Article

pubs.acs.org/IECR

Portland Cement Paste Modified by TiO2 Nanoparticles: A

Microstructure Perspective
Decheng Feng,† Ning Xie,*,†,‡,§ Chunwei Gong,† Zhen Leng,⊥ Huigang Xiao,‡ Hui Li,‡
and Xianming Shi*,†,§
†
School of Transportation Science and Engineering and ‡School of Civil Engineering, Harbin Institute of Technology, Harbin
150001, China
§
Corrosion and Sustainable Infrastructure Laboratory, Western Transportation Institute and Civil Engineering Department, P.O. Box
174250, College of Engineering, Montana State University, Bozeman, Montana 59717-4250, United States
⊥
Department of Civil and Environmental Engineering, Hong Kong Polytechnic University, 11 Yuk Choi Road, Hung Hom, Hong
Kong

ABSTRACT: Nanomodified Portland cement paste with a water/cement ratio of 0.4 was prepared with the addition of TiO2
nanoparticles at 0.1, 0.5, 1.0, and 1.5% by mass of cement. The flexural strengths of the prepared cement-based composites were
tested, and the fracture surfaces were observed by scanning electron microscopy (SEM). The flexural strength of the
nanomodified TiO2 Portland cement paste reached the highest value with a dosage of 1.0 mass %. The SEM observation shows
that admixing of the TiO2 nanoparticles largely decreased the quantity of internal microcracks in the cement paste. A new type of
needle-shaped hydration product was observed, and its potential growth mechanism was proposed. Atomic force microscopy was
introduced to observe the microstructure of nanomodified Portland cement paste, and the results show that the nanoroughness
of the hardened cement pastes with admixed TiO2 nanoparticles was much lower than that without the TiO2 nanoparticle
addition. Coupled with X-ray diffraction data, the morphological information obtained at the micrometer and nanometer scales
shed light on the role of TiO2 nanoparticles in the cement-based composite.

1. INTRODUCTION concrete matrix may also introduce microstructural regularity

Portland cement is a commonly used binder material to form and serve as a dense barrier and “fiber reinforcement”. Li et
the heterogeneous mortar or concrete matrix, and the durability al.15,16 claim that the nanoparticles can act as nuclei during the
of concrete structures and components in service environments hydration process, and Shah et al. further suggested that they
is of great interest to practicing engineers and researchers.1−5 In can fill the voids in the cement matrix and induce the formation
this context, many approaches have been investigated to of better C−S−H.17 Previous studies also demonstrated that
improve the durability properties of concrete, with a focus on nanoparticles can strengthen the interfacial transition zone
modification of the binder.6−9 As a promising emerging between the cement paste and aggregate, thus improving the
technology in construction, nanotechnology has been applied strength and impermeability of concrete.18 Makar and Chan19
in the production of concrete and proven to enhance the reported single-walled carbon nanotubes to accelerate the
mechanical properties (e.g., compressive strength, ductility, hydration reaction of the tricalcium silicate (C3S) in ordinary
impact resistance) and reduce shrinkage and permeability, all of Portland cement and affect the morphology and location of
which contribute to extension of the concrete’s service life.10−13 both the initial tricalcium aluminate (C3A) and the C3S
A wide variety of nanosized materials, such as nanoclays, hydration products. Vera-Agullo et al.20 reported that with
Fe2O3 and SiO2 nanoparticles, carbon nanotubes, and TiO2 proper dispersion the carbon nanofilaments (either multiwalled
nanoparticles, have been used to reduce the permeability or nanotubes or nanofibers) accelerated the cement hydration
improve the mechanical properties of concrete, thanks to the process and so did the nanosilica and nanoclays.
decreasing production cost of nanomaterials and the increasing Titanium exists in minerals, mostly rutile and ilmenite, which
need for multifunctional materials over the last 2 decades. He are widely distributed in the earth’s crust and lithosphere.
and Shi14 summarized the possible mechanisms responsible for Titanium is ubiquitous in the natural environment, such as
the beneficial effect of nanomaterials on the impermeability of rocks, water bodies, and soils. TiO2 nanoparticles have
mortar and concrete. These may include 1) working as exhibited many magnificent advantages in daily products,
nanosized fillers and leading to a denser and less permeable including white paint, plastics, papers, inks, foods, medicines,
microstructure, (2) acting as a “nucleus” to guide the formation makeups, and toothpastes. They have also shown desirable
and growth of cement hydration products, and (3) promoting properties for such applications as environmental preservation
the formation of high-density C−S−H structures via parallel
packing. In addition, SiO2 nanoparticles and nanomontmor- Received: April 11, 2013
illonites are used, and a pozzolanic reaction may occur between Revised: July 16, 2013
the Portland cement paste and SiO2 in nanomaterials.14 The Accepted: July 22, 2013
nanosheets of montmorillonites distributed in the mortar or Published: July 22, 2013

