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 CONCRETE MATERIALS SCIENCE AT THE NANOSCALE

DCorr
S P Shah
Northwestern University
United States of America

ABSTRACT. This review paper examines the relationship between nanotechnology and the
study of concrete materials science. In order for concrete nanotechnology to be brought to
the forefront of the construction industry, the benefits of the technology must be clearly
demonstrated by the research community. The authors have identified three broad areas of
nanoscale research that have the potential to increase the knowledge of the material: (1)
nanoscale materials characterization, (2) nanoscale sensing, and (3) nanomechanics and
modeling. The recent developments of each area are discussed, and future goals in each area
are outlined.

Keywords: Nanoscale, Nanomechanics, Sensors, Imaging.

David J Corr, Research Assistant Professor, Department of Civil and Environmental

Engineering, Northwestern University, USA. Dr. Corr's research interests are in durability of
concrete, structure-property relationships in concrete and cement-based materials, and
imaging and image processing technologies.

Surendra P Shah, Walter P. Murphy Professor, Department of Civil and Environmental

Engineering, Northwestern University, USA. Prof. Shah is the director of the Center for
Advanced Cement-Based Materials (ACBM), headquartered at Northwestern University. His
research interests include concrete fracture, fresh concrete properties, fiber reinforced
cement-based materials, and high-performance concrete.

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 2 Corr, Shah

INTRODUCTION

There is widespread agreement that nanotechnology has the potential to revolutionize the
world of concrete materials science. The fundamental processes that govern the most
pertinent issues to the study of concrete technology (strength, ductility, early age rheology,
creep and shrinkage, fracture behavior, durability, etc.) all are affected, if not dominated, by
the performance of the material at the nanoscale. Yet, there is a lack of agreement about how
to pursue concrete materials science research at the nanoscale, to improve the value of the
material, and how to develop these nanoscale ideas and bring them to the industry. It would
greatly benefit the research community to have well-defined goals in the pursuit of
nanotechnology in concrete materials science.

In many ways, the aspects of concrete that make it such an appealing building material make
it a difficult material to modify at the nanoscale. Concrete is an engineered product, but not
in the same sense that a nano-electromechanical (NEMS) device is an engineered product.
Whereas a NEMS device can be rigorously engineered from the atomic scale upwards, for
concrete the Portland cement and aggregate must, on some level, be considered a "given" in
the process. When constructing a multistory concrete structure, attention to the nanoscale
variations in the cement and aggregate are not a possibility.

Portland cement, particularly, has the drawback of being a material generated through a
macroscale process, but with nanoscale variations that affect performance. Portland cement
production is a relatively inexpensive process that is well-established and effective in
generating large volumes of material. If the material is to be improved at the nanoscale, it is
likely that new technology in cement production or admixtures will be the source. As such,
the materials that are considered to be "given" in the construction industry will be updated to
incorporate the improvements due to nanotechnology. The challenge is that without a clear
demonstration of the value that would be added, introduction of elaborate nanotechnology
into the cement production process would likely generate little industrial interest.

Thus, it is the charge of the leaders of the field of cement-based materials, both industrial and
academic, to transform this potential into valuable results. To this end, this review paper
strives to illuminate the recent advances in three main areas of nanoscale concrete and
cement-based materials science:

1. Nanoscale materials characterization

2. Nanoscale sensors and sensing
3. Nanomechanics and modeling

NANOSCALE MATERIALS CHARACTERIZATION

In order for improvements in cement and concrete at the nanoscale, a fundamental

understanding of cement chemistry and the resulting hydration products is necessary. The
most important, and least understood, hydration product in cement paste is the calcium
silicate hydrates (C-S-H, with C = CaO, S = SiO2, and H = H 2 O). C-S-H forms due to the
dissolution and hydration of the tricalcium and dicalcium silicates (C2S and C3S), the largest
constituents of Portland cement by volume. In concrete, C-S-H is a gel material with a high
specific surface area and a significant amount of gel porosity. At the microscale, C-S-H was
historically considered to be a layered and amorphous hydration product, lacking clearly
definable crystal structure.

