CLOSING

PAPER

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 NANOTECHNOLOGY AND CONCRETE: BACKGROUND,
OPPORTUNITIES AND CHALLENGES

P N Balaguru
Rutgers The State University of New Jersey
United States of America

ABSTRACT. Nanotechnology is a very active research area all over the world. The concept,
which started after the invention of carbon nano-tubes, is being utilized in a number of fields
including: electronics, bio-mechanics and machine components. Recently a number of
researchers started investigations that utilizes nano-technology concept in Portland cement
composites. The two initial areas of research deals with the understanding of the hydration of
cement particles and the use of nano-size silica particles. The author believes that if cement
with nano-size particles can be manufactured, it will open up a large number of opportunities
in the fields of ceramics, high strength composites and electronic applications. Portland
cement could become the high tech material as compared to its current status of conventional
construction material. Very few inorganic cementing materials can match the capabilities of
Portland cement in terms of cost. Basic background information, state of the art, opportunities
and challenges are discussed in this closing paper.

Keywords: Nanotechnology, Challenges, Hydration, Nano-size particles, Concrete.

Professor P N Balaguru is Distinguished Professor at Rutgers, the State University of New

Jersey, United States of America. He is an active member of the ACI and ASCE with
research interests in the fields of nanotechnology, reinforced concrete, and fibre-reinforced
concrete.

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 114 Balaguru

INTRODUCTION

Nanotechnology can be used for the creation of new materials, devices and systems at the
molecular level. Phenomena associated with atomic and molecular interactions strongly
influence macroscopic material properties; with significantly improved mechanical, optical,
chemical, electrical... properties.

To conduct competitive research in the nanotechnology areas, engineers need to be trained in

quantum mechanics, molecular dynamics, etc. The following are some of the key topics
across different scales.

• .10-12 m QUANTUM MECHANICS [TIGHT BINDING METHOD; DENSITYFTNAL

THEORY; HATREE-FOCK APPROX.; 1

• 10_9 M O L E C U L A R D Y N . [LENNARDJ0NES P0TENTIAL . . . ] ; N A N O M E C H A N I C S ;

M O L E C U L A R B I O L O G Y ; BIOPHYSICS

• 10"6 ELASTICITY; PLASTICITY; DISLOCATION...

• 10"3 MECHANICS OF MATERIALS

• 10"° STRUCTURAL ANALYSIS

MULTI-SCALE ANALYSES & SIMULATIONS...

Efficient civil infrastructure systems as well as high performance materials are essential for
these technologies. The solid mechanics and materials engineering (M&M) communities will
be well served if some specific linkages or alignments are made toward these technologies.
Some thoughtful examples for the M&M and other engineering communities are:

Bio-mechanics/materials
Thin-film mechanics/materials
Wave Propagation/NDT
Nano-mechanics/materials
Nano-electro-mechanical systems(NEMS)
Simulations/modeling
Micro-electro-mechanical systems (MEMS)
Smart materials/structures
Designer materials
Fire Retardant Materials and Structures

Active nano-technology research is being conducted around the world on various fields.
Support provided by the various agencies in the US is shown in Table 1. Information reported
in this paper focuses on composites and concrete. Since carbon Nano-tubes have excellent
potential for use in cement and concrete composites, basic mechanical properties of these
tubes are also presented.

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 Challenges of Nanotechnology 115

Table 1 Research Budget for Nanotechnology in US (M$)

FISCAL YEAR 2001 2005

National Science Foundation 150 305
Defense 125 276
Energy 88 211
National Institutes of Health 40 89
Commerce (NIST) 33 53
NASA 22 35
Agriculture 0 5
EPA 5 5
Justice 1 2
Homeland Security 0 1
TOTAL 464 982

NANO-COMPOSITES

Nano-tubes can be used as fibers to develop fiber composites that can inherit some of the
outstanding properties of the Nano-tubes. For example, carbon Nano-tubes can be mixed with
alumino-silicates to produce very thin wafers that are very strong and highly conductive. The
composite can also be used as a tough, durable, high temperature and low-friction coating.
Current alumino-silicate formulations consist of silica particles in the range of 50 to 100 nm
(Balaguru and Chang). It is possible to refine the process to reduce the maximum particle size
in the matrix to 5 or 10 nm. These matrices can be reinforced with as low as 0.5% of Nano-
tubes and still produce extraordinary strength and electrical conductivity improvements.

Researchers at NIST and other places have been building nano-clay filled polymers with
natural clay form platelet [less than 1 nm in thickness] and 1 to 5% by volume. These nano-
clay filled polymers can dramatically improve fire resistance as well as mechanical
properties. Metal oxide nano-particles have also been used in coatings for protection of UV
light, self-disinfecting surfaces, solar cells, indoor air cleaners, etc. Other nano-composites
have superior structural performance (see Figure 1).