© 2013 American Chemical Society 11575 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582
Industrial & Engineering Chemistry Research Article

and energy harvesting, including photocatalytic water splitting, hydration. It was also claimed that the hydration products
heterogeneous photocatalysis, charge transfer, Gratzel cells, formed on or near the surfaces of TiO2 nanoparticles and the
sensitized solar cells, organic photovoltaic cells, quantum dots, C3S surface as well. These results demonstrate that the addition
nanorods, nanotubes, photocurrent generation, and electro- of TiO2 nanoparticles accelerates the early-age hydration by
des.21 providing additional nucleation sites, laying the groundwork for
In recent years, some researchers fabricated cement-based the fabrication of cement-based materials with nanoparticles
concrete or asphalt concrete incorporating TiO2 nanoparticles incorporated.
to improve their durability or endow them with certain Calcium silicate hydrate (C−S−H), as the main binding
desirable functionality.22−24 Nanotechnology has demonstrated phase in concrete, has been extensively studied. It was claimed
its substantial benefits in empowering the development of that C−S−H in a hardened paste of C3S or Portland cements
concrete with enhanced durability and mechanical proper- generally has an average Ca/Si ratio of about 1.75 and ranges
ties.25−27 Yet, the mechanisms of concrete nanomodification, from about 1.2 to 2.1 in any given paste.35 There are some
particularly by TiO2 nanoparticles, remain unclear. One models that demonstrated the nanostructure of C−S−H,36
hypothesis to test is that the admixing of TiO2 nanoparticles mainly falling into two types. One type of C−S−H is where the
into cement not only leads to denser hardened cement paste silicate anions are entirely monomeric, and the other one is
but also alters the morphology and chemical compositions of where a linear silicate chain is present in 1.4 nm tobermorite
cement hydration products. (and a number of other minerals), i.e., dreierkette-based
The early-age performance of cement-based materials models.37 Yet another solid C−S−H model was developed by
modified by TiO2 nanoparticles has been studied by some using the H2O/D2O small-angle neutron scattering contrast
researchers. The admixing of TiO2 nanoparticles into cement- variation method. In this model, the nanoscale Ca(OH)2 phase
based materials was found to increase their heat of hydration was quantified and the solid C−S−H formula, (CaO)x(SiO2)-
and accelerate their hydration via heterogeneous nucleation.28 (H2O)y, was determined in terms of x and y, together with its
The early-age mechanical properties were reported to increase mass density.38 Bernal39 believed that most of the silica in the
with the addition of TiO2 nanoparticles. The later-age hydration products in cement paste can be divided into two
mechanical properties, however, decreased sharply as the types of hydrated calcium silicates, demonstrated as C2SH(II)
dosage of TiO2 nanoparticles increased from 5% to 10% by and CSH(I). It was claimed that both of these phases included
weight of cement.29 This is attributable to the increased the monomeric silicate anion [SiO2(OH)2]2− with the general
agglomeration of nanoparticles at higher dosage. formula given as Ca[SiO2(OH)2][Ca(OH)2]xH2Oy, where x
The effect of TiO2 nanoparticles on the early-age hydration would be 1 for C2SH(II) and between 0 and 0.5 for CSH(I).
kinetics of tricalcium silicate (C3S) was investigated by Lee and In the past decade, the rapid progress and improved
Kurtis30 via the Avrami model31−33 shown as availability of advanced nanomaterials and characterization
techniques have led to numerous engineering and mechanistic
X = 1 − exp[−(kavrt )n ] (1) studies of nanotechnology for cementitious materials.40−42
where X is the transformed volume fraction as a function of Recently, many technologies such as nuclear magnetic
time and kavr is the effective rate constant as a function of the resonance,43 small-angle X-ray scattering,44 small-angle neutron
constant linear growth rate. If eq 1 is differentiated with respect scattering,45 and the pair distribution function approach have
to time, the hydration rate can be obtained as been utilized to elucidate the microstructure of the paste clinker
at nanoscale.46 Scanning electron microscopy with energy-
R = Ankavr n(t − t0)n − 1 exp{−[kavr(t − t0)n ]} (2) dispersive spectrometry (SEM/EDS)47 and transmission
electron microscopy (TEM)48 have been used for observing
where R is the hydration rate, A is a normalization constant to the microstructure and morphology and for analyzing the
match the isothermal calorimetry data, and t0 is the time delay chemical composition of cement-based materials. Atomic force
between the time of mixing and the start of nucleation and microscopy (AFM) has been used for observing the
growth kinetics. morphology at nanoscale and for evaluating nanoscale
Recently, the boundary nucleation model was modified by mechanical properties.49 Furthermore, differential scanning
Thomas34 to describe the hydration kinetics of C3S, shown as calorimetry50 and X-ray diffraction (XRD)51 have been used
GT to analyze the hydration products and crystalline structures of
X = 1 − exp{− 2OvB ∫0 [1 − exp(−Y e)] dy}
(3) Portland cement paste, respectively.
The microstructures of Portland cement paste incorporating
where nanosized SiO2, Fe2O3, and carbon nanotubes have been
reported.16,52,53 However, to the best of our knowledge, the
πIB 2 3⎡ 3y 2 2y 3 ⎤ y
Ye = G t ⎢1 − 2 2 + 3 3 ⎥ if t > microstructure of the hardened Portland cement paste
3 ⎣ G t G t ⎦ G incorporating nanosized TiO2 has not yet been reported.
y This work aims to address this knowledge gap by shedding light
Ye = 0 if t < on the microstructure of nanomodified TiO2 cement paste,
G (4) particularly at the nanometer and submicrometer scales.
e
Here, y and Y are temporary variables that disappear after
integration, X depends on three well-defined physical 2. EXPERIMENTAL SECTION
parameters: G, the linear growth rate of the transformed The cement-based materials were made from normal Portland
phase; IB, the nucleation rate per unit area of the untransformed cement pastes (no. 42.5) purchased from Yatai Corp., and the
boundary; and OBv , the boundary area per unit volume. The TiO2 nanoparticles were offered by Kaier Corp., China. The
author claimed that the addition of TiO2 nanoparticles chemical compositions of the cement and TiO2 are listed in
increased the peak reaction rate and the degree of early-age Table 1. The water/cement ratio was 0.4 for all samples. No
11576 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582
Industrial & Engineering Chemistry Research Article