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 Concrete Materials Science 3

Recent research, however, has shed further light on the structure of C-S-H at the micro- and
nanoscales. Conclusive evidence is now available in the literature for two (or more) distinct
forms of C-S-H with different porosities, densities, and strength properties. The disparate
forms appear in the literature in several ways, including high-density / low-density models
[1, 2], inner product / outer product forms [3], among others [4, 5]. The development of these
two forms of C-S-H appears to depend on the diffusion processes governing the dissolution
of cement grains, which affects the Ca/Si ratio in the hydrate. The Ca/Si ratio typically varies
from 0.8 to 2.1 [6], and with higher calcium contents, the products tend to be more
amorphous and porous [7].

In addition, new information is available about the crystalline structure and growth of C-S-H.
Gartner, et al. [8] proposed a mechanism for the growth of C-S-H based on the dissolution of
a silica particle in a calcium-rich solution. As the silica dissolves, supersaturation of C-S-H
in solution near the particle surface will ensue, likely causing heterogenous nucleation of a
C-S-H crystal with low Ca/Si ratio. As the crystal grows away from the dissolving particle,
the Si content at the crystal front drops rapidly. This increases the Ca/Si ratio, and resulting
in a ribbon-like amorphous structure. Unimpeded in their growth, these crystals have a sheaf-
of-wheat morphology that has been examined in solution with transmission soft X-rays, with
a dense inner area of apparent crystalline C-S-H and outer amorphous areas. In the restricted
format of a hydrating cement paste matrix, the crystalline areas of C-S-H could correspond to
the high-density areas described above, with the amorphous areas corresponding to low-
density. At the nanoscale, atomic force microscopy of the structure of C-S-H reveals a highly
ordered hydrate, with ordered structures repeating in the sub-micron range [9].

The addition of nanoscaled materials to the Portland cement system can also have an effect
on the material. Nanosilica (nano-SiC^), silica particles with an average size of 10 nm, has
been successfully incorporated into Portland cement concrete materials in the laboratory [10].
Much like silica fume on the microscale, nanosilica improves the porosity of the hydrated
cement paste by filling the voids left in the spaces between larger particles (fly ash and
cement grains) at the nanoscale. In addition, nanosilica provides pozzolanic activation to fly
ash materials, resulting in a quicker gain in strength, and the potential to alleviate the
problems of slow strength gain in highly pozzolanic materials. Nanosilica could also reduce
the cement requirement for concrete; thus reducing the heat generation and shrinkage
problems associated with high cement contents.

Imaging is an important tool to concrete materials science, and a wide array of imaging
techniques are available for studying the micro structure of the material in two and three
dimensions. Scanning electron microscopy (SEM) has the potential for imaging at the
nanoscale, albeit in two dimensions. At the nanoscale, three dimensional information is
difficult to obtain, as the best tomography techniques can yield resolutions on the order of
one micron, and traditional serial sectioning techniques are restrained by the material removal
in the z-resolution which can typically not be below one micron. A new technique,
combining a focused ion beam (FIB) in conjunction with SEM has shown significant promise
for thee dimensional nanoscale imaging [11]. The FIB is used for cutting and erosion of the
material, and the SEM is used to image progressive slices of the specimen. The technique is
outlined in Figure 1, and is a form of in-situ serial sectioning with slices as fine as lOnm.

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 4 Corr, Shah

SEfVl

Figure 1 Illustration of 3D nanoscale serial sectioning with FIB and SEM [11]

FIB has been successfully used to examine the nanoscale porosity of hydrated cement paste.
Figure 2 shows the results of this study [11], pore structure for a 13 um field width of
specimen, where pore sizes below lOOnm in size can be imaged. With the technique, detailed
information on the pore structure of hydrated cement paste at the nanoscale can be extracted.