Traditional
Nanocomposite

STRAIN
Figure 1 Stress-strain characteristics of nano-composites [L. Schadler, RPI].

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 116 Balaguru

The most common and widely used construction material is Portland cement. The major
advantages of this material are: low cost, room temperature setting properties and
performance data for more than 150 years. The average particle size of micro cement is about
3 microns. If these cement particles can be packed with Nano-tubes and reactive Nano-size
silica particles; conductive, strong, tough and room temperature processed ceramics can be
developed both for electronic applications and coatings. Note that carbon oxidizes at
temperatures above 400 C and room temperature processing will be a boon to retain the
mechanical properties of carbon Nano-tubes.

In the area of composites, there is also a very good analogy between reinforced concrete and
fiber composites. At micro level the behavior of reinforced and pre-stressed concrete is
similar to composites made with continuous fibers and fabrics. The lessons learned on fiber
reinforced concrete can be effectively used for composites made using short discrete fibers,
both at micro and Nano-level. For example, considerable amount of fiber reinforced concrete
containing 0.5% of steel fibers are being used in actual construction. The enhancement of
properties provided by this 0.5% of steel fibers to concrete matrix are not that much different
from the enhancement provided by 0.5% of carbon Nano-tubes in high performance
composites (Balaguru and Shah, Srivastava). Note that carbon fibers provide enhancement to
both mechanical and electrical properties.

NANO-TUBES: GENERAL DESCRIPTION

The most popular Nano-tubes are carbon Nano-tubes, discovered by the Japanese Scientist
Sumio Iijima in 1991 ( Iijima et al). Within a short period, arc-evaporation techniques were
used to produce bulk quantities of Nano-tubes. These tubes were multilayered structures. A
single layer Nano-tube was synthesized in 1993 by adding metals such as Cobalt to Graphite
electrodes. In 1996, Smalley's group in Texas, USA developed a method that resulted in high
yield of single walled tubes with unusually uniform diameters. These uniform tubes had a
tendency to form aligned bundles than those prepared using arc-evaporation. The bundled
Nano-tubes are sometimes referred to as nano "ropes".

Other forms of carbon Nano-tubes are: nano-horns, Nano-test tubes and Nano-fibers. Nano-
horns are single walled carbon cones with remarkable adsorptive and catalytic properties.
They have excellent potential for use in fuel cells. Nano-test tubes have potential for use in a
number of applications, including medical fields. These tubes can be filled with materials
including biological molecules. Nano-fibers could become the ultimate carbon fibers because
of their very high strength, stiffness, aspect ratio and purity.

Single layer Nano-tube can be considered as the perfect thin walled cylinder because of the
uniformity in thickness, accurate geometry and linear elastic material behavior. The challenge
is to test them to obtain strength, stiffness and stability properties. A number of techniques
are being developed to use electro-mechanical devices to induce force and measure
responses. It is need less to say that the forces are measured in Nano-Newtons and the
displacements are measured in fractions of meters. Structural properties of single walled
(single layered) tubes, multi walled tubes and single wall bundled tubes are needed for
effective utilization these materials in electronic and bio applications and development of
nano/micro composites. The following sections provide some basic information on geometric
dimensions and mechanical properties of carbon Nano-tubes. Since, this is a very active
research area, the reader is advised to refer to latest Journals for up to date information.

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 Challenges of Nanotechnology 117

Dimensions of Carbon Nano-Tubes

The first Nano-tubes discovered were multi-walled tubes (Qian, et al). Transmission electron
microscopy studies indicate that these tubes look like nested shells with an interlayer spacing
of about 0.34 nm. The equivalent diameter of the tubes is in the range of 10 to 50 nm. The
typical length varies from 100 to lOOOnm. Single layer tube has a much smaller diameter (1
to 3 nm) and length (about 300 nm). The single layer tubes are often manufactured in "rope"
or "bundled" form, where many individual tubes are close-packed in parallel.

Mechanical Properties of Nano-Tubes

The basic information needed for analysis are elastic modulus, stress-strain behavior, strain
capacity in compression and tension, shear modulus and strengths in various modes. These
values can be obtained using either experimental techniques or theoretical formulations. The
small dimensions of the tubes impose a tremendous challenge for experimental study.
Various types of high-resolution microscopes with the recent innovative developments in the
area of nano manipulation have helped to obtain quantitative results. However, the numbers
reported on strengths and modulus values vary widely. The modulus values reported range
from 270 to 3600 GPa. Theoretical predictions indicate that the modulus can be as high as
5000 GPa. Typical stress-strain plots reported two investigators are shown in Fig 2
(Srivastava et al). The stresses were estimated assuming a uniform thickness of 0.34 nm for
the single tube. The strains reported are engineering strains.