Table 1. Chemical Composition (%) of the Cement and which reveals that the TiO2 nanoparticles are equiaxed
TiO2 Nanoparticles nanocrystals with average particle sizes of about 20−50 nm.
The morphology of the fracture surface of the hardened
cement TiO2
cement samples was observed by SEM coupled with EDS,
SiO2 20.4 performed on a FEI-Quanta 200F scanning electron micro-
Al2O3 3.7 scope. XRD of the samples was obtained on a Rigaku D/max-
Fe2O3 3.4 rA X-ray diffractometer with Cu Kα radiation (λ = 1.5406 Å).
SO3 2.6 The mechanically obtained AFM data were utilized to
CaO 63.3 visually illustrate the microstructure and to generate roughness
Na2O 0.1 and other morphological information about the paste. For AFM
K2O 0.4 imaging in this study, the cement paste surface examined was
MgO 3.2 the as-fabricated bottom surface without polishing so as to
TiO2 >99.5 avoid any potential disturbance of the surface condition by
loss of ignition 2.7 polishing. The AFM height and deflection images were
obtained in contact mode, where the tip of the atomic force
microscope stayed in contact with the sample while it was
admixtures or additives other than TiO2 nanoparticles were
moved across. Roughness measurements were made by
added into the cement paste. The dosages of TiO2 nano-
performing power spectral density measurements, as detailed
particles were 0.1%, 0.5%, 1.0%, and 1.5%, respectively, by mass
elsewhere.54 The phase images were obtained under the
of cement.
tapping mode.
Before mixing the TiO2 nanoparticles and cement, the TiO2
nanoparticles were soaked in water and ultrasonically vibrated 3. RESULTS AND DISCUSSION
for 30 min to achieve good distribution. This was followed by
another 3 min of mixing of the water with the cement under a Figure 2 presents the 28-day three-point flexural strength as a
stirring rate of 800 rph. A 1-L beaker was used for the stirring function of the TiO2 nanoparticle dosage by mass of cement,
process. After stirring, the mixture was poured into a plastic
Petri dish with dimensions of ⌀ 50 mm × 15 mm. The
specimens were demolded after 24 h and cured at room
temperature for 28 days under a relative humidity of 95%. After
curing, the samples were mechanically cut for the flexural
strength test with a size of 3 × 4 × 40 mm3. The flexural
strength test followed the ASTM D790 method, and the span
of the two end points was 33 mm and the loading speed was 0.5
mm/min.
The morphology of the TiO2 nanoparticles was observed by
TEM and selected area electron diffraction (SAED), which
were performed on a Phillips Tecnai 20 microscope with an
accelerating voltage of 200 kV. Figure 1 shows the TEM
morphology and the SAED pattern of the TiO2 nanoparticles,

Figure 2. Three-point flexural strength as a function of the TiO2

nanoparticle dosage in the cement paste.

