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Abstract: The effects of nanoalumina (NA) and graphene oxide (GO) on the early-age hydration and mechanical properties of portland
cement pastes were investigated in this study. The hydration heat release rate and cumulative heat of cement pastes incorporating different
dosages of NA and GO were evaluated using an isothermal calorimeter measurement method. Early-age electrical resistivity development was
investigated by a noncontact electrical resistivity technique. The results show that both NA and GO could efficiently accelerate cement
hydration. As a physical filler, NA significantly accelerates the hydration of tricalcium aluminate (C3 A) in cement. On the other hand,
GO is able to obviously reduce the dormant period of cement hydration and shift the heat flow peaks to the left by accelerating the hydration
of tricalcium silicate (C3 S) in cement. Compared to plain cement pastes, both the compressive and flexural strengths of cement pastes incor-
porating NA or GO are significantly increased. However, when NA and GO contents exceed the optimal amounts, improvements in flexural
strength tend to decline, which is probably due to particle agglomeration. NA-cement paste exhibited slightly higher electrical resistivity than
plain cement paste during hydration acceleration and deceleration stages. But GO-cement paste clearly showed lower electrical resistivity,
which might be attributed to iron diffusion caused by GO with large surface areas. DOI: 10.1061/(ASCE)MT.1943-5533.0001926. © 2017
American Society of Civil Engineers.
Author keywords: Cement paste; Nanoalumina (NA); Graphene oxide (GO); Hydration; Electrical resistivity.
Introduction cracks at the initial stage before these cracks develop into meso-/
macro-/microscale cracks (Konsta-Gdoutos et al. 2010). Previous
Cement-based materials are extensively used for building and researches showed that nanoalumina (NA) could significantly in-
construction. However, they usually have limited structural appli- crease the elastic modulus of cement paste by up to 143% at a
cations owing to their poor tensile strength and ductility. For dosage of 5% by weight of cement but had a limited effect on com-
example, weak tensile strength is associated with porous micro- pressive strength (Li et al. 2006). For cement mortars with NA ex-
structures and preexisting flaws. Recent advancements in nanotech- posed to high temperatures up to 800°C, NA enhanced compressive
nology have led to the production of nanosized particle, fibers, and strength by up to 16% and residual compressive strength and im-
sheets [e.g., nanoalumina, carbon nanotubes, and graphene oxide proved the relative elastic modulus and facilitated higher energy
(GO)], which can be used as reinforcements for cementitious com- absorption when 1% NA was added (Farzadnia et al. 2013). More-
posites (Sobolev and Shah 2015; Sanchez and Sobolev 2010). It has over, the frost resistance of concrete containing NA was better than
been reported that nanomaterials in cementitious composites are that containing the same amount of nanosilica. However, the com-
more effective than conventional steel bar and fiber reinforcements pressive strength of concrete containing nanosilica was higher than
at the millimeter scale because they can control nano-/microscale that containing the same amount of NA (Behfarnia and Salemi
2013). The microstructural refinement of cement mortar has also
1
Lecturer, ARC DECRA Fellow, Centre for Built Infrastructure been reported because NA caused a shift from pores greater than
Research, School of Civil and Environmental Engineering, Univ. of 1.0 μm to pores smaller than 0.1 μm (Campillo et al. 2007). The
Technology Sydney, Sydney, NSW 2007, Australia (corresponding author). increase in cement hydration and the faster dissolution of the Belite
E-mail: wengui.li@uts.edu.au phase due to the high reactivity of fine NA particles was probably
2
Research Fellow, Dept. of Civil Engineering, Monash Univ., Clayton, the reason for the refinement of microstructures. At the same time, a
VIC 3800, Australia. compact formation of hydration products and a reduced content of
3
ARC DECRA Fellow, Dept. of Civil Engineering, Monash Univ.,
calcium hydroxide (CH) crystals were also found when NA was
Clayton, VIC 3800, Australia.
4
Professor, School of Civil Engineering, National Engineering Labora- added in cementitious composites (Nazari and Riahi 2011). The
tory for High Speed Railway Construction, Central South Univ., Changsha enhanced mechanical properties of cementitious composites with
410075, Hunan, P.R. China. NA was reported to be mainly the result of their physical effects,
5
Ph.D. Candidate, Dept. of Civil Engineering, Monash Univ., Clayton, such as filling and nucleation effects, as well as the acceleration
VIC 3800, Australia. of early-age hydration due to the high surface area (Hemalatha et al.
6
Professor, ARC Future Fellow, Dept. of Civil Engineering, Monash 2015).
