (99%) was diluted in distilled water and the calculated amount of citric acid
(99%) (molar ratio of citric acid/metal was set at 1:1) were dissolved in distilled water. Both
solutions were mixed together to form stable metal citrate complexes. This mixture was heated
until 100 C for 1 h under magnetic stirring to evaporate excessive water and converted to a gel.
The gel was heated in muffle furnace. Its thermal decomposition, which results in a powder, was
processed at 350 C for 3 h (Bezerra and Dissertação 2007) . The high temperature ignited the gel
to swell into foam, undergoing a strong self-propagating combustion reaction with the evolution
of large volume of gases in several minutes. The processed powder was milled, sieved and
calcinated at different temperatures to obtain different phases of Al 2O3. The Cr2O3 nanoparticles
were prepared using the same procedure.
The X-ray diffraction (XRD) data was collected using K radiation. Approximately 200 mg
of powder was transferred to a glass XRD sample holder. This sample holder was then placed
inside an X’Pert Graphics X-Ray Powder Diffractometer. Transmission Electronic Microscopic
(TEM) analysis was carried out using a microscope type JEOL–JEM–1230 providing x60000
magnification.

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2.2 Materials
Ordinary Portland cement CEMI-42.5N in compliance with EN196-1 was used in this study.
Table 1 shows the chemical and physical properties of cement. Sand with bulk density of 2.55
and fineness modulus 2.2 was used. Water to cement ratio of 0.40 and superplasticizer type F
were used according to ASTM C494 of dose 0.7% of cement mass based on polycarboxylate
ether.
Table 1: The chemical composition and physical properties of the conducted cement
Chemical composition (%) CEM I-42.5N
Cao 65.4
SiO2 20.4
Al2O3 4.9
Fe2O3 3.1
MgO 1.7
Na2O 0.28
K2O 0.24
SO3 3.6
Specific gravity (gm/cm3) 3.15
Blaine fineness (cm2/gm) 3400

2.3 Sample preparation

Cement mortar was mixed according to ASTM C305 with mixing proportions as shown in Table
2. Water-binder ratio of 0.4 was used. Nanoparticles were used as a replacement for cement with
0.5%, 1.25%, and 2.5%. The dispersion process included mixing of water, superplasticizer, and
nanomaterials together. Stirring the previous solution for 20 min then sonication process started
for 45 min. The dry mix powder of cement and sand 2 min in a drum mixer, and nally the
mixture of water, nanoparticles and the superplasticizer was added. The mixing process
continued for min. The flow test was conducted according to ASTM C230M-14. Three groups
of each nano component containing 0.5%, 1.25, and 2.5% in 5 cm × 5 cm × 5 cm cubes were
casted. The comparative study was provided using two different control specimens, one of them
with superplasticizer and the other without. The mix proportion of the hole specimens is shown
in table 2. After 24 hours of batching, the samples were demolded and cured in normal tap water
until required for testing. The compressive strength of the cubes was measured at the ages of 7,
28 and 180 day. Each testing age accomplished three cubes.

3 Results and Discussion

3.1 Characterization of nanoparticles
The XRD diffraction patterns of the prepared samples are illustrated in Fig. 1. No impurities of
or secondary phases was recorded. The crystallite size for the three samples was estimated using
Williamson-Hall method (Prabhu et al. 2014) and were found to be 58.3, 21.7, and 167.5 nm for
Cr2O3, -phase Al2O3 and -phase Al2O3, respectively.
TEM was carried out to study the morphology and to find out exact particle size of
synthesized nanoparticles. Fig. 2 shows the TEM images and particle size distribution of the
synthesized Cr2O3 NPs. The images show that Cr2O3 NPs were regular in size and shape. We

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can observe a large quantity of uniform nanoparticles (NPs) with average particle size of 40-90
nm, indicates that our synthesis process is an easy method for the preparation of this
nanoparticles.

Table 2: Mix proportion of the specimens

Nanoparticles
Mix Cement Sand Water Nanoparticles Superplasticizer
Sample replacement
No. (gm) (gm) (gm) (gm) (gm)
(%)
Control
1 0.0 500 1375 242 0.0 0
without SP
Control
2 0.0 500 1375 242 0.0 3.5
with SP
3 0.5 497.5 1375 242 2.5 3.5
4 Al2O3 1.25 493.75 1375 242 6.25 3.5
5 2.5 487.5 1375 242 12.50 3.5
6 0.5 497.5 1375 242 2.5 3.5
7 Al2O3 1.25 493.75 1375 242 6.25 3.5
8 2.5 487.5 1375 242 12.50 3.5
9 0.5 497.5 1375 242 2.5 3.5
10 Cr2O3 1.25 493.75 1375 242 6.25 3.5
11 2.5 487.5 1375 242 12.50 3.5

Cr2O3
Intensity(a. u.)

Al2O3( )

Al2O3( )

20 30 40 50 60 70
2

Figure 1. XRD for Cr2O3, Al2O3 nanoparticles

Fig. 3 shows the TEM images and histograms of (a) -alumina and (b) -alumina nanoparticles.
Electronic Microscopic images reveal that severe agglomeration occurred at high temperatures,
and the size distribution of nanoparticle is mostly uniform. Due to the agglomeration, the
determination of the average diameter was difficult because individual particle boundaries were
not clearly distinguishable. But with more accuracy the size of crystallites (not particles) before

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the severe agglomeration is possible to estimate. From TEM images, and the distribution of the
-alumina particles are about 400- 700 nm, and those -alumina nanoparticles are about 10–40
nm as shown in the histogram fig.3.