when the water-to-cement mass ratio is fixed at 0.4. Each point

shown in Figure 2 shows the average value and the standard
deviation of flexural strength values from five specimens. Figure
2 reveals that admixing a small dosage (0.1 mass %) of the TiO2
nanoparticles into the cement can increase its flexural strength
by 4.5% (from 11.53 to 12.05 MPa). However, the benefits
diminished with a further increase in the dosage of the TiO2
nanoparticles. The flexural strength of cement paste reached
the peak value 12.48 MPa, with 1.0 mass % of the TiO2
nanoparticles admixed. As discussed later, the improvement of
the flexural strength by nanomodification may be attributed to
several mechanisms. First, the TiO2 nanoparticles acted as
nuclei to form needle-shaped hydration products, which can
bridge the microcracks and fill in the micropores. Second, the
TiO2 nanoparticles altered their adjacent environment for
Figure 1. TEM morphology and its SAED of the TiO2 nanoparticles. cement hydration reaction and facilitated the formation of high-
11577 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582
Industrial & Engineering Chemistry Research Article

Figure 3. SEM morphology of the fracture surfaces: (a) low magnification of regular cement paste; (b) low magnification of cement paste modified
by TiO2 nanoparticles; (c and d) high magnification of cement paste modified by TiO2 nanoparticles (inset: EDS data).

density C−S−H over low-density C−S−H. Finally, the TiO2 Ca/Si ratio of 2:1 and an Al/Si ratio of 1:6. These aluminum-
nanoparticles led to more evenly distributed hydration phases, rich and silicon-deficient needle-shaped precipitates could be a
which feature the higher fracture energy inherent in the cement new type of C−S−H, which needs to be further elucidated in
paste. Note that fully achieving the potential of nano- future studies. Compared with the regular Portland cement
modification hinges on the proper dispersion of the nano- hydrates, these precipitated nanosized needle-shaped products
particles in the heterogeneous matrix of a cement-based can fill the submicrometer pores and cracks in the paste more
composite. The agglomeration of nanoparticles may at least efficiently and reinforce the paste by bridging the cracks.
partly explain the trends observed in Figure 2, especially the In the past decades, the fiber-reinforced composites have
decrease of the flexural strength with the increase of TiO2 been extensively studied and the beneficial role of fibers in
nanoparticles from 1.0 to 1.5 mass %. improving the toughness of the composite has been
Figure 3 presents the low- and high-magnification SEM confirmed.55,56 The needle-shaped hydration products observed
images of the fracture surfaces of the hardened Portland cement in a nanomodified cement paste (Figure 3) will act as
paste with or without the addition of TiO2 nanoparticles (at 1.0 nanofibers to be pulled out of bent during propagation of
mass %). In the low-magnification mode, as shown in Figure 3a,
cracks and bridge the cracks at the microscopic level. In other
some microcracks perpendicular to the crack surface of the
words, they are expected to help toughen the cement paste.
sample can be observed (area A) along with some flat areas
These can be considered as in situ fiber reinforcement to
exhibiting surfaces of microcracks parallel to the crack surface
of the sample (area B) and some areas with clear internal feature higher bonding strength with the rest of the cement
defects and micropores (area C). As shown in Figure 3b, with paste matrix, related to admixed fibers. Additional research is
the addition of TiO2 nanoparticles, the hydration products were warranted to elucidate the quantity, dimensions, and
distributed more evenly in the cement-based composite (area mechanical properties of these needle-shaped hydration
D), and the density and size of the microcracks and micropores products and how they contribute to the macroscopic
were greatly decreased. Meanwhile, some nanosized needle- properties of the cement paste.
shaped hydration products can be observed (area E). Parts c Figure 4 presents the AFM data of the regular cement paste
and d of Figure 3 show the high-magnification image and EDS and the cement paste modified with TiO2 nanoparticles at 1.0
results of the needle-shaped hydration products in the area E in mass %, in a 1 × 1 μm2 area. As can be seen in this figure, the
Figure 3b. As can be seen from the EDS results, the chemical regular cement paste and nanomodified TiO2 cement paste
composition of the needle-shaped hydration products differed feature a microstructure with distinct characteristics. While the
from that of the other phase adjacent to it. Despite their microstructure of the regular concrete was very rough (Figure
comparable calcium contents, the former featured a Ca/Si ratio 4a), the nanomodified cement paste appeared to be much more
of 5:1 and an Al/Si ratio of 3:5, whereas the latter featured a flat (Figure 4b). It can be demonstrated from Figure 4c,d that
11578 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582
Industrial & Engineering Chemistry Research Article