CO

0.00 0.02 0.04 0.0!>

STRAIN, %

4 6 8 10 12
STRAIN, %

Figure 2 Stress -Strain relationships of nano-tubes (Srivastava et al)

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 118 Balaguru

In tension mode, the reported strain at failure is as high as 12% and the strengths vary from
10 to 63 GPa. The strengths of very long (about 2 mm) ropes were found to be in the range of
1.72 +/_ 0.64 GPa ( Qian et al).

NANOTECHNOLOGY AND CONCRETE

Concrete is a porous material containing air voids ranging in size to nanometer-scale pores.
Since these nano-scale pores control the properties of the calcium-silicate hydration product,
and hence the final product, nanotechnology plays a role in the behavior of concrete. The
scales of various constituent materials of concrete are shown in Fig. 3. Active research areas
in the area of concrete and nanotechnology are: characterization of cement hydration,
influence of the addition of nano-size silica and coatings (that contain Nano-size particles)
applied to protect concrete. These activities are briefly described in the following sections.

mwmm
~W -S -6 »7 -8 -S -4 -S -2 -I -O
10 10 10 10 10 10 18 ID 10 10 10
I—I—I—i i t i i—i i i

***

C-S-N <&L CEȣNT nm COARSE mi

£0Ll€iDS NEIWORK CLINKER AGGREGA'nE AGGRgGftTB CYUBDSR
GRAINS

Figure 3 Scales of various constituents of concrete (FHWA, USA)

Cement Reactivity Nanostrueture

A collaborative research activity pursued by FHWA (of USA), University of Connecticut and
German scientists deals with the use of nuclear resonance reaction analysis (NRRA) to study
cement hydration at a nano-scale level. They are investigating what takes place on the surface
of the cement particle as it hydrates.

In NRRA, a beam of nitrogen atoms is used to probe a reacting cement grain to locate
hydrogen atoms, a necessary component of water, or reaction by-products, Fig 4. Results of
the probe are used to create a hydrogen depth profile, which shows the rate of water
penetration as well as the arrangement of various surface layers formed during the reaction.

The four components that are active during cement hydration are shown in Fig 4. The 20-
nanometer-thick semi-permeable surface layer allows water to enter the cement grain and
leaches out calcium ions. The larger silicate ions in the cement are trapped behind this layer.
As the reaction continues, a silicate gel forms there, causing swelling within the cement
grain. This leads to eventual breakdown of the outermost layer. The surface disintegration
then releases accumulated silicate into the surrounding solution. The silicate reacts with
calcium ions to form a calcium-silicate hydrate gel, which binds cement grains together and
sets the concrete.

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 Challenges of Nanotechnology 119

Figure 4 Details of hydrating cement grain at Nano-scale

The evolution of the hydrogen profile shows the timing of the surface layer's breakdown.
This information can be used to study the concrete setting process as a function of time,
temperature, cement chemistry, and other factors. For example, researchers used NRRA to
determine that in cement hydrating at 30°C (86°F), the breakdown occurs at 1.5 hours.

Nano-Seale Silica fume for Improving Concrete Performance

Addition of Nano-scale silica fume, an industrial byproduct of glass manufacturing, to

concrete mixes is increasingly recognized as a means to improve durability of concrete
structures against natural elements and deicing salts. Ultra-fine amorphous colloidal silica
was found to be much more efficient than micron sized silica (Collepardi et al.). Reduced
amount of 15 to 20 kg/m 3 of fine silica was found to perform as well as 60 kg/m of regular
silica.

Alkali-Silicate Reaction (ASR) Studies

ASR occurs upon contact between cement alkalis and a reactive form of silica from
aggregates or supplementary additions, which can result in the formation of alkali/silica gel.
The gel can expand and cause significant material damage. Researchers at FHWA are using
neutron scattering and positron annihilation spectroscopy to measure nano- and sub-nano-
scale changes in gel microstructure as a function of gel chemistry, temperature and relative
humidity.

Fly Ash Reactivity Characterization

FHWA is funding research to examine interactions between fly ash and Portland cement gel
nanostructure, including ASR reactivity that affects concrete strength and durability. Small-
angle neutron scattering is being used to quantify the changes on a Nano-scale as a function
of time and fly ash composition. A unique vibrational spectroscopy is also being employed
for nondestructive measurement of the reactivity of fly ashes.