Univ., Clayton, VIC 3800, Australia. E-mail: wenhui.duan@monash Similarly, recent researches have reported that GO exhibits a
.edu
super high tensile strength and aspect ratio and a large surface area
Note. This manuscript was submitted on September 13, 2016; approved
on December 30, 2016; published online on April 12, 2017. Discussion (Xu and Gao 2011). Its extraordinary mechanical properties, com-
period open until September 12, 2017; separate discussions must be sub- bined with an effective dispersibility in water and inexpensive
mitted for individual papers. This paper is part of the Journal of Materials source, can make GO a promising material for enhancing the
in Civil Engineering, © ASCE, ISSN 0899-1561. mechanical properties of composites (Pan et al. 2015). It has been
cement hydration by a nucleation effect, and the permeability of ments (Cement and Concrete Resistivity-III) and mechanical tests.
cement paste is lower and the microstructure much denser when Therefore, the mechanical strength of cement paste was also exam-
GO is incorporated (Gong et al. 2014). ined and linked with early-age cement hydration processes.
During the early-age cement hydration, temperature is one of
the key indicators enabling a prediction of dormancy and strength
development based on the cement paste mix design, which is usu-
ally evaluated according to ASTM C1679 (ASTM 2008) using a
thermometric TAM Air (TA Instruments, New Castle, Delaware)
isothermal calorimeter (Zhang and Jahidul 2012). The temperature
gradient can be separated into five stages based on duration. It was
found that when nanosilica was introduced into cement composites,
the heat release of the hydration process obviously increased. The
temperature increase took place following a dormancy period and
into the acceleration period as a result of incorporating nanosilica
(Hou et al. 2013). On the other hand, measurement of electrical
resistivity development also indicated an early-age cement hydra-
tion process that relies on solid hydration products and ionic dif-
fusions through water-filled pores (Li et al. 2003; Wei and Li 2005).
The factors influencing the electrical resistivity of cementitious
composites are mainly controlled by the microstructure and porous
solution conductivity. A noncontact electrical resistivity method
has been used to measure the development of electrical resistivity
of fresh concrete and the pore solution within concrete mixtures
[Zhang et al. 2009; Z. Li and W. Li, “Contactless, transformer-based
measurement of the resistivity of materials.” U.S. Patent No.
6639401 (2003)]. The effects of cement type, water-to-cement ratio,
alkali content, superplasticizer selection, and blended cement on
the hydration process of cement composites were investigated cor-
respondingly (Wei and Li 2005, 2006).
Fig. 4. Effect of NA on hydration heat of cement paste during 48 h: (a) heat release rate; (b) difference in heat release rate; (c) cumulative hydration
heat; (d) difference in cumulative hydration heat
following the 28 days after sample casting. The cement pastes were
mixed, cast, compacted, and placed in a moist storage room
(20 2°C) for 24 h. Then the samples were demolded and moved
to a standard curing room up to 28 days to measure the compressive
and flexural strengths. At least three duplicate samples were tested
for each strength measurement to ensure reproducibility of results.
Test Methods
The effects of NA/GO on the early-age hydration process of cement
paste were investigated according to ASTM C 1679 by thermomet-
ric TAM air at a temperature of 25°C (Bentz et al. 2009, 2012;
Onuaguluchi et al. 2014). Temperature was selected to simulate
the standard curing condition. The calorimeter was conditioned at
25°C for a day before experiments, and the amplifier range was set
at 600 mW, as shown in Fig. 2. After the mixing, a sample of 5.0 g
was transferred to a sample ampoule. The calorimeter began to
record heat after the cementitious materials had been in contact
with water for approximately 30 min. Thus, the hydration heat gen-
erated initially during mixing and preparation was not captured.
The heat generated from the hydration was monitored every minute
for 48 h. The measurement was normalized by sample mass. The
normalized power output was then converted to heat generated in
the sample (in joules/gram). In the following results, each curve
Fig. 5. Effects of NA on mechanical strengths of cement paste at
represents the average of three easily reproduced measurements.