Figure 4. AFM observations of (a) height image of regular cement paste, (b) height image of cement paste modified by TiO2 nanoparticles, (c) step
height of regular cement paste, (d) step height of cement paste modified by TiO2 nanoparticles, (e) roughness of regular cement paste, and (f)
roughness of cement paste modified by TiO2 nanoparticles in a 1 × 1 μm2 area.

the step heights of the regular and nanomodified cement paste Ca3SiO5 + zCa 2SiO4 + w H 2O
were 2.882 and 1.006 nm, respectively.
The roughness test enables analysis of the microstructure → (1 + z)(CaO)x (SiO2 )(H 2O)y + pCa(OH)2 (5)
uniformity of the cement-based composite. In general, a more
uniform and dense microstructure (lower roughness value) In other words, because the total mole quantity of calcium is
should relate to a cement paste with higher mechanical a constant, calcium can exist in the cement hydration products
properties and lower permeability. Before analysis, each image either as C−S−H gel or Portlandite in the hardened cement
was plane fitted and flattened to eliminate image distortion paste. As such, a lower amount of Portlandite corresponds to a
from the microscope. Once image distortion was removed, the higher amount of C−S−H gel. It is thus desirable to convert
roughness values were calculated. Parts e and f of Figure 4 show the noncementitious Portlandite into cementitious C−S−H gel.
the roughness analysis results of the regular cement paste and Any increase in the C−S−H amount or decrease in the
the nanomodified TiO2 cement paste. As can be seen in these Portlandite amount in concrete will lead to a higher
performance of the hardened cement paste if the macrodefects
figures, the nanomodified TiO2 cement paste has a much lower
in the concrete are ignored for such a comparison.
roughness value (92.851 nm), relative to that of the regular
Figure 6 shows the XRD patterns of the ordinary Portland
cement paste (406.60 nm), confirming pore refinement by
cement paste and the Portland cement paste modified with
nanomodification. TiO2 nanoparticles at 1.0 mass %, using Portlandite as the
Figure 5 presents the AFM data of the height and phase reference. It further confirms that the chemical reactions during
images of the regular cement paste and cement paste modified the hydration process have been altered with the introduction
with TiO2 nanoparticles at 0.1 mass %, in a 10 × 10 μm2 area. of TiO2 nanoparticles. As shown in Figure 6, the three main
By a comparison of the height images of the two types of peaks characteristic of Ca(OH)2 decreased by about 20−30%
cement pastes (Figure 5a,b), it can be concluded that the after the addition of TiO2 nanoparticles, confirming the role of
incorporation of TiO2 nanoparticles into the cement paste led nanomodification in consuming Portlandite crystals. Such
to a flatter surface. Similarly, by comparing the phase images of consumption of Portlandite likely led to a denser micro-
the two types of cement pastes (Figure 5c,d), one can conclude structure and the formation of desirable C−S−H gel,
that the phases of the paste modified with TiO2 nanoparticles contributing to better engineering properties of the cement-
were much finer than those of the regular cement paste. based composite.
Assuming the general formula of C−S−H as (CaO)x(SiO2)- The direct reaction of Ca(OH)2 and TiO2 to form CaTiO3
(H2O)y, the hydration reaction of normal Portland cement normally occurs only at high temperature over 1000 K. As such,
(C3S/C2S) can be simplified as no obvious CaTiO3 peak was detected from the XRD data
11579 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582
Industrial & Engineering Chemistry Research Article

Figure 5. AFM observations of (a) height image of regular cement paste, (b) height image of cement paste modified by TiO2 nanoparticles, (c)
phase image of regular cement paste, and (d) phase image of cement paste modified by TiO2 nanoparticles in a 10 × 10 μm2 area.

(Figure 6), suggesting the absence of crystallized CaTiO3.

During the cement hydration process, there is a possibility that
the O2− in −O−Ti−O− bonding is altered by hydroxyls
(OH−) to form the H−O−Ti−O−H structure. Subsequently,
the H+ in O−H can be replaced by Ca2+ to form the O−Ca−
bond, which leads to the formation of the −Ca−O−Ti−O−
Ca− structure. Because the quantity of the TiO2 nanoparticles
is relatively small, only a small fraction of the Ca2+ cations are
consumed to form the nanosized −Ca−O−Ti−O−Ca−
structure, which serves as a template around which the
remaining Ca2+ cations react with Si4+ and OH− to grow the
needle-shaped amorphous hydration products.