Figure 2a SEM image of pore structure, Figure 2b Nanoscale pore structure

13 um field width (after [11]) (black = pores, white = solids)
for image 2a (after [11])

The study of material durability is an important goal of imaging and characterization of

cement-based materials on the nano- and microscales. Recent studies at the Georgia Institute
of Technology have yielded a new technique based on spatially resolved energy dispersive
X-ray diffraction (EDXRD). With this technique, crystal phase composition data in three
dimensions at spatial resolutions as low as 50 microns are possible [12]. This technique has
been used to examine the performance of cement-based materials subjected to sulfate attack.
Figure 3 shows the variability in gypsum concentration (a symptom of sulfate attack) with
depth for specimens subjected to 33,800 ppm solutions of sodium sulfate for varying lengths
of time. The EDXRD technique shows significant promise for evaluating microscale
variations in composition for cement-based materials.

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 Concrete Materials Science 5

4 weeks —
6 weeks
10 weeks —
16 weeks —
52 weeks —

0 0.5 1 1,5 2 2,5 3 3.5 4

DEPTH, mm
Figure 3 Gypsum content vs. depth from surface after varying time of exposure to
sodium sulfate solutions (after [12])

NANOSCALE SENSORS AND SENSING

The potential benefits of a self-monitoring structural material are clear, and the pursuit of
"smart" structures is an important pursuit of the structural engineering community. The
ability to actively monitor the viscosity, setting, temperature, strength development,
durability, and cracking behavior of concrete would all have an important effect on concrete
construction.

The advent of micro- and nano-electromechanical systems (MEMS and NEMS) has yielded a
host of cutting-edge sensor capabilities. For use in materials, MEMS-based sensors have
been developed for strain gauges [13, 14, 15]. Similar sensors have been developed for
viscosity, temperature, resonant frequency, and damage detection [16]. The advantage of
these sensors is that they can be wireless and remotely powered; the sensor packaging
includes electromagnetic coils for power generation, and circuitry for radio-frequency
transmission of data. One disadvantage of these sensors is that the packaging and shielding
from the high-pH environment results in a millimeter to centimeter sized sensor. At this size,
the sensor itself begins to affect the performance of the material it is attempting to sense.

Another sensing system, the high-frequency wave reflection (HFWR) method, is currently
under development at Northwestern University. HFWR is based on the wave propagation
properties of fluids and solids. The method involves embedding a steel plate in an
unhardened concrete specimen. An ultrasonic transducer is mounted on the steel plate, which
can transmit high-frequency shear waves, and measure the resulting wave echoes. Shear
waves cannot propagate in a fluid, so at the interface between steel and plastic concrete, the
shear waves will be totally reflected (no transmission). However, as the concrete begins to
harden, some of this energy will propagate into the material, and some will be reflected back
to the transducer. Comparing the amplitude of the initial wave (A2) to the
reflected wave (Ai),

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 6 Corr, Shah

r=- (1)

R L (t) = -20 1og(r(t)) (2)

RL is the reflection loss parameter, which gives a comparative value of the amount of wave
energy that is transmitted to the hardened material. The reflection loss parameter has been
correlated to the compressive strength and degree of hydration of hardening concrete, and has
been successfully applied in the field [17].

In order to probe the relationship between reflection loss and nano-microstructural evolution
of the cementitious materials, a numerical model, HYMOSTRUC [18, 19], has been used to
simulate the volume evolution of the phases in the microstructure [20]. In general, this
numerical model distinguishes between the solid phase and the pore phase by idealizing the
heterogeneous structure of Portland cement paste. A serial section algorithm and an overlap
criterion were used in the model to access the phase fraction and the connectivity of the
phases. The calculation of the volume fraction of connected solid phase is based on this
algorithm. The percolation threshold, which is defined as the critical degree of hydration
when the solid phases transition to percolated from unpercolated, can also be obtained by this
model. Figure 4 shows a 2D image of percolated solid phase for convenience of description.