28-day: (a) compressive strength; (b) flexural strength
The error of the specifical heat flow is 0.1 mW=g for hydration
durations. On the other hand, the electrical resistivity of cement
paste was measured by a noncontact electrical resistivity measure-
with increasing NA content. For instance, the main heat flow peak
ment device (CCR-III, Hong Kong Brilliant Concept Technologies,
appeared at around 8 h for the reference samples without NA,
Hong Kong, China) as shown in Fig. 3. The samples were cast into
whereas the main peaks were reached at around 5, 6, and 7 h for the
ring-shaped molds (1.67 L), of dimensions 770 mm ðperimeterÞ ×
NA-cement pastes with 2, 4, and 6% NA, respectively. The left shift
55 mm ðheightÞ × 42 mm ðwidthÞ including a cover for preventing
of the peak heat flow can be an indication of NA-promoting hydration
water evaporation during the test period. Data acquisition occurred at
product growth and, therefore, accelerating the cement particles from
5 s intervals over 48 h. The compression and three-point bending
reacting with water at an early age. Based on the results, it seems that
tests of NA/GO reinforced cement paste cylinders and nonnotch
there are two mechanisms by which NA can affect the early-age
beams were performed to evaluate mechanical properties at the
hydration of cement pastes. First, NA particles can function as fine
Concrete Structures Laboratory at Monash University Australia. The
fillers, providing additional surfaces for the nucleation and growth of
compressive and flexural strengths of the cement paste after 28 days
hydration products. In this case, the greatly increased surface area of
of standard curing were determined in accordance with ASTM C109
the NA is expected to accelerate the early-age hydration (Farzadnia
and ASTM C348. Compressive strength was measured using a Shi-
et al. 2013; Heikal et al. 2015). Second, NA probably provided
madzhu (Shimadzu Japan, Kyoto, Japan) universal testing machine
an additional source of alumina ions to the pore solution and signifi-
(AG-X 300 kN) on 25 × 50 mm cylinders with a displacement rate
cantly accelerated the hydration of tricalcium alumina (C3 A) by an
of 0.5 mm=min. Flexural strength was examined using an Instron
increase in the second peak of the heat release flow curve (Bullard
universal testing machine (33R4204) on a 140 × 30 × 15 mm beam
et al. 2011; Taylor 1997). It was also found that the time to reach the
with a displacement rate of 0.05 mm=min.
main peaks of cement hydration decreased as NA increased. This de-
duction still requires more comfirmation by further investigations.
Results and Discussions In comparison to the reference cement paste, the increase in
the maximum heat flow of NA-cement pastes containing different
dosages of NA after the first 48 h was 0.8 mW=g for 2% NA,
Effect of Nanoalumina
2.3 mW=g for 4% NA, and 4.1 mW=g for 6% NA, respectively.
Figs. 4(a and b) present the heat flow curves for the NA-cement Figs. 4(c and d) show the 48 h cumulative heat release of the
pastes with different dosages of NA from 2 to 6% during the first NA-cement pastes with different NA dosages. It was observed that
48 h. It can be observed that the hydration heat release accelerated during the first 24 h, the cumulative heat increased with the NA
other, even with different NA dosages. This trend may be attributed of cement pastes with dosages of 3 and 4% NA are relatively lower
to an inadequate supply of water to maintain hydration, reducing than that of cement with 2% NA but are still 28.7 and 23.8% those
the reaction surface area between cement particles and water (Bentz of the respective reference samples. Therefore, as NA content
et al. 2009; Lootens and Bentz 2016). As a result, the cement increases to 3 and 4%, the enhancement in flexural strength de-
hydration slowed down in comparison with the surface in the pure creases. This might be explained by particle agglomeration result-
cement system at a late age. ing from an excessive amount of NA, which is likely to surround
The compressive strength of NA-cement pastes incorporating fine cement particles and, hence, loosen the microstructures of ce-
different NA dosages at 28 days is illustrated in Fig. 5(a). With the ment paste (Li et al. 2006). The optimal amount of NA is 2% for
increase of NA dosage, the compressive strength of cement pastes cement paste based on the mechanical strength improvement.
correspondingly increases. The compressive strengths of the ce-
ment pastes with NA dosages of 1, 2, 3, and 4% are 32.1, 35.6,
Effect of Graphene Oxide
47.3 and, 52.3% higher than that of the respective reference sam-
ples. The reason for this is that NA, as a super fine aggregate, can The effect of GO on the rate of hydration heat development and
accelerate a higher rate of hydration and fill porous areas in ce- the corresponding cumulative heat release of cement pastes with
ment pastes to lead to a more compact and denser microstructure. GO dosages from 0.02 to 0.06% are shown in Figs. 6(a and b),
Fig. 6. Effect of GO on hydration heat of cement paste during 48 h: (a) hydration heat release rate; (b) difference in heat release rate; (c) cumulative
hydration heat; (d) difference in cumulative hydration heat
Acknowledgments
The authors gratefully acknowledge the financial support of
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