4. CONCLUSIONS
The mechanical properties and microstructure of the cement
pastes containing TiO2 nanoparticles have been investigated
through experimental research. The laboratory testing showed
that the 28-day three-point bend strength of the cement paste
with a water/cement ratio of 0.4 increased by 4.52%, 8.00%,
8.26%, and 6.71%, respectively, when 0.1%, 0.5%, 1.0%, and
1.5% TiO2 nanoparticles by mass of cement were incorporated.
Figure 6. XRD patterns of the nanomodified TiO2 Portland cement Such improvements in the mechanical properties can be
paste versus the regular Portland cement paste and Portlandite. attributed to improvement of the paste microstructure. By the
11580 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582
Industrial & Engineering Chemistry Research Article

addition of a small amount (1.0 mass %) of TiO2 nanoparticles (13) Birgisson, B.; Taylor, P.; Armaghani, J.; and Shah, S. P.
and achievment of good dispersion, nanomodification increased American Roadmap for Research for Nanotechnology-Based Concrete
the amount of cementitious phase in the paste, decreased the Materials. Transportation Research Record: Journal of the Transportation
microporosity and amount of internal microcracks and defects, Research Board, 2010; pp 130−138; No. 2142,
(14) He, X.; Shi, X. Chloride Permeability and Microstructure of
obtained a denser microstructure with reduced nanoroughness,
Portland Cement Mortars Incorporating Nanomaterials. Trans-
and led to the formation of needle-shaped nanoprecipitates. portation Research Record: Journal of the Transportation Research
The morphological information obtained at the micrometer Board, 2008; pp 13−21; No. 2070.
and nanometer scales shed light on the role of TiO 2 (15) Zhang, M. H.; Li, H. Pore Structure and Chloride Permeability
nanoparticles in the cement-based composite. In summary, of Concrete Containing Nano-Particles for Pavement. Constr. Build.
the admixing of TiO2 nanoparticles into cement not only leads Mater. 2011, 25, 608−616.
to denser hardened cement paste but also alters the (16) Li, H.; Xiao, H. G.; Yuan, J.; Ou, J. P. Microstructure of Cement
morphology and chemical compositions of cement hydration Mortar with Nano-Particles. Compos., Part B: Eng. 2004, 35, 185−189.
products. (17) Shah, S. P.; Konsta-Gdoutos, M. S.; Metaxa, Z. S.; Mondal, P.

■
Nanoscale Modification of Cementitious Materials. Nanotechnol.
AUTHOR INFORMATION Constr. 3 2009, 125−130.
(18) Li, Z.; Wang, H.; He, S.; Lu, Y.; Wang, M. Investigations on the
Corresponding Author Preparation and Mechanical Properties of the Nano-Alumina
*E-mail: xiening@hit.edu.cn (N.X.), xianming_s@coe. Reinforced Cement Composite. Mater. Lett. 2006, 60, 356−359.
montana.edu (X.S.). (19) Makar, J. M.; Chan, G. W. Growth of Cement Hydration
Notes Products on Single-Walled Carbon Nanotubes. J. Am. Ceram. Soc.
2009, 92, 1303−1310.
The authors declare no competing financial interest.

■
(20) Vera-Agullo, J.; et al. Mortar and Concrete Reinforced with
Nanomaterials. Nanotechnol. Constr. 3 2009, 383−388.
ACKNOWLEDGMENTS (21) Kamat, P. V. TiO2 Nanostructures. Recent Physical Chemistry
This work was financially supported by the Natural Scientific Advances. J. Phys. Chem. C 2012, 116, 11849−11851.
Research Innovation Foundation in Harbin Institute of (22) Dylla, H.et al. Evaluation of Environmental Effectiveness of
Technology (Grant HIT-NSRIF-2009100), The Lianyungang Titanium Dioxide Photocatalyst Coating for Concrete Pavement.
Transportation Research Record: Journal of the Transportation Research
Scientific Plan-Industrial Program (Grant CG1204), The
Board, 2010; pp 46−51; No. 2164.
Jiangsu Province Ocean Resource Development Research (23) Hassan, M. M.; et al. Evaluation of the Durability of Titanium
Institute Science Open Fund Project (JSIMR11B10), and the Dioxide Photocatalyst Coating for Concrete Pavement. Constr. Build.
China Postdoctoral Science Foundation (Grant 20110491065).