Figure 4 Percolation of solid phase during hydration (after [20])

In a preliminary study the development of the volume fraction of the solid phase (= solid
hydration products + unhydrated cement) during the course of hydration was calculated for a
cement paste (w/c = 0.5) and compared to the measured reflection loss. Additionally, the
amount of the solid phase that is percolated was determined. The comparison of the amount
of the total solid, the connected solid and the reflection loss is given in Figure 5. It can be
seen from this figure that the reflection loss starts to increase very closely to the time of the
occurrence of the percolation threshold of the solid phase.

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 Concrete Materials Science 7

Portland cement paste

w/c = 0.5, cured @ 25°C
— * - * —

0.6 - 7.5 ^

Reflection Loss O
Q
O 0.4 -
/3

o
P 0.2 2.5

-A-total solid
- o - connected solid
/
— Reflection Loss
0.0
0
Percolation 24 48 72
Threshold
TIME (hours)
Figure 5 Development of the solid phase and the reflection loss for cement paste with w/c=0.5

The percolation threshold is defined as the time when the fraction of the connected solid
phase is larger than zero. When the percolation threshold has occurred, the reflection loss
increases rapidly. This indicates that the connectivity of the solid phase is a governing
parameter of the reflection loss during this time of the hydration process. After approx. 36
hours of hydration, the difference between the total solid and connected solid phase reaches a
constant value indicating that no new bonds between the cement particles are generated. At
this time the rate of increase of the reflection coefficient also decreases and the reflection loss
follows the trend of the total solid phase.

Recent advances in AC impedance spectroscopy (AC-IS) of fiber-reinforced cement-based

materials have shown the potential of conducting fibers for determination of fiber dispersion
characteristics through the theory of intrinsic conductivity [21]. With this technique, the
orientation and arrangement (e.g. clumped or dispersed) of fibers within the material is
determined by measuring the surface-measured AC impedance of the composite. At the
nanoscale, similar approaches are being investigated at Northwestern University using
conductive carbon nanotubes as fibers. If the carbon nanotubes have a preferred orientation
or attraction to a particular phase of the hydrated cement paste, AC-IS analysis could be used
as a nanoscale sensing system.

NANOMECHANICS AND MODELING

The durability, cracking, and fracture behavior of concrete are highly dependent on the
nanoscale properties of the materials. It is widely known that microcracks are dispersed
throughout the hydrated cement paste matrix, and are likely to exist even at low stress levels.
In the fracture and failure of the material, microcracks act as initial defect in the material,
hastening the onset of failure. In durability, microcracks can act as conduits through which
water and aggressive ions can penetrate the material. Clearly, controlling the onset of
microcracking and would be beneficial to the material. An understanding of the factors that
contribute to microcrack development most probably lie at the nanoscale, where variations in
the material lead to discontinuities and cracking.

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 8 Corr,Shah

Nanoindentation is a procedure for determining the modulus of elasticity of materials. With

this technique, a small tip of a very stiff material is indented into a relatively soft material,
and then pulled out of the material, with the load vs. depth data collected throughout the
insertion and removal (Figure 6). From the load-depth data, the elastic modulus of the
specimen can be determined using the following equations:

4K
1
(3,4)
E.

Where S = dP/dh is the experimentally measured stiffness of the upper portion of the
unloading data; Er is a reduced elastic modulus defined in equation (4); A is the projected
area of the elastic contact (evaluated based on indenter geometry); E and v are Young's
modulus and Poisson's ratio for the specimen; and Et and v,- are the same parameters for the
indenter [22].