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 120 Balaguru

Cement Hydration Kinetics

It is difficult to attain an accurate model for the rate of cement's reaction with water as a
function of temperature, water/cement ratio, and grain size using conventional analytical
methods because the reactions occur in the Nano-scale pores of the cement gel. Neutron
scattering methods can measure motions and reactions of water on such a scale. Therefore, in
collaboration with the National Institute for Science & Technology's Center for Cold Neutron
Research, FHWA researchers have been applying an array of neutron scattering methods to
determine the effects of various factors on the rate of development of cement's fractal Nano-
scale structure.

COATINGS FOR CONCRETE

Coatings are routinely used as protective barriers against abrasion, chemical attack,
hygrothermal variations and to improve aesthetics. Currently, most of these coatings are in
the micrometer range. New materials and techniques are being developed to develop
nanometer thick coatings that are durable and generate less heat due to reduced friction.
Coatings could be self-cleaning and self-healing. In most cases the performance of these
coatings are evaluated using experimental techniques. The major parameters evaluated are:
durability of coatings under various exposure conditions, abrasion resistance, friction
resistance, high temperature resistance and electrical characteristics. Performance of the
(coating) film and the interface between the film and the parent material play important role
in the overall durability of the system. The author believes that analytical models are needed
to predict the performance of various types of coatings, so that optimum design approaches
can be developed.

The models could become quite complex because of the interaction of the coating-film with
the parent material through the interface. For most cases, the mechanical properties of parent
surfaces and some of the available coating materials are known. But very little is known
about the performance of the interface under mechanical, hygrothermal and magnetic forces.
For the Nano-coatings, the properties of the coatings themselves need investigation.

Brittle coatings usually fail by cracking, delaminating and spalling rather than "wearing out".
Robust analytical models are needed to predict the initiation and growth of cracks and their
contribution to final degradation. We believe that the knowledge base developed to analyze
the thin walled structures can be effectively used to develop the aforementioned analytical
models.

Most existing coatings tend to accumulate grime reducing aesthetics. The deposited materials
also degrade the parent surface over time. Coatings with a nano-scale of roughness that will
repel water and dirt, modeled after the coating of the lotus leaf are being created. The lotus
leaf has extraordinary ability to keep itself clean and dry. Now nanotechnology is being used
to mimic the lotus leaf surface and create new products that outperform existing no-stick
products. Typically, on a hydrophobic or water-repellent surface, particles of dirt are
removed by moving water. But on a Lotus simulated surface, dirt particles are collected by
water drops and rinsed off.

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 Challenges of Nanotechnology 121

NANO-SENSORS FOR CONCRETE STRUCTURES

The feasibility of Cyberliths, or Smart Aggregates, as wireless sensors embedded in concrete

is being evaluated. In the future these micro-sensors might be reduced to dust-particle size,
with the ability to coat an entire bridge with Smart Dust for optimum monitoring capabilities
via a smart sensor net. These sensors can be used to monitor the condition of the concrete and
reinforcement without damaging the structures and remotely.

OPPORTUNITIES AND CHALLENGES

If Portland cement can be formulated with nano size cement particles, it will open up a large
number of opportunities. For example, the cement can be used as an inorganic adhesive with
carbon fibers. Currently the micron size cement particles are not conducive for use with 7
micron diameter carbon fibers. The cement will not only be more economical than organic
polymers but also will be fire resistant. In addition it will emit any voc and the composites
can be attached to parent concrete substrate using a compatible adhesive. It will be also very
competitive with current inorganic composites because they have to be processed at high
temperature.

A number of investigations have been carried out for developing smart concrete using carbon
fibers. This will become a reality with nano-cement because nano carbon tubes are much
more effective than carbon fibers. The thickness of the composite can reduced to microns and
hence flexible and smart cement composite can be manufactured.

The primary challenge is to manufacture nano size cement particles. Chemical vapor
deposition shows promise. Other avenue is high tech grinding. The second challenge is the
heat of hydration. Special organic and inorganic additives need to be developed to control the
setting and heat of hydration. Even though this is a risky and tough venture, the author
believes that the risk is worth taking.

SUMMARY

Large amount of funds and effort are being utilized to develop Nanotechnology. Even though
cement and concrete may constitute only a small part of this overall effort, it could pay
enormous dividends in the areas of technological breakthroughs and economic benefits.

Current efforts are focused on understanding cement particle hydration, nano size silica and
super plasticizer additions and sensors. Unique opportunity exists for the development of
nano-cement that can lead to major long standing contributions.

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BALAGURU, P. AND CHANG, P. (2003). High strength composites for repair,

rehabilitation and strengthening of concrete structures. ICI Journal. 3,7-18.

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BALAGURU, P.AND SHAH, S. P. (1992). Fiber Reinforced Cement Composites, McGraw-

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