■
Mater. 2010, 24, 1456−1461.
(24) Shen, S.; Burton, M.; Jobson, B.; Haselbach, L. Pervious
REFERENCES Concrete with Titanium Dioxide as a Photocatalyst Compound for a
(1) Richardson, I. G. The Calcium Silicate Hydrates. Cem. Concr. Res. Greener Urban Road Environment. Constr. Build. Mater. 2012, 35,
2008, 38, 137−158. 874−883.
(2) Bullard, J. W.; et al. Mechanisms of cement hydration. Cem. (25) Chang, T. P.; Shih, J. Y.; Yang, K. M.; Hsiao, T. C. Material
Concr. Res. 2011, 41, 1208−1223. Properties of Portland Cement Paste with Nanomontmorillonite. J.
(3) Jennings, H. M. Refinements to Colloid Model of C−S−H in Mater. Sci. 2007, 42, 7478−7487.
Cement: CM-II. Cem. Concr. Res. 2008, 38, 275−289. (26) Mondal, P.; Shah, S. P.; Marks, L. A Reliable Technique to
(4) Shi, X.; Fay, L.; Peterson, M. M.; Yang, Z. Freeze−Thaw Damage Determine the Local Mechanical Properties at the Nanoscale for
and Chemical Change of a Portland Cement Concrete in the Presence Cementitious Materials. Cem. Concr. Res. 2007, 37, 1440−1444.
of Diluted Deicers. Mater. Struct. 2010, 43, 933−946. (27) Jo, B. W.; Kim, C. H.; Tae, G. H. Characteristics of Cement
(5) Rozière, E.; Loukili, A. R.; Hachem, E.; Grondin, F. Durability of Mortar with Nano-SiO2 Particles. Constr. Build. Mater. 2007, 21,
Concrete Exposed to Leaching and External Sulphate Attacks. Cem. 1351−1355.
Concr. Res. 2009, 39, 1188−1198. (28) Jayapalan, A. R.; Lee, B. Y.; Kurtis, K. E. Effect of nano-sized
(6) Nehdi, M.; Pardhan, M.; Koshowski, S. Durability of Self- titanium dioxide on early age hydration of Portland cement.
Consolidating Concrete Incorporating High-Volume Replacement Nanotechnol. Constr. 3 2009, 267−273.
Composite Cements. Cem. Concr. Res. 2004, 34, 2103−2112. (29) Meng, T.; Yu, Y.; Qian, X.; Zhan, S.; Qian, K. Effect of nano-
(7) Shi, X.; Xie, N.; Fortune, K.; Gong, J. Durability of Steel TiO2 on the mechanical properties of cement mortar. Constr. Build.
Reinforced Concrete in Chloride Environments: An Overview. Constr. Mater. 2012, 29, 241−245.
Build. Mater. 2012, 30, 125−138. (30) Lee, B. Y.; Kurtis, K. E. Influence of TiO2 Nanoparticles on
(8) Bagheri, A. R.; Zanganeh, H.; Moalemi, M. M. Mechanical and Early C3S Hydration. J. Am. Ceram. Soc. 2010, 93, 3399−3405.
Durability Properties of Ternary Concretes Containing Silica Fume (31) Avrami, M. Kinetics of Phase Change 1General Theory. J.
and Low Reactivity Blast Furnace Slag. Cem. Concr. Compos. 2012, 34, Chem. Phys. 1939, 7, 1103−12.
663−670. (32) Avrami, M. Kinetics of Phase Change 2Transformation-Time
(9) Pacheco-Torgal, F.; Ding, Y.; Jalali, S. Properties and durability of Relations for Random Distribution of Nuclei. J. Chem. Phys. 1940, 8,
concrete containing polymeric wastes (tyre rubber and polyethylene 212−24.
terephthalate bottles): An overview. Constr. Build. Mater. 2012, 30, (33) Avrami, M. Granulation, Phase Change, and Microstructure-
714−724. Kinetics of Phase Change III. J. Chem. Phys. 1941, 9, 177−84.
(10) Sanchez, F.; Sobolev, K. Nanotechnology in ConcreteA (34) Thomas, J. J. A New Approach to Modeling the Nucleation and
Review. Constr. Build. Mater. 2010, 24, 2060−2071. Growth Kinetics of Tricalcium Silicate Hydration. J. Am. Ceram. Soc.
(11) Birgisson, B.; et al. Nanotechnology in Concrete MaterialsA 2007, 90, 3282−3288.
Synopsis. Transp. Res. Circ. E-C170 2012. (35) Richardson, I. G. The Nature of C−S−H in Hardened Cements.
(12) Balaguru, P.; Chong, K. Nanotechnology and Concrete: Cem. Concr. Res. 1999, 29, 1131−1147.
Research Opportunities. Proceedings of ACI Session on Nanotechnology (36) Allen, A. J.; Thomas, J. J.; Jennings, H. M. Composition and
of Concrete: Recent Developments and Future Perspectives, Nov 7, 2006, Density of Nanoscale Calcium−Silicate−Hydrate in Cement. Nat.
Denver, CO. Mater. 2007, 6, 311−316.