For the case of concrete, nanoindentation has the potential to evaluate the variability in the
elastic modulus of different hydration products, as well as for the varying phases of C-S-H as
discussed above. Recent nanoindentation studies by Constantinides and Ulm [23] focused on
the elastic modulus of the hydrated cement paste (hep) and the interfacial transition zone
(ITZ) between bulk hep and large aggregate particles. Findings include preliminary results
suggesting intrinsic moduli for the phases of C-S-H (regardless of water-to-cement ratio and
other effects), as well as a clearly observable decrease in elastic modulus through the -20 urn
thickness of the ITZ. These results are also being used as the baseline nanoscale properties in
a multi-scale model of the behavior of the material. In addition, Zhu, et al. [22] evaluated the
interfacial transition zone between steel reinforcement and hydrated cement paste, and their
results are presented in Figure 7. Again, a decrease in elastic modulus is seen a finite
distance (~20fj,m) from the steel surface, and the modulus tends to return to the bulk cement
paste value roughly 40-50um from the steel surface. Further investigation is necessary to
fully ascertain the effects of elastic modulus variability on the crack development and
propagation, but it is clear that nanoindentation has the potential to shed significant light on
nanoscale material variability.

40
• Below steel bar
a
Pmax

CO
>

O
1 20 OQ

10
ooo
o

0
hp hmax 0 10 20 30 40 50 60 70 80
DISPLACEMENT, DEPTH DISTANCE FROM THE INTERFACE, jim

Figure 6 Load vs. depth relationship Figure 7 Elastic modulus results of nano-
for nanoindentation (after [22]) indentation near steel surface (after [22])

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 Concrete Materials Science 9

Widely available computational power has led to the recent development of sophisticated
models for the hydration and mechanical behavior of cement-based materials. At the US
National Institute of Standards and Technology, the Virtual Cement and Concrete Testing
Laboratory houses a number of models for cement dissolution and hydration, rheology, and
other properties. Studies with this model have yielded significant results in evaluation of the
interfacial transition zone [24], and other microscale effects in hydrated cement paste. At
Delft University, the HYMOSTRUC model mentioned above is pursuing similar goals, with
significant results generated for the contact area and percolation of solid materials in
hydrating systems [18, 19]. In each of these cases, extension of the modeling capability to
the nanoscale is easily attainable once physical parameters governing material behavior at
that scale are determined.

Models based on "moving-window" analysis are being developed for the quantitative
analysis of meso-, micro-, and nano-structural images [25, 26]. In this model, a window of
fixed pixel size is scanned across a digital image, and a homogenization technique (such as
the generalized method of cells [27]) is applied to determine the mechanical properties within
the window. Results of a sample analysis using this technique on the meso scale are shown in
Figure 8. Here, the variability in local elastic modulus has been determined directly from a
digital image of the concrete mesostructure. The moving-window approach has the benefit of
not requiring assumptions about the size and shape of the matrix and inclusion phases of the
material; all that is required is a digital image with differentiable phases, and knowledge of
the mechanical properties of the individual phases. Further, with this approach, the
variability in the material properties can be used to simulate (through stochastic simulation
techniques [28]) the variability in the behavior of materials. This type of analysis is
applicable to model the nanoscale variability of the material, and this work is underway at
Northwestern University.

x104MPa

1800

1200
O
O
u BOO

400

0 4U0 S00 1200 1800

X 3 COORD, urn
Figure 8 Contour map of local elastic modulus of concrete mesostructure (after [25])

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 10 Corr, Shah

CONCLUSIONS

Nanoscale materials science applied to the field of concrete has already led to a number of
advances in the research and high-performance material areas. The three main areas
addressed in this paper are nanoscale materials characterization, nanoscale sensors and
sensing, and nanomechanics and modeling. The potential exists to bring these advances and
technologies into wide use, and the leaders of the field must lead this pursuit. In doing so it is
important for concrete researchers and industry leaders to steer the focus away from "what is"
the nanoscale of concrete science to "what could be" at the nanoscale of concrete materials of
the future.

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