(a) TEM images for Cr2O3 nanoparticles

25 21.6
19.8 Cr2O 3
20 16.7
Percentage, %

14.1
15
11.0
10
4.4 4.4
5 3.1 2.2
1.3 0.9 0.4
0
20 30 40 50
60 70 80 90 100 110 120 130
Particles size, nm
(b) Particle size distribution of Cr2O3 nanoparticles
Figure 2. (a) TEM images and (b) Particle size distribution of Cr2O3 nanoparticles

(a) TEM images for -Al2O3 nanoparticles

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 International Conference on Advances in Structural and Geotechnical Engineering (ICASGE 2015)

25
Al2 O3 (alpha)
20
16.6 17.1

Percentage, %
14.5
15
9.3 9.8
10 7.8
6.2 5.2 6.2
4.7
5 2.6
0
200 300 400 500 600 700 800 900 1000 1100 1200
Particles size, nm
(b) Particle size distribution of -Al2O3 nanoparticles

(c) TEM images for -Al2O3 nanoparticles

25
Al2 O3 (gamma)
20
15.6
Percentage, %

15 13.2 14.4 12.3

13.6
10.7 11.1
10
4.1
5 2.9 2.1
0
5 10 15 20 25 30 40 50 60 70
Particles size, nm
(d) Particle size distribution of -Al2O3nanoparticles
Figure 3. TEM images and particle size for (a), (b) - Al2O3 and (c), (d) - Al2O3 nanoparticles

3.2 Consistency
Fig. 4 shows the flow ability of cement mortar. Where the initial flow percentage indicates the
spreading value of the cement mortar after lifting the conical mold without chaking the table.
The final flow percentage measured after standard number of chaking cycles equal to 25. The

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high concentration of nanoparticles additives reduces the flow significantly due to its high
specific area. The final flow value also reduced with increasing the dose of nanoparticles except
for -Al2O3. The -Al2O3 nano particles replacements show the minimum flow values between
nanoparticles. This may be due to the smaller size of such nano as shown from TEM results,
thus increase the ability of filling the spaces of the produced specimens.

3.3 Compressive strength

It is clear that the control samples without using superplasticizer have larger compressive
strength compared to that one with SP as shown in Fig. 5. For other tested samples with using of
both nanoparticles as a replacement and SP, it was found that, 1.25% had the maximum
compressive strength value. Using 1.25% of -Al2O3 nanoparticles as a replacement raised
compressive strength up to 16%.
264
Initial flow, %
231 Final flow, %
216
205 205 205 200
195
198 184
163
165 153
Flow, %

132 137
132 121
111 105
100
99 89
68 74
66 53

33 21
5 11
0

Figure 4. Effect of using different nanoparticles on cement mortar consistency

3.4 Scanning electron microscopy

Specimens were broken of the compressive strength testing using a hammer to small pieces.
The microscope used was operated with high vacuum and accelerated voltages of 5 kV.
Specimens were coated with platinum. Several regions were examined. Fig. 6 represents the
scanning electron microscope images of control specimen without SP, that with 1.25% nano -
Al2O3, and that with 1.25% nano Cr2O3 nanoparticles.

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50 50 50

45 45 45
Compressive strength, MPa

40 40 40

35 35 35

30 30 30
Control without SP Control without SP Control without SP
Control with SP Control with SP Control with SP
25 Al2O3- - 0.5% 25 Al2O3- - 1.25% 25 Al2O3- - 2.5%
Al2O3- - 0.5% Al2O3- - 1.25% Al2O3- - 2.5%
Cr2O3 - 0.5% Cr2O3 - 1.25% Cr2O3 - 2.5%
20 20 20
0 60 120 180 0 60 120 180 0 60 120 180
Age, days Age, days Age, days
Figure 5. Compressive strength of cement replaced with 0%, 0.5%, 1.25% and 2.5%
examined nanoparticles

The structure was found to have more and larger voids compared with control specimen
without SP. SEM analysis reveals formation of much denser microstructure using both nano -
Al2O3, and nano Cr2O3. Images revealed that the nano-particles were not only acting as a ller,
but also as an activator to promote hydration proves. Agglomerations of nano -Al2O3, and
nano Cr2O3 particles were also observed as represented by the white circles in the SEM
images.

(a) control without SP (b) 1.25% nano -Al2O3

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(c) 1.25% nano Cr2O3

Figure 6. SEM of (a) control without SP, (b) 1.25% nano -Al2O3, and (c) 1.25% nano Cr2O3

4 Conclusions
From the experimental results obtained, the following conclusions are drawn:
Using 1.25% of -Al2O3 nanoparticles as a replacement raised compressive strength up to
16%.
Addition of nano-Cr 2O3 does not improve the compressive strength of cement paste.
SEM con rms the formation of much denser microstructure with nano - Al2O3 addition
and agglomeration of nano- Al2O3 particles.
Further study in this direction is recommended.

5 References
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