11581 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582

Industrial & Engineering Chemistry Research Article

(37) Taylor, H. F. W. Proposed Structure for Calcium Silicate

Hydrate Gel. J. Am. Ceram. Soc. 1986, 69, 464−467.
(38) Thomas, J. J.; Jennings, H. M.; Allen, A. J. Determination of the
Neutron Scattering Contrast of Hydrated Portland Cement Paste
Using H2O/D2O Exchange. Adv. Cem.-Based Mater. 1998, 7, 119−122.
(39) Bernal, J. D. The structure of cement hydration compounds.
Proc. 3rd Int. Symp. Chem. Cem., London 1952, 216−236.
(40) Ye, Q.; Zhang, Z. N.; Kong, D. Y. Influence of nano-SiO2
addition on properties of hardened cement paste as compared with
silica fume. Constr. Build. Mater. 2007, 21, 539−545.
(41) Han, B.; Yang, Z.; Shi, X.; Yu, X. Transport Properties of
Carbon-Nanotube/Cement Composites. J. Mater. Eng. Perform. 2013,
22, 184−189.
(42) Li, H.; Zhang, M. H.; Ou, J. P. Flexural fatigue performance of
concrete containing nano-particles for pavement. Int. J. Fatigue 2007,
29, 1292−1301.
(43) Edwards, C. L.; Alemany, L. B.; Barron, A. R. Solid-State Si-29
NMR Analysis of Cements: Comparing Different Methods of
Relaxation Analysis for Determining Spin-Lattice Relaxation Times
to Enable Determination of the C3S/C2S Ratio. Ind. Eng. Chem. Res.
2007, 46, 5122−5130.
(44) Haeussler, F.; Tritthart, J.; Amenitsch, H. Time-Resolved
Combined SAXS and WAXS Studies on Hydrating Tricalcium Silicate
and Cement. Adv. Cem. Res. 2009, 21, 101−111.
(45) Allen, A. J.; Thomas, J. J. Analysis of C−S−H Gel and Cement
Paste by Small-Angle Neutron Scattering. Cem. Concr. Res. 2007, 37,
319−324.
(46) Skinner, L. B.; Chae, S. R.; Benmore, C. J.; Wenk, H. R.;
Monteiro, P. J. M. Nanostructure of Calcium Silicate Hydrates in
Cements. Phys. Rev. Lett. 2010, 104, 195502.
(47) Chen, J. J.; Sorelli, L.; Vandamme, M. A Coupled Nano-
indentation/SEM-EDS Study on Low Water/Cement Ratio Portland
Cement Paste: Evidence for C−S−H/Ca(OH)(2) Nanocomposites. J.
Am. Ceram. Soc. 2010, 93, 1484−1493.
(48) Xu, Z.; Viehland, D. Observation of a Mesostructure in Calcium
Silicate Hydrate Gels of Portland Cement. Phys. Rev. Lett. 1996, 77,
952−955.
(49) Sáez de Ibarra, Y.; Gaitero, J. J.; Erkizia, E.; Campillo, I. Atomic
Force Microscopy and Nanoindentation of Cement Pastes with
Nanotube Dispersions. Phys. Status Solidi A 2006, 203, 1076−1081.
(50) Wei, Y. Q.; Yao, W.; Xing, X. M.; Wu, M. J. Quantitative
Evaluation of Hydrated Cement Modified by Silica Fume Using
QXRD, 27Al MAS NMR, TG-DSC and Selective Dissolution
Techniques. Constr. Build. Mater. 2012, 36, 925−932.
(51) Scrivener, K. L.; Füllmann, T.; Gallucci, E.; Walenta, G.;
Bermejo, E. Quantitative Study of Portland Cement Hydration by X-
Ray Diffraction/Rietveld Analysis and Independent Methods. Cem.
Concr. Res. 2004, 34, 1541−1547.
(52) Berra, M.; Carassiti, F.; Mangialardi, T. Effects of Nanosilica
Addition on Workability and Compressive Strength of Portland
Cement Pastes. Constr. Build. Mater. 2012, 35, 666−675.
(53) Anastasia, S.; Viktor, M.; Vyacheslav, K. Dispersion of Carbon
Nanotubes and Its Influence on the Mechanical Properties of the
Cement Matrix. Cem. Concr. Compos. 2012, 34, 1104−1113.
(54) Gavrila, R.; Dinescu, A.; Mardare, D. A Power Spectral Density
Study of Thin Films Morphology Based on AFM Profiling. Rom. J. Inf.
Sci. Technol. 2007, 10, 291−300.
(55) Kanda, T.; Li, V. C. Effect of Fiber Strength and Fiber-Matrix
Interface on Crack Bridging in Cement Composites. J. Eng. Mech.
1999, 125, 290−299.
(56) Tucker, C. L., III; Liang, E. Stiffness Predictions for
Unidirectional Short-fiber Composites: Review and Evaluation.
Compos. Sci. Technol. 1999, 59, 655−671.

11582 dx.doi.org/10.1021/ie4011595 | Ind. Eng. Chem. Res. 2013, 52, 11575−11582